CN112062936A

CN112062936A - Ultraviolet-curable resin composition, method for producing light-emitting device, and light-emitting device

Info

Publication number: CN112062936A
Application number: CN202010520601.0A
Authority: CN
Inventors: 浦冈祐辅; 池上裕基; 山本广志
Original assignee: Panasonic Intellectual Property Management Co Ltd
Current assignee: Panasonic Intellectual Property Management Co Ltd
Priority date: 2019-06-10
Filing date: 2020-06-09
Publication date: 2020-12-11

Abstract

The invention provides an ultraviolet-curable resin composition, a method for manufacturing a light-emitting device, and a light-emitting device. The ultraviolet-curable resin composition contains a cationically polymerizable compound (F) and a cationic curing catalyst (G). The cationic curing catalyst (G) contains a plurality of ionic photoacid generators having different strengths of conjugate acids of anionic species from each other. The ultraviolet-curable resin composition is used for producing an optical component that transmits light emitted from a light source.

Description

Ultraviolet-curable resin composition, method for producing light-emitting device, and light-emitting device

Technical Field

The present invention relates to an ultraviolet-curable resin composition, a method for producing a light-emitting device, and more particularly, to an ultraviolet-curable resin composition containing a cationically polymerizable compound and a cationic curing catalyst, a method for producing a light-emitting device using the ultraviolet-curable resin composition, and a light-emitting device provided with a sealing material containing a cured product of the ultraviolet-curable resin composition.

Background

Light-emitting devices including light-emitting elements such as organic EL elements and micro LEDs are used for illumination, display, and the like, and are expected to spread in the future.

The light emitting element in the light emitting device is covered with a sealing material so that the light emitting element is not deteriorated by moisture. In this case, light emitted from the light-emitting element is emitted to the outside through the sealing material. The sealing material can be produced, for example, from a composition containing a cationic curable resin and a cationic polymerization initiator (see japanese patent No. 5703429). In this case, since the composition can be cured by ultraviolet irradiation or the like to produce the sealing material, the sealing material can be produced without applying a load due to heat to the light-emitting element.

Disclosure of Invention

The subject of this application is: provided is an ultraviolet-curable resin composition which is used for manufacturing an optical component for transmitting light emitted by a light source, is not easy to reduce the transparency of the optical component even if the curability is improved, and is easy to realize low viscosity and high storage stability; a method for producing a light-emitting device using the ultraviolet-curable resin composition; and a light-emitting device provided with an optical component that includes a cured product of an ultraviolet-curable resin composition.

Means for solving the problems

The ultraviolet-curable resin composition according to one embodiment of the present invention contains a cationically polymerizable compound (F) and a cationic curing catalyst (G), and the cationically polymerizable compound (F) contains an epoxy compound and a compound (F22) having an oxyalkylene group and an oxetanyl group. The ultraviolet curable resin composition is used for manufacturing an optical component for transmitting light emitted by a light source.

A method for manufacturing a light-emitting device according to one aspect of the present application is a method for manufacturing a light-emitting device including a light-emitting element and a sealing material covering the light-emitting element. The method comprises the following steps: the sealing material is produced by forming a coating film by discharging the ultraviolet curable resin composition to a position through which light emitted from the light source passes by an ink jet method, and irradiating the coating film with ultraviolet light.

A light-emitting device according to one aspect of the present application includes a light source and an optical member that transmits light emitted from the light source. The optical member includes a cured product of the ultraviolet-curable resin composition.

Drawings

Fig. 1 is a schematic cross-sectional view showing a first example of a light-emitting device according to an embodiment of the present application.

Fig. 2 is a schematic cross-sectional view showing a second example of a light-emitting device according to an embodiment of the present application.

Detailed Description

The composition used for producing an optical member such as a sealing material is preferably low in viscosity for easy moldability, and preferably contains no easily volatile component so that the viscosity does not increase even after long-term storage. Further, in order to improve the efficiency of producing an optical component, it is preferable that the composition has high curability when irradiated with ultraviolet light.

However, according to the examination of the inventors, when the curability of the cationically polymerizable composition is improved, the transparency of the optical member is likely to be lowered. If the transparency of the optical member is lowered, the light-emitting performance of the light-emitting element or the like is lowered.

Accordingly, the present inventors have conducted intensive studies and developments to provide an ultraviolet-curable resin composition which is used for producing an optical component that transmits light emitted from a light source, is less likely to cause a decrease in the transparency of the optical component even when the curability is improved, and is likely to realize a low viscosity and high storage stability, and as a result, have completed the present application.

Hereinafter, one embodiment of the present application will be described.

The ultraviolet-curable resin composition according to the present embodiment (hereinafter also referred to as composition (X)) is used for producing an optical component that transmits light emitted from a light source. The optical member is a member for transmitting light in a device having an optical system (e.g., a light-emitting device). The optical member is, for example, a sealing material for a light emitting element. The optical member is, for example, a thin film, more specifically, a film of 2 μm or more and 50 μm or less, or a film of 2 μm or more and 30 μm or less.

The composition (X) contains a cationically polymerizable compound (F) and a cationic curing catalyst (G). The cationically polymerizable compound (F) contains an epoxy compound and a compound (F22) having an oxyalkylene group and an oxetanyl group.

According to the present embodiment, the curability of the composition (X) is likely to be improved when the composition (X) is irradiated with ultraviolet rays, and the composition (X) is less likely to be cured excessively sharply at this time, so that the cured product is less likely to suffer from deterioration in transparency due to cloudiness or the like. It can be presumed that: the mechanism by which this effect occurs is as follows. Since the reactivity of the compound (f22) is lower than that of the epoxy compound, when the composition (X) is irradiated with ultraviolet light, the epoxy compound reacts first. The epoxy compound is reacted, whereby the curability of the composition (X) tends to be high. Next, the compound (f22) is reacted, whereby the epoxy compound and the compound (f22) are less likely to react at a time. This is considered to be unlikely to cause an excessively violent reaction.

Further, since the compound (f22) has a low viscosity, the composition (X) can be easily made to have a low viscosity. Further, since the compound (f22) is less likely to volatilize, even when the composition (X) is stored, the composition (X) is less likely to change in composition due to volatilization of the compound (f 22). Therefore, the compound (f22) tends to improve the storage stability of the composition (X).

Further, in the case where the composition (X) is ejected by an ink jet method, the compound (f22) is less likely to cause defective droplets called satellite droplets (サテライト), and satellite droplets are less likely to be generated even when the speed of the droplets ejected by the ink jet method is increased. Further, as described above, since the compound (f22) can improve the storage stability of the composition (X), the characteristics of the composition (X) in which satellite droplets are not easily generated can be easily maintained even when the composition (X) is stored for a long period of time.

