JP2018145430A - Ultraviolet-curable resin composition, method of manufacturing organic el light-emitting device, and organic el light-emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet curable resin composition which can have good ultraviolet curability and can have a low viscosity, and thereby can be applied by an inkjet method. An ultraviolet curable resin composition contains a polyfunctional cationically polymerizable compound (A) having no siloxane skeleton, a cationic curing catalyst (C), and a monofunctional cationically polymerizable compound (E). The polyfunctional cationically polymerizable compound (A) contains an epoxy compound (A1) represented by the formula (1). [Selection diagram] None

Description

  The present invention is produced from 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 the ultraviolet curable resin, and the ultraviolet curable resin. The present invention relates to an organic EL light emitting device including a sealing material.

  Organic EL light-emitting devices are applied to lighting applications, display applications, and the like, and are expected to spread in the future.

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

  A sealing material suppresses generation | occurrence | production and growth of the dark spot in an organic EL element by suppressing the penetration | invasion of the water | moisture content to an 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 sealing material is produced from a composition containing, for example, 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 the encapsulant, the encapsulant can be produced without applying a heat load to the organic EL element.

Japanese Patent No. 5703429 Japanese Patent No. 5887467

  The conventional organic EL sealing composition has not been required to have such a low viscosity. For example, the viscosities of the compositions described in Patent Document 1 and Patent Document 2 were 50 mPa · s or more. When a low-viscosity component is contained in the composition to lower the viscosity, the component is likely to volatilize from the composition, and thus the composition of the composition is likely to change during storage.

  An object of the present invention is to provide an ultraviolet curable resin composition that can have good ultraviolet curable properties and can be reduced in viscosity without impairing storage stability, and can be applied by an ink jet method. It is providing the manufacturing method of the organic electroluminescent light emitting device using an ultraviolet curable resin composition, and an organic electroluminescent light emitting device.

  The ultraviolet curable resin composition which concerns on 1 aspect of this invention contains the polyfunctional cation polymeric compound (A) which does not have a siloxane skeleton, a cation curing catalyst (C), and a monofunctional cation polymeric compound (E). To do. The polyfunctional cation polymerizable compound (A) contains an epoxy compound (A1) represented by the following formula (1).

In the formula (1), independently of each R ¹ to R ^12, a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms.

  The manufacturing method of the organic EL light-emitting device which concerns on 1 aspect of this invention is a method of manufacturing an organic EL light-emitting device provided with the organic EL element and the sealing material which covers the said organic EL element, The said ultraviolet curable resin composition And forming the sealing material by irradiating the ultraviolet curable resin composition with ultraviolet rays and then curing the ultraviolet curable resin composition.

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

  According to one embodiment of the present invention, an ultraviolet curable resin composition that can have good ultraviolet curable properties and can be reduced in viscosity without impairing storage stability, and can also be applied by an inkjet method. Product, a method for producing an organic EL light emitting device using the ultraviolet curable resin composition, and an organic EL light emitting device.

It is a schematic sectional drawing which shows the 1st example of an organic electroluminescent light-emitting device. It is a schematic sectional drawing which shows the 2nd example of an organic electroluminescent light-emitting device.

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

  A first 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 that faces the support substrate 2 with a space therebetween, an organic EL element 4 on the surface of the support substrate 2 that faces the transparent substrate 3, and the support substrate 2. The sealing material 5 filled between the transparent substrates 3 is provided. In the example shown in FIG. 1, the organic EL light emitting device 1 includes a passivation layer 6 that covers the surface of the support substrate 2 facing the transparent substrate 3 and the organic EL element 4.

  The support substrate 2 is made of, for example, a resin material, but is not limited to this. The transparent substrate 3 is made from a material having translucency. 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 located between the electrodes. The passivation layer 6 is preferably made from silicon nitride or silicon oxide.

  A second example of the structure of the organic EL light emitting device 1 will be described with reference to FIG. Elements common to the first example shown in FIG. 1 are denoted by the same reference numerals as those in FIG. 1, and detailed description thereof is omitted as appropriate. The organic EL light emitting device 1 shown in FIG. 2 is also a top emission type. The organic EL light-emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 with a gap, an organic EL element 4 on the surface of the support substrate 2 facing the transparent substrate 3, and the organic EL element 4 The sealing material 5 which covers is provided.

  As in the case of the first example, the organic EL element 4 includes, for example, a pair of electrodes 41 and 43 and an organic light emitting layer 42 between the electrodes 41 and 43. The organic light-emitting layer 42 includes, for example, a hole injection layer 421, a hole transport layer 422, an organic light-emitting layer 423, and an electron transport layer 424, and these layers are stacked in the order described above.

  The organic EL light emitting device 1 includes a plurality of organic EL elements 4, and the plurality of organic EL elements 4 constitutes an array 9 (hereinafter referred to as an element array 9) on the support substrate 2. The element array 9 also includes a partition wall 7. The partition wall 7 is on the support substrate 2 and partitions between the two adjacent organic EL elements 4. The partition wall 7 is produced, for example, by molding a photosensitive resin material by a photolithography method. The element array 9 also includes connection wirings 8 that electrically connect the electrodes 43 and the electron transport layers 424 of the adjacent organic EL elements 4. The connection wiring 8 is provided on the partition wall 7.

  The organic EL light emitting device 1 also includes a passivation layer 6 that covers the organic EL element 4. The passivation layer 6 is preferably made from silicon nitride or silicon oxide. The passivation layer 6 includes a first passivation layer 61 and a second passivation layer 62. The first passivation layer 61 covers the organic EL element 4 by covering the element array 9 while in direct contact with the element array 9. The second passivation layer 62 is disposed at a position opposite to the element array 9 with respect to the first passivation layer 61, and a space is provided between the second passivation layer 62 and the first passivation layer 61. ing. A sealing material 5 is filled between the first passivation layer 61 and the second passivation layer 62. That is, the first passivation layer 61 is interposed between the organic EL element 4 and the sealing material 5 that covers the organic EL element 4.