As described above, according to the present embodiment, when an optical component is produced from the composition (X), even if the curability of the composition (X) is improved, the transparency of the optical component is not easily lowered, and the low viscosity and the high storage stability of the composition (X) are easily achieved.

The cured product obtained by heating the composition (X) after irradiation with light preferably has a glass transition temperature of 80 ℃ or higher. In this case, the cured product can have good heat resistance. Therefore, for example, when a cured product is subjected to a treatment involving a temperature increase, the cured product is less likely to deteriorate. The glass transition temperature of the cured product is more preferably 90 ℃ or higher, and still more preferably 100 ℃ or higher.

The viscosity of the composition (X) at 25 ℃ is preferably 1 mPas to 40 mPas. In this case, the composition (X) can be applied at room temperature by a casting method or can be formed by discharging the composition (X) by an ink jet method. The viscosity is more preferably 35mPa · s or less, still more preferably 30mPa · s or less, particularly preferably 20mPa · s or less, and most preferably 15mPa · s or less. The viscosity is preferably 5 mPas or more, and more preferably 8 mPas or more. For example, the viscosity is preferably 8 mPas or more and 35 mPas or less.

It is also preferable that the viscosity of the composition (X) at 40 ℃ is 1 mPas or more and 40 mPas or less. In this case, regardless of the viscosity of the composition (X) at room temperature, the viscosity can be reduced by slightly heating the composition (X). Therefore, if heating is performed, the composition (X) can be easily molded by a method such as a casting method, and the composition (X) can be discharged by an ink jet method. In addition, since the viscosity of the composition (X) can be reduced without substantially heating the composition (X), a change in the composition of the composition (X) due to volatilization of components in the composition (X) can be prevented. The viscosity is more preferably 35mPa · s or less, still more preferably 30mPa · s or less, particularly preferably 20mPa · s or less, and most preferably 15mPa · s or less. The viscosity is preferably 5 mPas or more, and more preferably 8 mPas or more. For example, the viscosity is preferably 8 mPas or more and 35 mPas or less.

The low viscosity at 25 ℃ or 40 ℃ of the composition (X) as described above can be achieved by the composition of the composition (X) as described in detail below.

The total light transmittance of the cured product of the composition (X) is preferably 90% or more in the case where the thickness dimension is 10 μm. In this case, when the cured product is applied to an optical member such as the sealing material 5 in the light-emitting device 1, the extraction efficiency of light emitted to the outside through the optical member can be particularly improved. The light transmittance of the cured product can also be achieved by the composition of the composition (X) described in detail below.

The surface tension of the composition (X) is preferably 20mN/cm or more and 40mN/cm or less. In this case, when the composition (X) is ejected by an ink jet method, the ejection stability is good, and defective droplets called satellites can be less likely to be generated. The surface tension is more preferably from 30mN/cm to 40mN/cm, still more preferably from 31mN/cm to 38 mN/cm.

Hereinafter, the present embodiment will be described in further detail.

1. Structure of light-emitting device

First, the structure of the light-emitting device 1 in the case where the device having an optical system is the light-emitting device 1 and the optical member is the sealing material 5 for sealing the light-emitting element 4 in the light-emitting device 1 will be described. The light-emitting device 1 includes a light-emitting element 4 and a sealing material 5 covering the light-emitting element 4. The sealing material 5 may cover the light-emitting element 4 in a state of directly contacting the light-emitting element 4, or may cover the light-emitting element 4 with some layers interposed between the sealing material 5 and the light-emitting element 4. The light-emitting device 1 may be, for example, an illumination device or a display device (display).

The light emitting element 4 includes, for example, a light emitting diode. The light emitting diode includes, for example, at least one of an organic EL element (organic light emitting diode) and a micro light emitting diode. When the light-emitting element 4 includes an organic light-emitting diode, the light-emitting device 1 including the light-emitting element 4 is, for example, an organic EL display. When the light-emitting element 4 includes a micro light-emitting diode, the light-emitting device 1 including the light-emitting element 4 is, for example, a micro LED display. EL means electroluminescence, and LED means a light emitting diode.

A first example of the structure of the light-emitting device 1 will be described with reference to fig. 1. The light emitting device 1 is of a top emission type. The light-emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 with a gap therebetween, a light-emitting element 4 located on a surface of the support substrate 2 facing the transparent substrate 3, and a sealing material 5 filled between the support substrate 2 and the transparent substrate 3. In the first example, the light-emitting device 1 includes the passivation layer 6 covering the surface of the support substrate 2 facing the transparent substrate 3 and the light-emitting element 4. That is, the passivation layer 6 is interposed between the light emitting element 4 and the sealing material 5 covering the light emitting 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 material having translucency. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate. When the light-emitting element 4 includes an organic EL element, the organic EL element includes, for example, a pair of electrodes and an organic light-emitting layer located between the electrodes. The organic light-emitting layer includes, for example, a hole injection layer, a hole transport layer, an organic light-emitting layer, and an electron transport layer, and these layers are stacked in this order. Although only one light emitting element 4 is shown in fig. 1, the light emitting device 1 may be provided with a plurality of light emitting elements 4, and the plurality of light emitting elements 4 may be arrayed on the support substrate 2. The passivation layer 6 is preferably made of silicon nitride or silicon oxide.

A second example of the structure of the light-emitting device 1 will be described with reference to fig. 2. In fig. 2, the same reference numerals as in fig. 1 are given to elements common to the first example shown in fig. 1, and detailed description thereof is omitted as appropriate. The light emitting device 1 shown in fig. 2 is also of a top emission type. The light-emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 with a gap therebetween, a light-emitting element 4 positioned on a surface of the support substrate 2 facing the transparent substrate 3, and a sealing material 5 covering the light-emitting element 4.

When the light-emitting element 4 includes an organic EL element, the organic EL element includes, for example, a pair of

electrodes

41 and 43 and an organic light-emitting layer 42 located between the

electrodes

41 and 43, as in the case of the first example. 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 this order.

The light-emitting device 1 includes a plurality of light-emitting elements 4, and the plurality of light-emitting elements 4 form an array 9 (hereinafter referred to as an element array 9) on the support substrate 2. The element array 9 further includes a partition wall 7. The partition wall 7 is positioned on the support substrate 2 to partition between the adjacent two light emitting elements 4. The partition wall 7 is formed by, for example, molding a photosensitive resin material by photolithography. The element array 9 further includes a connection wiring 8 for electrically connecting the electrodes 43 of the adjacent light-emitting elements 4 and the electron transit layer 424 to each other. The connection wiring 8 is provided on the partition wall 7.