  Further, a second sealing material 52 is filled between the second passivation layer 62 and the transparent substrate 3. The second sealing material 52 is made of, for example, a transparent resin material. The material of the second sealing material 52 is not particularly limited. The material of the second sealing material 52 may be the same as or different from that of the sealing material 5.

  The sealing material 5 can be produced from the ultraviolet curable resin composition (hereinafter referred to as composition (X)) according to this embodiment. That is, preferably, the sealing material 5 is a cured product of the composition (X), and the composition (X) is a composition for sealing an organic EL element or a composition for preparing a sealing material in an organic EL light emitting device. It is.

  Hereinafter, the composition (X) will be described.

  The composition (X) contains a polyfunctional cation polymerizable compound (A) having no siloxane skeleton, a cation curing catalyst (C), and a monofunctional cation polymerizable compound (E). The polyfunctional cationically polymerizable compound (A) contains an epoxy compound (A1) represented by the following formula (1).

In formula (1), each of R ^{1 to} R ¹² is independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The hydrocarbon group having 1 to 20 carbon atoms is, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group or a propyl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group or an allyl group; or an ethylidene group or propylidene group An alkylidene group having 2 to 20 carbon atoms such as a group;

Each of R ^{1 to} R ¹² is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. R ^{1 to} R ¹² are particularly preferably all hydrogen atoms, that is, the epoxy compound (A1) preferably contains a tetrahydroindene diepoxide represented by the following formula (1a).

  When this composition (X) is irradiated with ultraviolet rays, the composition (X) is cured by a cationic photopolymerization reaction to become a cured product.

  The epoxy compound (A1) and the monofunctional cationic polymerizable compound (E) have a low viscosity, and in particular, the epoxy compound (A1) has a high cationic polymerization reactivity. Therefore, the composition (X) can have good ultraviolet curability and a low viscosity. For this reason, the applicability | paintability in the case of apply | coating composition (X) at the time of producing the sealing material 5 is favorable. For this reason, it is also possible to apply the composition (X) by a casting method, an ink jet method or the like.

  Furthermore, the epoxy compound (A1) has a property of being less volatile in spite of having a low viscosity. Therefore, even if the composition (X) contains the epoxy compound (A1), the composition (X) hardly changes in composition due to volatilization of the epoxy compound (A1). For this reason, composition (X) can be made low viscosity without impairing storage stability by containing an epoxy compound (A1).

  The composition (X) preferably has fluidity at 25 ° C. 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 form the composition (X) into a film or the like, and the composition (X) can be formed 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 form the composition (X) by an inkjet method. It is also preferable that the viscosity at 50 ° C. of the composition (X) is in the range of 5 to 20 mPa · s. In this case, even if the viscosity of the composition (X) at room temperature is any value, the viscosity can be lowered by slightly heating the composition (X). For this reason, the composition (X) can be reduced. It is easy to mold by an inkjet method. Such a low viscosity of the composition (X) can be achieved by the composition of the composition (X) described in detail below.

  A cured product produced by ultraviolet curing the composition (X) is suitable as the sealing material 5 in the organic EL light emitting device 1.

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

  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 in the range of 2 to 4, more preferably in the range of 2 to 3.

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

  As above-mentioned, a polyfunctional cation polymeric compound (A) contains an epoxy compound (A1).

  The epoxy compound (A1) has two alicyclic epoxy structures and thus has a good cationic polymerization reactivity. Furthermore, the epoxy compound (A1) has a very low viscosity for a compound having two alicyclic epoxy structures. For this reason, an epoxy compound (A1) can contribute to the improvement of ultraviolet curable property of composition (X), and low viscosity.

  Furthermore, in this embodiment, the epoxy compound (A1) can contribute to the improvement of the storage stability of the composition (X) as described above. This will be described in detail.

  The epoxy compound (A1) tends to be less volatile than the monofunctional cation polymerizable compound (E). Therefore, even if the composition (X) is stored, the composition (X The composition change is less likely to occur. Therefore, the composition (X) can have good coating properties even when stored for a long period of time. In addition, since the epoxy compound (A1) and the monofunctional cation polymerizable compound (E) can cooperate to lower the viscosity of the composition (X), the composition is composed only of the monofunctional cation polymerizable compound (E). The amount of the monofunctional cation polymerizable compound (E) in the composition (X) can be small compared to the case of lowering the viscosity of the product (X). Since the monofunctional cation polymerizable compound (E) tends to be more volatile than the epoxy compound (A1), if the amount of the monofunctional cation polymerizable compound (E) is small, the composition (X) is stored. However, the composition change of the composition (X) due to volatilization of the monofunctional cation polymerizable compound (E) hardly occurs. Also in this respect, the composition (X) can have good storage stability.

  In particular, when the epoxy compound (A1) contains the tetrahydroindene diepoxide represented by the above formula (1a), the tetrahydroindene diepoxide can particularly contribute to the lowering of the viscosity of the composition (X). Thus, when the composition (X) is applied, the composition (X) can be stably discharged. Further, tetrahydroindene diepoxide has a particularly high cationic polymerization reactivity, and therefore, for example, the hardness and homogeneity of the cured product of the composition (X) can be improved.

  The epoxy compound (A1) can be produced by a conventionally known method. For example, an epoxy compound (A1) can be synthesized by oxidizing a cyclic olefin compound having a tetrahydroindene skeleton represented by the following formula (1b) using an oxidizing agent. Hereinafter, the reaction for synthesizing the epoxy compound (A1) is referred to as an epoxidation reaction.

R ^{1 to} R ¹² in the formula (1b) are the same as those in the formula (1).