The light-emitting device 1 further includes a passivation layer 6 covering the light-emitting element 4. The passivation layer 6 is preferably made of 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 element array 9 in a state of directly contacting the element array 9, thereby covering the light emitting elements 4. 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 the second passivation layer 62 is spaced apart from the first passivation layer 61. The 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 light emitting element 4 and the sealing material 5 covering the light emitting element 4.

Further, the second sealing material 52 is filled between the second passivation layer 62 and the transparent substrate 3. The second sealing member 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 member 52 may be the same as or different from that of the sealing member 5.

The sealing material 5 in the light-emitting device 1 having the structure exemplified above can be produced from the composition (X). That is, the composition (X) is used to prepare the sealing material 5 for the light-emitting element 4. In other words, the composition (X) is preferably a composition for producing a sealing material, a composition for sealing a light-emitting element, or a composition for producing a light-emitting device.

2. Ultraviolet-curable resin composition

The composition (X) contains a curable component having ultraviolet curability. The curable component contains a cationically polymerizable compound (F) and a cationic curing catalyst (photo-cationic curing catalyst) (G).

As described above, the cationically polymerizable compound (F) contains the epoxy compound (F1) and the compound (F22) having an oxyalkylene group and an oxetanyl group.

The cationic polymerizable compound (F) contains at least one of the polyfunctional cationic polymerizable compound (F1) and the monofunctional cationic polymerizable compound (F2), for example. The polyfunctional cationically polymerizable compound (F1) and the monofunctional cationically polymerizable compound (F2) are components contained in the cationically polymerizable compound (F) which are defined based on the number of functional groups in one molecule. Therefore, the epoxy compound (F1) may contain at least one of the component contained in the polyfunctional cationically polymerizable compound (F1) and the component contained in the monofunctional cationically polymerizable compound (F2). The compound (F22) having an oxyalkylene group and an oxetanyl group may contain at least one of a component contained in the polyfunctional cationically polymerizable compound (F1) and a component contained in the monofunctional cationically polymerizable compound (F2).

The polyfunctional cationic polymerizable compound (F1) may contain either one or both of the polyfunctional cationic polymerizable compound (F11) having no siloxane skeleton and the polyfunctional cationic polymerizable compound (F12) having a siloxane skeleton.

The polyfunctional cationically polymerizable compound (F11) has no siloxane skeleton and two or more cationically polymerizable functional groups per molecule. The number of the cationic polymerizable functional groups per molecule of the polyfunctional cationic polymerizable compound (F11) is preferably 2 to 4, and more preferably 2 to 3.

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

The polyfunctional cationic polymerizable compound (F11) contains, for example, at least one compound selected from the group consisting of a polyfunctional alicyclic epoxy compound, a polyfunctional heterocyclic epoxy compound, a polyfunctional oxetane compound, an alkylene glycol diglycidyl ether, and an alkylene glycol monovinyl monoglycidyl ether.

The polyfunctional alicyclic epoxy compound contains, for example, either one or both of a compound represented by the following formula (1) and a compound represented by the following formula (20).

In the formula (1), R¹～R¹⁸Each independently a hydrogen atom, a halogen atom or a hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably in the range of 1 to 20. The hydrocarbon group is an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, etc.; alkenyl groups having 2 to 20 carbon atoms such as vinyl groups and allyl groups; or an alkylidene group (アルキリデン group) having 2 to 20 carbon atoms such as an ethylidene group or a propylidene group. The hydrocarbon group may contain an oxygen atom or a halogen atom. R¹～R¹⁸Preferably, each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and furtherPreferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.

In the formula (1), X is a single bond or a divalent organic group such as-CO-O-CH₂-。

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 (1 b).

In the formula (20), R¹～R¹²Each independently represents 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, a propyl group; alkenyl groups having 2 to 20 carbon atoms such as vinyl groups and allyl groups; or an alkylidene group having 2 to 20 carbon atoms such as ethylidene group or propylidene group. The hydrocarbon group having 1 to 20 carbon atoms may contain an oxygen atom or a halogen atom.

R¹～R¹²Preferably, each independently represents 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.

Examples of the compound represented by formula (20) include tetrahydroindene diepoxide represented by formula (20a) below.

The polyfunctional heterocyclic epoxy compound contains, for example, a trifunctional epoxy compound represented by the following formula (2).

The polyfunctional oxetane compound contains, for example, a difunctional oxetane compound represented by the following formula (3).

The alkylene glycol diglycidyl ether contains, for example, at least one compound selected from the compounds represented by the following formulae (4) to (7).

The alkylene glycol monovinyl monoglycidyl ether contains, for example, a compound represented by the following formula (8).

More specifically, the polyfunctional cation polymerizable compound (F11) may contain at least one component selected from the group consisting of CELLOXIDE 2021P and CELLOXIDE 8010 manufactured by Celluosite, TEPIC-VL manufactured by Nissan Chemicals, OXT-221 manufactured by Toyao, and 1, 3-PD-DEP, 1, 4-BG-DEP, 1, 6-HD-DEP, NPG-DEP, and butanediol monovinyl monoglycidyl ether manufactured by Siraido.

The polyfunctional cationically polymerizable compound (F11) preferably further contains a polyfunctional alicyclic epoxy compound. In this case, the composition (X) may have particularly high cationic polymerization reactivity.

The polyfunctional alicyclic epoxy compound particularly preferably contains either one or both of the compound represented by formula (1) and the compound represented by formula (20). In this case, the composition (X) may have higher cationic polymerization reactivity.

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

In addition, since the compound represented by formula (20) has a low viscosity in particular, in the case where the compound represented by formula (20) is contained, the composition (X) can have good ultraviolet curability and can have a particularly low viscosity. Further, the compound represented by the formula (20) has a low viscosity, but has a property of being less volatile. Therefore, even if the composition (X) contains the compound represented by the formula (20), the composition (X) is less likely to undergo a change in composition due to volatilization of the compound represented by the formula (20). Therefore, by containing the compound represented by formula (20), the composition (X) can be reduced in viscosity without impairing storage stability.

The compound represented by formula (20) can be synthesized, for example, by oxidizing a cyclic olefin compound having a tetrahydroindene skeleton with an oxidizing agent.

The compound represented by formula (20) can contain 4 stereoisomers based on the stereoconfiguration of 2 epoxy rings. The compound represented by formula (20) may contain any of 4 stereoisomers. That is, the compound represented by formula (20) may contain at least one component selected from 4 stereoisomers. The total amount of exo-endo forms and endo forms in the 4 stereoisomers in the compound represented by formula (20) is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total epoxy compound (a 1). In this case, the heat resistance of the cured product can be improved. The ratio of the specific stereoisomer in the compound represented by formula (20) can be determined based on the peak area ratio appearing in the chromatogram obtained by gas chromatography.

In order to reduce the amount of exo-endo forms and endo-endo forms in the compound represented by formula (20), the following suitable method may be applied: a method of subjecting the compound represented by the formula (20) to precision distillation, and a method of applying column chromatography using silica gel or the like as a filler.

When the composition (X) contains the polyfunctional cationically polymerizable compound (F11), the ratio of the polyfunctional cationically polymerizable compound (F11) to the total amount of the resin components is preferably in the range of 5 to 95% by mass. The resin component is a compound having cationic polymerizability in the composition (X), and includes a polyfunctional cationic polymerizable compound (F1) and a monofunctional cationic polymerizable compound (F2). When the proportion of the polyfunctional cationically polymerizable compound (F11) is 5% by mass or more, the composition (X) can have particularly excellent reactivity in the photo cationic polymerization reaction, and thus the cured product can have high strength (hardness). When the proportion of the polyfunctional cation polymerizable compound (F11) is 95% by mass or less, the moisture absorbent (C) can be easily dispersed particularly uniformly in the composition (X) when the composition (X) contains the moisture absorbent (C). The proportion of the polyfunctional cation polymerizable compound (F11) is more preferably 12% by mass or more, still more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more. The proportion of the polyfunctional cation polymerizable compound (F11) is preferably 85% by mass or less, more preferably 60% by mass or less. For example, the proportion of the polyfunctional cationically polymerizable compound (F11) is preferably in the range of 20 to 60 mass%.

When the polyfunctional cationically polymerizable compound (F11) contains a polyfunctional alicyclic epoxy compound, the polyfunctional alicyclic epoxy compound may be a part of or the whole polyfunctional cationically polymerizable compound (F11). The ratio of the polyfunctional alicyclic epoxy compound to the polyfunctional cationically polymerizable compound (F11) is preferably in the range of 15 to 100% by mass. When the proportion is 15% by mass or more, the polyfunctional alicyclic epoxy compound can contribute particularly to improvement in ultraviolet curability of the composition (X).

The polyfunctional cationically polymerizable compound (F12) has a siloxane skeleton and two or more cationically polymerizable functional groups per molecule. The number of the cationic polymerizable functional groups per molecule of the polyfunctional cationic polymerizable compound (F12) is preferably 2 to 6, and more preferably 2 to 4. The polyfunctional cationically polymerizable compound (F12) can contribute to the improvement of the cationic polymerization reactivity of the composition (X) and can contribute to the improvement of the thermal discoloration resistance of the cured product and the optical member. The polyfunctional cationically polymerizable compound (F12) can also contribute to a low elastic modulus of a cured product and an optical member. When the composition (X) contains a moisture absorbent, the polyfunctional cation polymerizable compound (F12) can also contribute to improvement in dispersibility of the moisture absorbent in the composition (X) and in the cured product.

The polyfunctional cationically polymerizable compound (F12) is preferably liquid at 25 ℃. In particular, the viscosity of the polyfunctional cationic polymerizable compound (F12) at 25 ℃ is preferably in the range of 10 to 300mPa ■ s. In this case, the viscosity of the composition (X) can be inhibited from increasing.

The cationic polymerizable functional group of the polyfunctional cationic polymerizable compound (F12) is, for example, at least one group selected from an epoxy group, an oxetanyl group and a vinyl ether group.

The siloxane skeleton of the polyfunctional cationic polymerizable compound (F12) may be linear, branched, or cyclic. The number of Si atoms in the siloxane skeleton is preferably in the range of 2 to 14. In this case, the composition (X) may have a particularly low viscosity. The number of Si atoms is more preferably in the range of 2 to 10, still more preferably in the range of 2 to 7, and particularly preferably in the range of 3 to 6.

The polyfunctional cationically polymerizable compound (F12) contains at least one of the compound represented by the formula (10) and the compound represented by the formula (11), for example.

R in each of the formulae (10) and (11) is a single bond or a divalent organic group, and is preferably an alkylene group. Y is a siloxane skeleton, and may be any of linear, branched and cyclic, and the number of Si atoms is preferably in the range of 2 to 14, more preferably in the range of 2 to 10, even more preferably in the range of 2 to 7, and particularly preferably in the range of 3 to 6. n is an integer of 2 or more, preferably in the range of 2 to 4.

More specifically, for example, the polyfunctional cation polymerizable compound (F12) contains a compound represented by the following formula (10 a).

R in the formula (10a) is a single bond or a divalent organic group, preferably an alkylene group having 1 to 4 carbon atoms. N in the formula (10a) is an integer of 0 or more. n is preferably in the range of 0 to 12, more preferably in the range of 0 to 8, even more preferably in the range of 0 to 5, and particularly preferably in the range of 1 to 4.

More specifically, the polyfunctional cationic polymerizable compound (F12) preferably contains at least one component selected from the group consisting of X-40-2669, X-40-2670, X-40-2715, X-40-2732, X-22-169AS, X-22-169B, X-22-2046, X-22-343, X-22-163 and X-22-163B, all available from shin-Etsu chemical Co., Ltd.

The polyfunctional cationically polymerizable compound (F12) preferably has an alicyclic epoxy structure, and the polyfunctional cationically polymerizable compound (F12) is particularly preferably a compound represented by the formula (10 a). The compound represented by the formula (10a) can contribute particularly to the improvement of the cationic polymerization reactivity and the reduction of the viscosity of the composition (X), and can contribute particularly to the improvement of the heat discoloration resistance and the reduction of the elastic modulus of a cured product and an optical member. When the composition (X) contains the moisture absorbent (C), it is also possible to contribute to improvement of dispersibility of the moisture absorbent (C) in the composition (X).

When the composition (X) contains the polyfunctional cationically polymerizable compound (F12), the ratio of the polyfunctional cationically polymerizable compound (F12) to the total amount of the resin components is preferably in the range of 5 to 95% by mass. In this case, particularly if the composition (X) contains the moisture absorbent (C), the dispersibility of the moisture absorbent (C) in the composition (X) and in the cured product is particularly improved, and the composition (X) can have particularly high photo cation polymerization reactivity.