  The oxidizing agent for the epoxidation reaction is, for example, persulfate, hydrogen peroxide, aliphatic percarboxylic acid, organic peroxide, or a mixture of two or more thereof. The usage-amount of an oxidizing agent is 1 mol or more normally with respect to 1 mol of cyclic olefin compounds, and it is preferable to exist in the range of 1-2 mol.

  The epoxidation reaction is preferably performed in a solvent. Solvents include, for example, aliphatic hydrocarbons such as hexane and cyclohexane; aromatic hydrocarbons such as toluene; esters such as ethyl acetate and methyl acetate; alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; and nitriles such as acetonitrile. At least one component selected from the group consisting of: The solvent may further contain water. When the solvent contains water and the solvent is phase-separated into an organic phase and an aqueous phase, it is preferable to add a phase transfer catalyst to the solvent.

  The reaction temperature of the epoxidation reaction is usually in the range of 0 ° C. or higher and the boiling point of the solvent or lower, and preferably in the range of 20 to 70 ° C. The reaction time may be determined according to the reaction scale and the like, but is usually in the range of 10 minutes to 100 hours, preferably in the range of 1 to 50 hours. After completion of the reaction, the produced epoxy compound (A1) is recovered from the solvent by, for example, a method of precipitating with a poor solvent, a method of adding hot water under stirring and distilling off the solvent, or a direct desolvation method. it can.

  The epoxy compound (A1) can contain four stereoisomers based on the configuration of two epoxy rings. The epoxy compound (A1) may contain any of the four stereoisomers. That is, the epoxy compound (A1) can contain at least one component selected from the group consisting of four stereoisomers. In the epoxy compound (A1), the percentage of the total amount of the exo-endo form and the endo-endo form of the four stereoisomers is preferably 10% by mass or less with respect to the entire epoxy compound (A1). If it is 5 mass% or less, it is still more preferable. In this case, the heat resistance of the cured product can be improved. In addition, the ratio of the specific stereoisomer in an epoxy compound (A1) can be calculated | required based on the peak area ratio which appears in the chromatogram obtained by gas chromatography.

  In order to reduce the amount of exo-endo and endo-endo in the epoxy compound (A1), a method of precision distillation of the epoxy compound (A1) and column chromatography using silica gel or the like as a packing material are applied. An appropriate method such as a method can be applied.

  The epoxy compound (A1) may be a part or all of the polyfunctional polymerizable compound (A). The percentage ratio of the epoxy compound (A1) to the polyfunctional cationic polymerizable compound (A) is preferably in the range of 15 to 100% by mass. When the percentage is 15% by mass or more, the epoxy compound (A1) can particularly contribute to the improvement of the ultraviolet curable property and the low viscosity of the composition (X).

  The percentage of the epoxy compound (A1) with respect to the total amount of the resin component in the composition (X) is preferably in the range of 5 to 95% by mass. The resin component refers to a compound having cationic polymerizability in the composition (X), and includes a polyfunctional cationic polymerizable compound (A) and a monofunctional cationic polymerizable compound (E). When the composition (X) contains a polyfunctional cation polymerizable compound (B) described later, the resin component also contains this polyfunctional cation polymerizable compound (B). When this percentage is 5% by mass or more, the epoxy compound (A1) can particularly contribute to the improvement of the ultraviolet curable property, the viscosity reduction, and the storage stability of the composition (X). When the percentage is 95% by mass or less, the viscosity change of the composition (X) during storage is suppressed. For example, when the composition (X) is applied by an ink jet method or the like even when stored for a long period of time, the composition ( X) can be discharged stably. It is more preferable that this percentage is in the range of 10 to 80% by mass. In this case, for example, when the composition (X) is applied by an inkjet method or the like, the composition (X) can be accurately and stably discharged.

  When the epoxy compound (A1) is a part of the polyfunctional polymerizable compound (A), the polyfunctional polymerizable compound (A) further contains a compound (A2) other than the epoxy compound (A1). Compound (A2) is, for example, a bifunctional alicyclic epoxy compound represented by the following formula (31), a trifunctional epoxy compound represented by the following formula (32), or a bifunctional oxetane represented by the following formula (33) Among the compounds, alkylene glycol diglycidyl ether as shown in the following formulas (34) to (37), and alkylene glycol monovinyl monoglycidyl ether as shown in formula (38), at least one component can be contained.

In Formula (31), R ^{1 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group. The hydrocarbon group may contain an oxygen atom or a halogen atom. In the formula (1), X is a single bond or a divalent organic group, and the organic group is, for example, —CO—O—CH ₂ —.

  Examples of the compound represented by the formula (31) include a compound represented by the following formula (31a) and a compound represented by the following formula (31b).

  More specifically, the compound (A2) includes, for example, Daicel-made Celoxide 2021P and Celoxide 8010, Nissan Chemical's TEPIC-VL, Toagosei's OXT-221, and Yokkaichi-Synthetic 1,3-PD-DEP. , 1,4-BG-DEP, 1,6-HD-DEP, NPG-DEP and at least one component selected from the group consisting of butylene glycol monovinyl monoglycidyl ether.

  The compound (A2) preferably has an alicyclic epoxy structure, and particularly preferably contains a compound represented by the formula (31). In this case, the composition (X) can have higher cationic polymerization reactivity.

  In particular, the compound (A2) preferably contains a compound represented by the formula (31a). In this case, the composition (X) can have a higher cationic polymerization reactivity and a particularly low viscosity.

  The percentage of the polyfunctional cation polymerizable compound (A) with respect to the total amount of the resin component is preferably in the range of 10% by mass or more and less than 100% by mass. If this percentage is 10% by mass or more, the composition (X) can have particularly excellent reactivity during the photocationic polymerization reaction, and the cured product can thereby have high strength. The amount of the polyfunctional cation polymerizable compound (A) is more preferably 12% by mass or more, further preferably 15% by mass or more, and particularly preferably 25% by mass or more. The amount of the polyfunctional cation polymerizable compound (A) is more preferably 85% by mass or less, and further preferably 60% by mass or less.