The monofunctional cationically polymerizable compound (F2) has only one cationically polymerizable functional group in one molecule. The cationically polymerizable functional group is, for example, at least one group selected from an epoxy group, an oxetanyl group and a vinyl ether group.

The viscosity of the monofunctional cationically polymerizable compound (F2) at 25 ℃ is preferably 8 mPas or less. In this case, the monofunctional cation polymerizable compound (F2) can reduce the viscosity of the composition (X) even if the composition (X) does not contain a solvent. In particular, the viscosity of the monofunctional cationically polymerizable compound (F2) at 25 ℃ is preferably in the range of 0.1 to 8 mPas.

The monofunctional cation polymerizable compound (F2) may contain, for example, at least one compound selected from the group consisting of compounds represented by the following formulae (12) to (17) and limonene oxide.

The proportion of the monofunctional cationically polymerizable compound (F2) to the total amount of the resin component is preferably in the range of 5 to 50% by mass. When the proportion of the monofunctional cationically polymerizable compound (F2) is 5% by mass or more, the viscosity of the composition (X) can be particularly reduced. When the proportion of the monofunctional cationically polymerizable compound (F2) is 50% by mass or less, the composition (X) can have particularly excellent reactivity in the photo-cationic polymerization reaction, and thus the cured product can have high strength (hardness). The proportion of the monofunctional cation polymerizable compound (F2) is more preferably 10% by mass or more, and still more preferably 15% by mass or more. The proportion of the monofunctional cation polymerizable compound (F2) is more preferably 40% by mass or less, still more preferably 35% by mass or less, and particularly preferably 30% by mass or less. When the proportion of the monofunctional cation polymerizable compound (F2) is 35% by mass or less, the volatilization amount of components in the composition (X) during storage of the composition (X) can be effectively reduced, and therefore, the properties of the composition (X) are not easily impaired even if the composition (X) is stored for a long period of time. Further, the occurrence of tackiness in the cured product can be particularly suppressed. For example, the proportion of the monofunctional cationically polymerizable compound (F2) is preferably within a range of 10 to 35% by mass.

The cationically polymerizable compound (F) may not contain the monofunctional cationically polymerizable compound (F2). In the present embodiment, even if the cationically polymerizable compound (F) does not contain the monofunctional cationically polymerizable compound (F2), the transparency of the optical member is not easily lowered even if the curability of the composition (X) is improved, and low viscosity and high storage stability of the composition (X) are easily achieved.

In particular, when the composition (X) contains the polyfunctional cationic polymerizable compound (F11) and the polyfunctional cationic polymerizable compound (F12), the ratio of the polyfunctional cationic polymerizable compound (F11) is preferably within a range of 30 to 60 mass%, the ratio of the polyfunctional cationic polymerizable compound (F12) is preferably within a range of 15 to 30 mass%, and the ratio of the monofunctional cationic polymerizable compound (F2) is preferably within a range of 15 to 40 mass%, based on the total amount of the resin components. In this case, the composition (X) can achieve a good balance between good storage stability and low viscosity and good cationic polymerization reactivity, and further, a cured product can achieve a good balance between excellent transparency, excellent moisture absorption, and a high refractive index.

When the cationically polymerizable compound (F) contains the compound represented by the formula (3) and the compound represented by the formula (16), the ease of the curing reaction when a photo-cured product is produced from the composition (X) can be appropriately adjusted by adjusting the ratio of the two compounds, and the composition (X) can be reduced in viscosity and improved in storage stability.

The amount of the compound represented by formula (16) may be suitably adjusted so that the composition (X) has the above-mentioned properties. For example, the amount of the compound represented by the formula (16) is preferably 10% by mass or more and 40% by mass or less with respect to the total amount of the resin components.

The cation polymerizable compound (F) preferably contains a compound (F11) (hereinafter also referred to as aromatic epoxy compound (F11)) represented by the following formula (30).

In the formula (30), X is at least one selected from the group consisting of halogen, H, a hydrocarbon group and an alkylene glycol group, and when a plurality of X are present in one molecule, they may be the same or different from each other. Hydrocarbyl is for example alkyl or aryl. The carbon number of X when X is a hydrocarbon group is, for example, in the range of 1 to 10. R is a single bond or a divalent organic group. In the case where R is a divalent organic group, the divalent organic group is, for example, an alkylene group, an oxyalkylene group, a carbonyloxyalkylene group (e.g., -CO-O-CH)₂-, or-C (Ph)₂-O-CH 2-group. If the divalent organic radical is-CH₂-, -O-CH 2-or-CO-O-CH 2-, are particularly preferred. Y is H or a monovalent organic group. In the case where Y is a monovalent organic group, the monovalent organic group is, for example, an alkyl group or an aryl group.

When the cationically polymerizable compound (F) contains the aromatic epoxy compound (F11), the aromatic epoxy compound (F11) has a low viscosity, and therefore the aromatic epoxy compound (F11) tends to lower the viscosity of the composition (X). Further, since the aromatic epoxy compound (f11) is not easily volatilized, even when the composition (X) is stored, the composition (X) is not easily changed in composition by volatilization of the aromatic epoxy compound (f 11). Therefore, the aromatic epoxy compound (f11) tends to improve the storage stability of the composition (X). In addition, since the aromatic epoxy compound (f11) has high reactivity, unreacted components are less likely to remain in the cured product, and therefore, outgassing from the cured product is less likely to occur. Further, the aromatic epoxy compound (f11) tends to increase the glass transition temperature of the cured product, and therefore tends to improve the heat resistance of the cured product.

In addition, in the case where the composition (X) is ejected by an ink jet method, the aromatic epoxy compound (f11) is less likely to generate defective droplets called satellites. Satellite droplets refer to: when a droplet is ejected by an ink jet method, the droplet is separated from an original droplet and attached to a position different from the position where the original droplet is attached in an object to be coated. When the satellite droplets are generated, the dimensional accuracy of the optical member such as a sealing material made of the composition (X) is deteriorated.

R in formula (30) is preferably a single bond or an alkylene group. In the case where n in formula (30) is 2 or 3, at least one of the plurality of R in formula (30) is preferably a single bond or an alkylene group. In these cases, the reactivity of the aromatic epoxy compound (111) tends to be high, and thus the curability of the composition (X) when the composition (X) is irradiated with ultraviolet rays tends to be high.

The aromatic epoxy compound (111) preferably contains at least one compound selected from the compounds represented by the following formulae (301) to (318), for example.

In particular, the aromatic epoxy compound (f11) preferably contains at least one component selected from the group consisting of the compounds represented by formulae (301) to (305), (312), (314), and (318). These compounds are likely to have high reactivity by bonding an epoxy group (ethylene oxide) in the compound to a benzene ring by a single bond or an alkylene group, and thus are likely to improve curability of the composition (X).

The cationically polymerizable compound (F) contains a compound (F2) having an oxyalkylene skeleton. The oxyalkylene skeleton means a linear skeleton containing one or more linear oxyalkylene units.

When the cationically polymerizable compound (F) contains the compound (F2), the compound (F2) has a low viscosity, and therefore the compound (F2) tends to lower the viscosity of the composition (X). Further, since the compound (f2) is less likely to volatilize, even when the composition (X) is stored, the composition (X) is less likely to change in composition due to volatilization of the compound (f 2). Therefore, the compound (f2) tends to improve the storage stability of the composition (X).

In addition, in the case where the composition (X) is ejected by an ink jet method, the compound (f2) is less likely to generate defective droplets called satellites. Further, the compound (f2) can be prevented from generating satellite droplets even when the velocity of the droplets discharged by the ink jet method is increased. Therefore, although the conditions for ink jet vary, the ejection speed of droplets by the ink jet method can be set to 4m/s or more without generating satellite droplets, for example. If the speed of the droplets can be increased, the trajectories of the droplets are less likely to be affected by disturbance, and therefore, the dimensional accuracy of an optical component such as a sealing material made of the composition (X) can be improved. Further, as described above, since the compound (f2) can improve the storage stability of the composition (X), the characteristics of the composition (X) that satellite droplets are not easily generated can be easily maintained even when the composition (X) is stored for a long period of time.

The oxyalkylene skeleton particularly preferably contains a structure of "-C-O-", i.e., an oxymethylene unit. In this case, satellite droplets are particularly less likely to be generated, and for example, even if the driving frequency at which the composition (X) is discharged by the ink jet method is changed, satellite droplets are less likely to be generated. Further, the compound (f2) is less volatile and tends to attain a lower viscosity, and further, the affinity (wettability) of the composition (X) for inorganic materials tends to be improved.

The number of oxyalkylene units in the oxyalkylene skeleton in the compound (f2) is preferably 1 or more and 8 or less. In this case, the compound (f2) tends to have a lower viscosity, and therefore, satellite droplets are particularly less likely to be generated, and the crosslinking density of the cured product tends to be high, and thus the glass transition temperature of the cured product tends to be particularly high. The number of oxyalkylene units is more preferably 1 to 6, still more preferably 1 to 4.

In the compound (f2), a substituent other than hydrogen may be bonded to the oxyalkylene unit in the oxyalkylene skeleton. For example, the oxymethylene unit contained in the oxyalkylene skeleton may have "-CH (CH)₃)-CH₂-O- "structure.

The proportion of the compound (F2) is preferably 10% by mass or more relative to the cationically polymerizable compound (F). In this case, the ink ejection property is good, and the wettability to the substrate is good. The proportion is preferably 70% by weight or less. In this case, the glass transition temperature of the optical member is easily increased. The proportion is more preferably 15% by mass or more and 60% by mass or less, and still more preferably 20% by mass or more and 50% by mass or less.

The compound (f2) contains a compound (f22) having an oxyalkylene group and an oxetanyl group. That is, the cationically polymerizable compound (F) contains a compound (F22) having an oxyalkylene group and an oxetanyl group. The compound (f2) may further contain a compound (f21) having an oxyalkylene skeleton and an epoxy group.

The compound (f21) contains, for example, at least one compound selected from the group consisting of the compound represented by the above formula (1b), the compound represented by the formula (4), the compound represented by the formula (5), the compound represented by the formula (6), the compound represented by the formula (7), the compound represented by the formula (8), the compound represented by the formula (13), the compound represented by the formula (14), and the like. The component that can be contained in the compound (f221) is not limited to the above-mentioned components.

The compound (f22) contains, for example, at least one compound selected from the group consisting of the compound represented by the above formula (3), the compound represented by the above formula (12), the compound represented by the above formula (16), and the compound represented by the above formula (17). The component that compound (f22) can contain is not limited to the above-mentioned components.

As described above, the cationically polymerizable compound (F) contains the epoxy compound (F1) and the compound (F22). The epoxy compound (F1) contains, for example, at least one compound having an epoxy group among the compounds that the cationically polymerizable compound (F) can contain.

The proportion of the compound (F22) to the cationically polymerizable compound (F) is preferably 10% by mass or more. In this case, the compound (f22) makes it particularly easy to reduce the viscosity of the composition (X) and improves the storage stability of the composition (X). Further, the compound (f22) can particularly easily improve the curability of the composition (X). The proportion of the compound (f22) is also preferably 90% by mass or less. In this case, the curability of the cured product can be sufficiently improved. The proportion of the compound (f22) is more preferably 10% by mass or more and 90% by mass or less, and still more preferably 20% by mass or more and 80% by mass or less.

The proportion of the epoxy compound (F1) is preferably 10% by mass or more and 90% by mass or less with respect to the total amount of the cationically polymerizable compound (F), more preferably 20% by mass or more and 80% by mass or less, and still more preferably 25% by mass or more and 75% by mass or less. In these cases, the unreacted groups in the cured product can be sufficiently reduced, and the curability of the cured product can be sufficiently improved.

The epoxy compound (f1) is preferably a compound having at least one oxirane ring which does not constitute a glycidyl ether group. In this case, the epoxy compound is particularly likely to improve the curability of the composition (X). It is more preferable that the epoxy compound contains a compound having 2 or more oxirane rings not constituting a glycidyl ether group. The epoxy compound also preferably contains a compound having no glycidyl ether group. It is particularly preferable that the epoxy compound contains a compound having 2 or more oxirane rings not constituting a glycidyl ether group and having no glycidyl ether group.

The epoxy compound (f1) is particularly preferable to contain the aromatic epoxy compound (f 11). In this case, the composition (X) tends to have particularly excellent storage stability, and when the composition (X) is ejected by an ink jet method, defective droplets called satellites are particularly unlikely to be generated. Further, even if the speed of the liquid droplets discharged by the ink jet method is increased, satellite droplets are particularly less likely to be generated. Further, even when the composition (X) is stored for a long period of time, the characteristics of the composition (X) are particularly easily maintained, in which the formation of satellite droplets is not likely to occur.