  The composition (X) may contain a polyfunctional cation polymerizable compound (B) having a siloxane skeleton. The polyfunctional cationically polymerizable compound (B) has a siloxane skeleton and two or more cationically polymerizable functional groups per molecule. The number of cation polymerizable functional groups per molecule of the polyfunctional cation polymerizable compound (B) is preferably 2 to 6, more preferably 2 to 4. The polyfunctional cation polymerizable compound (B) can contribute to the improvement of the cationic polymerization reactivity of the composition (X) and can contribute to the improvement of the heat discoloration of the cured product and the sealing material 5. When the heat resistant discoloration of the sealing material 5 is high, it is possible to suppress deterioration over time of the light emission intensity and change over time of the emission color of the organic EL light emitting device 1 including the sealing material 5. Further, the polyfunctional cation polymerizable compound (B) can also contribute to lowering the elastic modulus of the cured product and the sealing material 5, and for this reason, organic EL light emission including the sealing material 5 including the sealing material 5. It is also possible to impart flexibility to the device 1. When the composition (X) contains a hygroscopic agent (D), the polyfunctional cationic polymerizable compound (B) improves the dispersibility of the hygroscopic agent (D) in the composition (X) and in the cured product. Can contribute. For this reason, even if it is a case where surface treatment for a dispersibility improvement etc. is not given to a hygroscopic agent (D), a hygroscopic agent (D) can disperse | distribute favorably in a composition (X) and hardened | cured material. .

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

  The cationically polymerizable functional group possessed by 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 cation 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 2-15. 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, more 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 at least one of, for example, a compound represented by the formula (10) and a compound represented by the formula (11).

  R in each of the formula (10) and the formula (11) is a single bond or a divalent organic group, and is preferably an alkylene group. Y is a siloxane skeleton and may be linear, branched or cyclic, and the number of Si atoms is preferably in the range of 2 to 10, more preferably in the range of 2 to 7, If it is in the range of 3-6, it is still more preferable. n is an integer greater than or equal to 2, and it is preferable to exist in the range of 2-4.

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

  R in 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 formula (10a) is an integer of 0 or more. The compound represented by the formula (10a) preferably contains a compound represented by the following formula (2). That is, it is preferable that the polyfunctional cation polymerizable compound (B) contains a compound represented by the following formula (2).

  In Formula (2), n is an integer greater than or equal to 0, and it is preferable to exist in the range of 0-8. It is more preferable that n is in the range of 0 to 5, and even more preferably in the range of 1 to 4.

  Examples of the compound represented by the formula (2) include a compound represented by the following formula (10a-1).

  The polyfunctional cation polymerizable compound (B) is replaced with the compound represented by the formula (10a) or together with the compound represented by the formula (10a), and the following formulas (10b) to (10d) and (11a) to (11b): You may contain at least 1 type of compound among the compounds shown to.

  R in 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 formula (10d) is an integer of 0 or more. M in the formula (10d) is an integer of 2 or more.

  R in 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 preferably in the range of 8-80. M in the formula (11a) is an integer of 2 or more, and preferably in the range of 2 to 6.

  R in 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 preferably in the range of 8-80.

  More specifically, the polyfunctional cation 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. It contains 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 preferred.

  The polyfunctional cation polymerizable compound (B) preferably has an alicyclic epoxy structure, and it is particularly preferable if the polyfunctional cation polymerizable compound (B) contains a 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, as well as the improvement of the heat discoloration and the low elastic modulus of the cured product and the sealing material 5. Can particularly contribute. When composition (X) contains a hygroscopic agent (D), it can contribute especially to the improvement of the dispersibility of the hygroscopic agent (D) in composition (X).

  It is preferable that the quantity of the polyfunctional cation polymeric compound (B) with respect to the whole quantity of a resin component exists in the range of 5-95 mass%. If the amount of the polyfunctional cationically polymerizable compound (B) is 5% by mass or more, when the composition (X) contains the hygroscopic agent (D), the moisture absorption in the composition (X) and the cured product By particularly improving the dispersibility of the agent (D), the transparency of the cured product is particularly improved. Further, if the amount of the polyfunctional cationically polymerizable compound (B) is 95% by mass or less, the composition (X) can have particularly high photocationic polymerization reactivity, and therefore the cured product has particularly high strength. Can have. The amount of the polyfunctional cation polymerizable compound (B) is more preferably 6% by mass or more, and further preferably 13% by mass or more. The amount of the polyfunctional cation polymerizable compound (B) is more preferably 70% by mass or less, and further preferably 45% by mass or less.

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

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

  The cationic curing catalyst of the nonionic photoacid generator is, for example, at least one selected from the group consisting of nitrobenzyl esters, sulfonic acid derivatives, phosphate esters, phenol sulfonate esters, diazonaphthoquinone, and N-hydroxyimide phosphonates. The component of this can be contained.

More specific examples of components contained in the cationic curing catalyst (C) include DPI series (105, 106, 109, 201, etc.), BI-105, MPI series (103, 105, 106, 109, etc.) manufactured by Midori Chemical. ), BBI series (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, 01, etc.), SI series (105, 106, etc.), PI-106, NDI series (105, 106, 109, 1001, 1004, etc.), PAI series (01, 101, 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, etc.) 104, 107, 108, 109, 110, 113, 114, 118, 122, 123, 203, 204, etc.), NBC-101, ANC-101, TPS-Acetate, DTS-Acetate, Di-Boc Bispinol A, tert- Butyl lit ocholate, tert-Butyl deoxycholate, tert-Butyl cholate, BX, BC-2, MPI-103, BDS-105, TPS-103, NAT-103, BMS-105, and TMS-105;
Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, and Cyracure UVI-950 from Union Carbide, USA;
Irgacure 250, Irgacure 261 and Irgacure 264 made by BASF;
CG-24-61 manufactured by Ciba Geigy;
Adekaoptomer SP-150, Adekaoptomer SP-151, Adekaoptomer SP-170 and Adekaoptomer SP-171 manufactured by ADEKA Corporation;
DAICAT II manufactured by Daicel Corporation;
UVAC1590 and UVAC1591 manufactured by Daicel-Cytec Corporation;
CI-2064, CI-2638, CI-2624, CI-2434, CI-2734, CI-2855, CI-2823, CI-2758, and CIT-1682 manufactured by Nippon Soda Co., Ltd .;
PI-2074, a tetrakis (pentafluorophenyl) borate toluylcumyl iodonium salt manufactured by Rhodia;
FFC509 manufactured by 3M;
CD-1010, CD-1011 and CD-1012 from Sartomer, USA;
CPI-100P, CPI-101A, CPI-110P, CPI-110A and CPI-210S manufactured by San Apro Co., Ltd., and UVI-6922 and UVI-6976 manufactured by Dow Chemical Co., Ltd. are included. The cationic curing catalyst (C) can contain at least one component among these components.

  The amount of the cationic 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.

  Composition (X) may contain a hygroscopic agent (D) as described above. When the composition (X) contains a hygroscopic agent (D), the cured product can have hygroscopicity. The average particle diameter of the moisture absorbent (D) is not limited. When the composition (X) contains a hygroscopic agent (D) having an average particle size of 200 nm or less, particularly an average particle size of 100 nm or less, the cured product can also have high transparency. Moreover, even if the particle size of the hygroscopic agent (D) is small, the composition (X) can have a low viscosity by containing the epoxy compound (A1) and the monofunctional cation polymerizable compound (E). .

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

  Preferably, the hygroscopic agent (D) contains zeolite particles having an average particle size of 200 nm or less. Particularly preferably, the hygroscopic agent (D) contains zeolite particles having an average particle diameter of 100 nm or less. Zeolite particles having an average particle size of 200 nm or less or an average particle size of 100 nm or less can be produced, for example, by pulverizing general industrial zeolite. The zeolite may be pulverized and then crystallized by hydrothermal synthesis or the like. In this case, the zeolite particles can have particularly high hygroscopicity. Such a method for producing zeolite particles is known from Japanese Patent Application Laid-Open Nos. 2006-69266 and 2013-049602.

  A specific example of a method for producing zeolite particles having an average particle size of 200 nm or less or an average particle size of 100 nm or less is shown. First, zeolite powder is prepared. The zeolite powder is preferably a zeolite containing sodium such as LTA type (A type zeolite), but is not limited thereto. The zeolite powder is physically pulverized. For example, the zeolite powder can be physically pulverized by mixing the zeolite powder with water to prepare a slurry and applying this slurry to a bead mill pulverizer.

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

  Subsequently, if necessary, the zeolite powder is subjected to 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 performed, for example, by dispersing a zeolite powder in an aqueous solution containing magnesium ions to prepare a mixture and heating the mixture. More specifically, the ion exchange process is performed as follows, for example. First, the zeolite powder is mixed with magnesium chloride and water, and the resulting mixture is stirred while heating. During this treatment, it is preferable to repeat the operation of temporarily stopping the stirring and then discarding the supernatant of the mixture, and then replenishing the mixture with water and 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 in the range of, for example, 2-3 hours. Subsequently, if necessary, the dried zeolite powder is crushed using a mortar or the like and then sieved to adjust the particle size.

  Thereby, zeolite particles having an average particle size of 200 nm or less or an average particle size of 100 nm or less can be obtained.

Crystallization of the zeolite powder can also be performed in the presence of silicate and alkali metal oxide. The specific example of the manufacturing method of the zeolite particle of the average particle diameter 200nm or less in that case or an average particle diameter of 100 nm or less is shown. First, zeolite powder is prepared. The zeolite powder preferably has a composition of aM1 ₂ O · bSiO ₂ · Al ₂ O ₃ · cMe. M1 is an alkali metal, proton, or ammonium ion (NH ₄ ⁺ ), Me is an alkaline earth metal, a is a number in the range of 0.01 to 1, and b is in the range of 20 to 80. C is a number within the range of 0-1. The zeolite powder may be, for example, FAU type, CHA type, BEA type, MFI type, MOR type, or FER type.

  The zeolite powder is physically pulverized. For example, zeolite powder can be physically pulverized by applying it to a bead mill pulverizer.

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

  Thereby, zeolite particles having an average particle size of 200 nm or less or 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 not easily broken, and therefore the sealing material made from the composition (X) containing the zeolite particles can have a particularly high hygroscopic property. Moreover, when the pH of the zeolite particles is 9 or less, the zeolite particles hardly inhibit the curing when the composition (X) is cured. More preferably, the pH of the zeolite particles is in the range of 6-8, more preferably in the range of 6.5-8.

  The pH of the zeolite particles was determined by heating the 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 adjusting the pH of the supernatant of the dispersion to a pH measuring device. It is a value obtained by measuring with. As a 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 made of FAU Y type zeolite having protons as counter cations.

  In the process of producing zeolite particles, when hydrothermal synthesis of zeolite is performed, a treatment for adjusting pH may be performed. The treatment for adjusting the pH is performed, for example, before heating the slurry containing the zeolite powder prepared for hydrothermal synthesis, during the heating of the slurry, or after the heating of the slurry. Adjustment of pH is performed by adding an acid to a slurry, for example. The acid contains at least one component selected from the group consisting of 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 diameter of the hygroscopic agent (D) is preferably in the range of 10 to 100 nm. If this average particle diameter is 100 nm or less, the cured product can have particularly high transparency. Moreover, if this average particle diameter is 10 nm or more, the good hygroscopicity of the hygroscopic agent (D) can be maintained. In addition, the average particle diameter of the hygroscopic agent (D) is a median diameter calculated from a measurement result by a dynamic light scattering method, that is, a cumulative 50% diameter (D50). In addition, as a measuring apparatus, the nano track Nanotrac Wave series of Microtrack Bell Inc. can be used.