The ratio of the total of the aromatic epoxy compound (F11) and the compound (F22) to the cationically polymerizable compound (F) is preferably 55% by mass or more. In this case, the effect brought about by the combination of the aromatic epoxy compound (f11) and the compound (f22) can be obtained particularly remarkably. The proportion is more preferably 60% by mass or more, and still more preferably 70% by mass or more. The cation polymerizable compound (F) is particularly preferably one containing only the aromatic epoxy compound (F11) and the compound (F22).

The cationic curing catalyst (G) is not particularly limited as long as it generates a protonic acid or a lewis acid by being irradiated with light. The cationic curing catalyst (G) contains an ionic photoacid generator. The cationic curing catalyst (G) may further contain a nonionic photoacid generator.

The ionic photoacid generator may contain at least one of an onium salt and an organic metal complex. Examples of onium salts include aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts. Examples of the organic metal complex include iron-allene complexes, titanocene complexes, and aryl silanol-aluminum complexes. The ionic photoacid generator may contain at least one of these components.

The nonionic photoacid generator may contain at least one member selected from the group consisting of nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenol sulfonic acid esters, diazonaphthoquinones, and N-hydroxyimide phosphonic acid esters, for example.

More specific examples of the compound that the cationic curing catalyst (G) can contain include: midori Kagaku Co., Ltd, DPI series (105, 106, 109, 201, etc.), BI-105, MPI series (103, 105, 106, 109, etc.), 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, 201, 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 series (101, 1003, 100, 200, etc.), NAI series (103, 300, 1000, etc.) 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-Acetate, DTS-Acetate, Di-Boc Bisphinol A, tert-Butyl lithocholate, 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 manufactured by Union Carbide Corporation, USA;

IRGACURE250, IRGACURE 261 and IRGACURE 264 manufactured by BASF corporation;

CG-24-61 made by CIBA-GEIGYAG;

ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-151, ADEKA OPTOMER SP-170 and ADEKA OPTOMER SP-171, manufactured by ADEKA, Inc.;

DAICAT II made of Daiiol, Inc.;

UVAC1590 and UVAC1591 manufactured by Daicel Cytech Company Ltd;

CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758 and CIT-1682, all of which are available from Nippon Caoda corporation;

PI-2074, toluoyl cumyl iodonium tetrakis (pentafluorophenyl) borate manufactured by RHODIA corporation;

FFC509 manufactured by 3M;

CD-1010, CD-1011 and CD-1012, manufactured by Sartomer, USA;

CPI-100P, CPI-101A, CPI-110P, CPI-110A and CPI-210S manufactured by San-Apro; and

UVI-6992 and UVI-6976, manufactured by Dow Chemical Company. The cationic curing catalyst (G) may contain at least one compound selected from these compounds.

The cationic curing catalyst (G) preferably contains a plurality of ionic photoacid generators having different strengths of conjugate acids of anionic species from each other. In this case, among the plurality of types of ionic photoacid generators, an ionic photoacid generator having a higher conjugate acid strength can improve the reactivity of the composition (X), and therefore, the efficiency for producing an optical member from the composition (X) can be improved. When the composition (X) contains the plurality of ionic photoacid generators, the composition (X) is less likely to gel during storage of the composition (X), that is, the storage stability of the composition (X) is less likely to decrease. This is presumably because, even when the anionic species having a high conjugate acid strength are released from the ionic photoacid generator during storage of the composition (X), the anionic species having a low conjugate acid strength are easily released by an exchange reaction of an acid with another ionic photoacid generator, and therefore, the concentration of the anionic species having a high conjugate acid strength in the composition (X) is not easily increased. Further, even when the composition (X) is irradiated with ultraviolet light, the composition (X) is less likely to be cured too sharply, and therefore, deterioration in transparency due to cloudiness or the like is less likely to occur in the cured product. This is presumably because, even if an anionic species having a high conjugate acid strength is released from the ionic photoacid generator by irradiation of ultraviolet rays, an anionic species having a low conjugate acid strength is easily released by the same mechanism as in the above case, and thus an excessively vigorous reaction due to an anionic species having a high conjugate acid strength can be suppressed.

The cationic curing catalyst (G) preferably contains: a first agent (g1) comprising an ionic photoacid generator comprising an anionic species having a higher strength of a conjugated acid, and a second agent (g2) comprising an ionic photoacid generator comprising an anionic species having a lower strength of a conjugated acid.

The first agent (g1) particularly preferably comprises a conjugate acid having a strength of HSbF₆An ionic photoacid generator of an anionic species having a strength of not less than (1). In addition, the second agent (g2) particularly preferably contains HSbF having a strength ratio of conjugate acid₆The ionic photoacid generator of (1) preferably further comprises an ionic photoacid generator having an anionic species with a low strength, and further preferably comprises HPF₆An ionic photoacid generator of an anionic species having a strength of less than or equal to (1).

The first agent (g1) contains, for example, a compound selected from the group consisting of compounds having (Rf)_nPF_6-n ^-The ionic photoacid generator of (5) has (Rx)_nBX_4-n ^-The ionic photoacid generator of (1), and a compound having (Rx)_nGaX_4-n ^-And at least one ionic photoacid generator of (1). In addition, the second agent (g2) contains, for example, a compound selected from the group consisting of those having PF₆ ^-An ionic photoacid generator having BF₄ ^-The ionic photoacid generator of (5) having (Rf) SO₃ ^-And an ion having a sulfite ionAnd at least one ionic photoacid generator such as a photoacid generator.

In addition, (Rf)_nPF_6-n ^-And (Rf) SO₃ ^-Rf in (A) is a perfluoroalkyl group, (Rf)_nPF_6-n ^-N in (1) is an arbitrary number from 1 to 5. (Rf)_nPF_6-n ^-In (3), Rf has, for example, 1 to 3 carbon atoms, and when Rf is plural, Rf may be the same or different. (Rf) SO₃ ^-Rf in (2) has a carbon number of 1 to 8, for example.

(Rx)_nBX_4-n ^-And (Rx)_nGaX_4-n ^-Rx in each is a phenyl group in which a part of hydrogen atoms is substituted with a halogen atom or an electron-withdrawing substituent. The halogen atom is fluorine atom, chlorine atom or bromine atom. Examples of the electron-withdrawing substituent include a trifluoromethyl group, a nitro group, and a cyano group. (Rx)_nBX_4-n ^-And (Rx)_nGaX_4-n ^-X in each is a halogen atom, preferably a fluorine atom. (Rx)_nBX_4-n ^-And (Rx)_nGaX_4-n ^-N in each is an arbitrary number from 1 to 4. In the case where there are a plurality of Rx, Rx may be the same or different from each other. Rx is e.g. C₆F₆、(CF₃)₂C₆H₃、CF₃C₆H₄Or C₆H₃F₂And the like. (Rx)_nBX_4-n ^-Is for example (C)₆F₅)₄B^-、((CF₃)₂C₆H₃)₄B^-、(CF₃C₆H₄)₄B^-、(C₆F₅)₂BF₂ ^-、C₆F₅BF₃ ^-Or (C)₆H₃F₂)₄B^-And the like.