  It is particularly preferable if the average particle diameter 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 (D) with respect to the total amount of the composition (X) is preferably in the range of 1 to 20% by mass. If the amount of the hygroscopic agent (D) is 1% by mass or more, the cured product can have particularly high hygroscopicity. Further, if 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 that can be applied by an ink jet method. You can also. The amount of the hygroscopic agent (D) is more preferably in the range of 1 to 20% by mass, and further preferably in the range of 5 to 15% by mass.

  The composition (X) contains a monofunctional cation polymerizable compound (E). Therefore, even if the composition (X) does not contain a solvent, the monofunctional cationic polymerizable compound (E) can reduce the viscosity of the composition (X).

  The viscosity at 25 ° C. of the monofunctional cationic polymerizable compound (E) is preferably 8 mPa · s or less. In this case, the monofunctional cation polymerizable compound (E) can particularly contribute to lowering the viscosity of the composition (X). This viscosity is preferably in the range of 0.1 to 8 mPa · s.

  The monofunctional cationic polymerizable compound (E) has only one cationic polymerizable functional group per molecule. The cationically polymerizable functional group in the monofunctional cationically polymerizable compound (E) 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 cation polymerizable compound (E) can contain at least one compound selected from the group consisting of compounds represented by the following formulas (12) to (17), for example.

  The monofunctional cation polymerizable compound (E) preferably contains a compound represented by the above formula (16). In this case, not only can the viscosity of the composition (X) be reduced, but also the increase in viscosity over time can be effectively suppressed. Therefore, even when the composition (X) is stored for a long period of time, the composition (X) can have good coatability and can maintain good ink jet coatability.

  The percentage of the monofunctional cation polymerizable compound (E) with respect to the total amount of the resin component is preferably 25% by mass or less. In this case, volatilization of the monofunctional cation polymerizable compound (E) from the composition (X) during storage of the composition (X) can be suppressed. Therefore, the change of the composition (X) is suppressed and the composition (X) can have good storage stability.

  It is also preferable that the percentage of the monofunctional cation polymerizable compound (E) is 20% by mass or less. In this case, the change in the composition of the composition (X) due to the volatilization of the monofunctional cation polymerizable compound (E) is further suppressed. In particular, when the monofunctional cation polymerizable compound (E) is a compound represented by the formula (16), the polyfunctional cation polymerizable compound (A) may contain an epoxy compound (A1), Even when the percentage of the monofunctional cationically polymerizable compound (E) is 20% by mass or less, the composition (X) can have a low viscosity.

  Moreover, it is also preferable that the percentage of this monofunctional cation polymerizable compound (E) is 3 mass% or more. In this case, the monofunctional cation polymerizable compound (E) can particularly contribute to lowering the viscosity of the composition (X). More preferably, this percentage is 5% by mass or more.

  The composition (X) may contain a dispersant (F). When the composition (X) contains the dispersant (F), the dispersibility of the hygroscopic agent (D) can be particularly improved when the composition (X) contains the hygroscopic agent (D), and the composition (X) In particular, the viscosity of can be reduced.

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

  The silane coupling agent can contain at least one component selected from the group consisting of vinyl silane, epoxy silane, methacryl silane, amine silane, and alkoxy silane.

  The dispersant (F) is preferably non-amine-based. This is because amine-based dispersants may inhibit photocationic polymerization. For this reason, it is more preferable that a dispersing agent (F) does not contain said 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, generation | occurrence | production of the outgas from a composition (X) can be suppressed and adhesiveness with hardened | cured material and a glass-made board | substrate etc. can be improved. The amount of the dispersing agent (F) is more preferably in the range of 20 to 40% by mass relative to the total amount of the filler, and further preferably in the range of 25 to 35% by mass. In addition, a filler is an inorganic particle in composition (X) and contains a hygroscopic agent (D). When the composition (X) contains an inorganic filler other than the moisture absorbent (D) described later, the filler also contains an inorganic filler.

  The composition (X) may contain an inorganic filler other than the hygroscopic agent (D). The inorganic filler preferably contains nano-sized high refractive index particles. Examples of high refractive index particles include zirconia particles. When composition (X) contains high refractive index particles, the cured product can have a higher 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 light that passes through the sealing material 5 and is emitted to the outside. The average particle diameter 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 the 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) such that the cured product has a refractive index 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 those described above. For example, the composition (X) may contain a sensitizer.

  The composition (X) preferably contains no solvent. In this case, when producing a cured product from the composition (X), it is not necessary to dry the composition (X) and volatilize the solvent.

  Composition (X) can be prepared by mixing the above-mentioned components.

  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 the sealing material 5 in the organic EL light-emitting device 1, it is possible to particularly improve the extraction efficiency of light that passes through the sealing material 5 and is emitted to the outside. The high light transmittance of such a cured product is that the average particle diameter of the hygroscopic agent (D) is 200 nm or less or 100 nm or less even when the composition (X) contains the hygroscopic agent (D). Is achievable.

When the composition (X) contains the hygroscopic agent (D), the moisture absorption rate of the cured product is preferably 0.5% by mass or more, more preferably 1% by mass or more, and 2% by mass or more. Most preferred. In addition, a moisture absorption rate is calculated | required with 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 / cm ² , 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. This measurement result is defined as an initial mass (M ₀ ). Subsequently, the film is sufficiently absorbed. For this purpose, for example, the film is exposed under conditions of 85 ° C. and 85% RH for 24 hours. The mass of the film after moisture absorption is measured. This measurement result is referred to as mass after moisture absorption (M). From these initial mass (M ₀ ) and mass after moisture absorption (M), the moisture absorption rate can be calculated by the formula (M−M ₀ ) / M ₀ × 100 (% by mass).

  The cured product can have high adhesion between silicon nitride and silicon oxide. Silicon nitride and silicon oxide may be used as a material for the passivation layer 6 in the organic EL light emitting device 1. For this reason, 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. Polyfunctional cation polymerizable compound (A) (when composition (X) contains polyfunctional cation polymerizable compound (B), polyfunctional cation polymerizable compound (A) and polyfunctional cation polymerizable compound (B)) When at least one of them has an epoxy group, the cured product can have particularly high adhesion to silicon nitride and silicon oxide.

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

  In the present embodiment, it is preferable to prepare the encapsulant 5 by molding the composition (X) by an ink jet method and then curing the composition (X) by irradiating the composition with ultraviolet rays. In the present embodiment, the composition (X) can be applied and molded by an inkjet method.

  In applying the composition (X) by the ink jet method, if the composition (X) has a sufficiently low viscosity at room temperature, the composition (X) is applied by the ink jet method without heating. it can.

  In the case where the composition (X) has a property of lowering viscosity by being heated, the composition (X) may be heated and then applied by an inkjet method to be molded. When the viscosity at 50 ° C. of the composition (X) is 1 mPa · s or more and 30 mPa · s or less, the composition (X) is heated to reduce the viscosity, and then the composition (X) is discharged by an ink jet method. It is preferable. The heating temperature of the composition (X) is, for example, 20 ° C. or higher and 70 ° C. or lower.

  A method for producing the organic EL light emitting device 1 of the first example shown in FIG. 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 produced by an appropriate method such as a vapor deposition method or a coating method. In particular, the organic EL element 4 is preferably produced by a coating method such as an inkjet method.

  Next, a passivation layer 6 is provided. The passivation layer 6 can be produced by, for example, 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 for applying the composition (X) is, for example, a casting method or an inkjet method. In this embodiment, since the viscosity of the composition (X) can be reduced, 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 application 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 overlaid 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. The ultraviolet rays pass through the transparent substrate 3 and reach the composition (X). Thereby, cationic polymerization reaction advances in composition (X), composition (X) hardens | cures, and the sealing material 5 which consists of hardened | cured material is produced. The thickness of the sealing material 5 is in the range of 5 to 50 μm, for example.

  A method for producing the organic EL light emitting device 1 of the second example shown in FIG. 2 will be described.

  First, the support substrate 2 is prepared. A partition wall 7 is formed on one surface of the support substrate 2 by, for example, a photolithography method using a photosensitive resin material. Subsequently, a plurality of organic EL elements 4 are provided on one surface of the support substrate 2. The organic EL element 4 can be produced by an appropriate method such as a vapor deposition method or a coating method. In particular, the organic EL element 4 is preferably produced by a coating method such as an inkjet method. Thereby, the element array 9 is produced on the support substrate 2.

  Next, a first passivation layer 61 is provided on the element array 9. The first passivation layer 61 can be produced by a vapor deposition method such as a plasma CVD method.

  Next, composition (X) is shape | molded on the 1st passivation layer 61, for example with the inkjet method, and a coating film is produced. If the inkjet method is applied to both the formation of the organic EL element 4 and the application of the composition (X), the production efficiency of the organic EL light-emitting device 1 can be particularly improved. Subsequently, the encapsulant 5 is produced by curing the coating film by irradiating it with ultraviolet rays. The thickness of the sealing material 5 is, for example, 5 μm or more and 50 μm or less.

  Next, a second passivation layer 62 is provided on the sealing material 5. The second passivation layer 62 can be produced by an evaporation method such as a plasma CVD method.

  Next, an ultraviolet curable resin material is provided on one surface of the support substrate 2 so as to cover the second passivation layer 62, and then the transparent substrate 3 is overlaid on the resin material. 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. The ultraviolet rays pass through the transparent substrate 3 and reach the ultraviolet curable resin material. Thereby, the ultraviolet curable resin material is cured and the second sealing material 52 is produced.

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

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

Details of the components shown in the table are as follows. Moreover, the viscosity of each of the following components is a value measured using a rheometer (manufactured by Anton Paar Japan, model number DHR-2) under conditions of a temperature of 25 ° C. and a shear rate of 100 s ⁻¹ .

(1) Polyfunctional cationically polymerizable compound having no siloxane skeleton. THI-DE: JX Energy Corporation, product number THI-DE, compound represented by formula (1a), viscosity 20 mPa · s.
OXT-221: manufactured by Toagosei Co., Ltd., product number OXT-221, compound represented by formula (33), viscosity 10 mPa · s.
Celoxide 8010: manufactured by Daicel, product name Celoxide 8010, a compound represented by the formula (31a), viscosity 60 mPa · s.
LDO: manufactured by Arkema, product name LDO, compound represented by the following formula, viscosity 6 mPa · s.

(2) Polyfunctional cationically 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, compound represented by formula (10a) (mixture of n = 3 to 6, R = C ₂ H ₄ ), viscosity 20 mPa · s.
X-22-169AS: manufactured by Shin-Etsu Chemical Co., Ltd., product number X-22-169AS, compound represented by formula (10a) (n = 10, R = C ₂ H ₄ ), viscosity 25 mPa · s.
X-22-169B: manufactured by Shin-Etsu Chemical Co., Ltd., product number X-22-169B, compound having the structure of the compound represented by formula (10a) (n = 20, R = C ₂ H ₄ ), viscosity 80 mPa · s.

(3) Monofunctional cationically polymerizable compound / 3-allyloxymethyl-3-ethyloxetane: produced by Yokkaichi Synthesis, formula (16), viscosity 2 mPa · s.

(4) Catalyst / DTS-200: manufactured by Midori Chemical, product number DTS-200, C ₆ H ₅ —S—C ₆ H ₄ —S ⁺ (C ₆ H ₅ ) ₂ .B (C ₆ F ₅ ) ₄ ⁻ .

2. Evaluation Test The following evaluation tests were conducted on the examples and comparative examples. The results are shown in the table.

(1) Inkjet property (initial)
The composition is put in a cartridge of an ink jet printer (Seiko Epson Corporation, model PX-B700), and after confirming that the composition in the cartridge can be discharged from the nozzle in the ink jet printer, the composition is discharged from the nozzle. The test pattern was printed continuously. As a result, “A” when the composition can be discharged for 1 hour and the discharge operation is stable, “B” when the composition can be discharged for 1 hour but the discharge operation becomes intermittently unstable. The case where the nozzle was clogged 1 hour after the start of discharge and the composition could not be discharged was evaluated as “C”.

(2) Viscosity at 25 ° C. The viscosity of the composition was measured using a rheometer (manufactured by Anton Paar Japan, model number DHR-2) under conditions of a temperature of 25 ° C. and a shear rate of 100 s ⁻¹ .

(3) Inkjet property (after 60 ° C., 1 hour)
The composition was put in a resin bottle with a capacity of 200 cc, and the composition was kept at a temperature of 60 ° C. for 1 hour, and then the inkjet property was confirmed by the same method as (1).

(4) Viscosity at 50 ° C. The viscosity of the composition was measured using a rheometer (manufactured by Anton Paar Japan, model number DHR-2) under conditions of a temperature of 50 ° C. and a shear rate of 100 s ⁻¹ .

(5) Heat-resistant discoloration After applying the composition on a smooth table, an LED-UV irradiator manufactured by Panasonic Electric Works Co., Ltd. was used, and ultraviolet light was applied under conditions of a peak wavelength of 365 nm and an output of 300 mW / cm ^2. Was cured by irradiation for 10 seconds. Thereby, a film having a thickness of 10 μm was produced.

The light transmittance (τ ₀ ) at a wavelength of 430 nm of this film was measured using a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation. Subsequently, the film was heated at 150 ° C. for 24 hours, and then the light transmittance (τ) at a wavelength of 430 nm of the film was measured. The light transmittance retention was calculated by the formula (τ / τ ₀ ) × 100, and based on the result, the heat discoloration was evaluated as follows.
AA: Retention rate is 90% or more.
A: Retention rate is 80% or more and less than 90%.
B: Retention rate is 70% or more and less than 80%.
C: Retention rate is less than 70%.

(6) Storage property 10 g of the composition was placed in a petri dish having a diameter of 130 mm, placed in an Ar atmosphere dry box and allowed to stand for 5 hours, and then the composition was weighed. From the results, storage properties were evaluated as follows.
AA: Weight loss is less than 0.1%.
A: The weight reduction amount is 0.1% or more and less than 0.4%.
B: The weight loss is 0.4% or more and less than 1.5%.
C: Weight reduction amount is 1.5% or more.

(7) Curability After applying the composition on a smooth base, using an LED-UV irradiator manufactured by Panasonic Electric Works Co., Ltd., ultraviolet rays were applied under conditions of a peak wavelength of 365 nm and an output of 300 mW / cm ^2. Photocured by irradiation for 10 seconds. Thereby, 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 tester did not feel tack was evaluated as “A”, and the case where the tester felt tack was evaluated as “B”.

Claims (13)

Containing a polyfunctional cation polymerizable compound (A) having no siloxane skeleton, a cation curing catalyst (C), and a monofunctional cation polymerizable compound (E);
The polyfunctional cation polymerizable compound (A) contains an epoxy compound (A1) represented by the following formula (1),
In the formula (1), each of R ^{1 to} R ¹² independently represents a hydrogen atom, a halogen atom, or a carbon number of 1 to
20 hydrocarbon groups,
UV curable resin composition. The percentage ratio of the epoxy compound (A1) to the polyfunctional cation polymerizable compound (A) is in the range of 15 to 100% by mass.
The ultraviolet curable resin composition according to claim 1. The percentage of the epoxy compound (A1) with respect to the total amount of the resin components in the ultraviolet curable resin composition is in the range of 10 to 80% by mass.
The ultraviolet curable resin composition according to claim 1 or 2. The percentage of the monofunctional cation polymerizable compound (E) with respect to the total amount of the resin component in the ultraviolet curable resin composition is in the range of more than 0% by mass and 25% by mass or less.
The ultraviolet curable resin composition according to any one of claims 1 to 3. Further containing 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, wherein the number of Si atoms of the siloxane skeleton in the polyfunctional cation polymerizable compound (B) is in the range of 2 to 15. The polyfunctional cation polymerizable compound (B) contains a compound represented by the following formula (2),
In the formula (2), n is an integer of 0 or more.
The ultraviolet curable resin composition according to claim 5 or 6. In the formula (2), n is an integer in the range of 0-8.
The ultraviolet curable resin composition according to claim 7. Does not contain solvent,
The ultraviolet curable resin composition according to any one of claims 1 to 8. The viscosity at 25 ° C. is in the range of 5 to 50 mPa · s.
The ultraviolet curable resin composition according to any one of claims 1 to 9. Used to produce a sealing material for organic EL elements,
The ultraviolet curable resin composition according to any one of claims 1 to 10. An organic EL light emitting device comprising an organic EL element and a sealing material covering the organic EL element,
The ultraviolet curable resin composition according to any one of claims 1 to 11 is molded by an ink jet method, and then the ultraviolet curable resin composition is irradiated with ultraviolet rays to be cured to thereby form the sealing material. Including producing,
Manufacturing method of 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 the ultraviolet curable resin composition according to any one of claims 1 to 11.
Organic EL light emitting device.