The cationic curing catalyst (G) contains a catalyst having PF₆ ^-The ionic photoacid generator of (2) has PF₆ ^-Ionic property ofThe amount of the photoacid generator is preferably 50% by mass or less with respect to the total amount of the cationic curing catalyst (G). PF is sometimes used₆ ^-A trace amount of hydrofluoric acid is generated, and this hydrofluoric acid may attack inorganic materials such as silicon nitride and silicon oxide, which are materials of the passivation layer. However, with PF₆ ^-When the amount of the ionic photoacid generator (2) is 50% by mass or less as described above, the risk of hydrofluoric acid attacking the inorganic material can be reduced.

The cationic curing catalyst (G) contains a compound having (Rf)_nPF_6-n ^-The ionic photoacid generator of (4) has (Rf)_nPF_6-n ^-The amount of the ionic photoacid generator(s) is preferably 75% by mass or less with respect to the total amount of the cationic curing catalyst (G). Albeit not like a PF₆ ^-In the case of (B), but sometimes (Rf)_nPF_6-n ^-Trace amounts of hydrofluoric acid are also produced. But has (Rf)_nPF_6-n ^-When the amount of the ionic photoacid generator (2) is 75% by mass or less as described above, the risk of hydrofluoric acid attacking the inorganic material can be reduced.

The cationic curing catalyst (G) further contains a catalyst having PF₆ ^-The ionic photoacid generator of (5) and the compound having (Rf)_nPF_6-n ^-In the case of both of the ionic photoacid generators of (3), the total amount of these ionic photoacid generators is preferably 80 mass% or less with respect to the total amount of the cationic curing catalyst (G).

On the other hand, has (Rx)_nBX_4-n ^-The ionic photoacid generator of (1) and a compound having (Rx)_nGaX_4-n ^-The ionic photoacid generator of (3) is preferable in that hydrofluoric acid is less likely to be generated.

The cationic species in the ionic photoacid generator contained in the first agent (g1) and the cationic species in the ionic acid generator contained in the second agent (g2) are not particularly limited, and may be, for example, at least one species selected from various aromatic oniums, more specifically, various aromatic diazonium salts, aromatic halonium salts, aromatic sulfonium salts, and the like.

When the cationic curing catalyst (G) contains the first agent (G1) and the second agent (G2), the composition (X) has good curability, and particularly, cloudiness is less likely to occur in a cured product of the composition (X), and the storage stability of the composition (X) is particularly likely to be high.

The ratio of the first agent (g1) to the total amount of the first agent (g1) and the second agent (g2) is preferably 50% by mass or more. In this case, the composition (X) may have good curability. Further, the ratio is preferably 90% by mass or less. In this case, cloudiness is particularly unlikely to occur in the cured product, and the storage stability of the composition (X) is particularly likely to be high. The proportion is more preferably 60% by mass or more and 90% by mass or less, and still more preferably 70% by mass or more and 85% by mass or less.

In the present embodiment, the strength of the conjugate acid of the compound contained in the cationic curing catalyst (G) may be the same. That is, for example, the cationic curing catalyst (G) may contain only one compound.

The proportion of the cationic curing catalyst (G) to the total amount of the resin components is preferably 1 mass% or more and 4 mass% or less. When the proportion is 1% by mass or more, the composition (X) can have particularly good cationic polymerization reactivity. In addition, by setting the ratio to 4% by mass or less, the composition (X) can have good storage stability, and by not containing an excessive amount of the cationic curing catalyst (G), the production cost can be reduced.

The composition (X) may contain a sensitizer (H). The sensitizer (H) contains, for example, either or both of 9, 10-dibutoxyanthracene and 9, 10-diethoxyanthracene. The proportion of the sensitizer (H) to the total amount of the resin components is preferably in a range of more than 0 mass% and 1 mass% or less. In this case, the sensitizer (H) does not easily interfere with the transparency of the cured product, and therefore the cured product can have good transparency. Further preferably: the amount of the sensitizer (H) is more than 0 mass% and 0.8 mass% or less with respect to the total amount of the resin components.

The composition (X) may further contain a moisture absorbent (C). When the composition (X) contains the moisture absorbent (C), the cured product can have excellent moisture absorption. The average particle diameter of the moisture absorbent (C) is preferably 200nm or less. In this case, the cured product may have high transparency even if the moisture absorbent (C) is contained. In particular, when the composition (X) is discharged by an ink jet method, if the average particle diameter of the moisture absorbent (C) is 200nm or less, there is an advantage that the composition (X) is less likely to block the nozzle. Further, when the average particle diameter of the moisture absorbent (C) is 200nm or less, the moisture absorbent (C) is less likely to impair the smoothness of the surface of the optical member produced from the composition (X). Therefore, the surface of the optical member can have good smoothness.

As described above, the solidified material can have high hygroscopicity due to the moisture absorbent (C). The moisture absorption rate 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 moisture absorption rate can be determined by the following method. A film having a thickness of 10 μm was prepared by applying the composition (X) in an argon atmosphere and then irradiating the composition with ultraviolet light. The ultraviolet irradiation conditions were: for example, the peak wavelength of ultraviolet light is 365nm, and the intensity of ultraviolet light is 3000mW/cm²And ultraviolet irradiation time 10 seconds. The film is vacuum-dried, for example, by a vacuum dryer under conditions of a heating temperature of 120 ℃ and a heating time of 3 hours. The mass of the dried film was measured. The measurement result was used as an initial mass (M)₀). Next, the film was allowed to sufficiently absorb moisture. For this purpose, the film is exposed, for example, to 85 ℃ and 85% RH for 24 hours. The mass of the film after moisture absorption was measured. The measurement result is referred to as a mass after moisture absorption (M). Can utilize (M-M)₀)/M₀X 100 (mass%) of the formula₀) And calculating the moisture absorption rate by mass (M) after moisture absorption.

The moisture absorbent (C) is preferably an inorganic particle having moisture absorption properties, and preferably contains at least one component selected from zeolite particles, silica gel particles, calcium chloride particles, and titanium oxide nanotube particles, for example. It is particularly preferable that the moisture absorbent (C) contains zeolite particles.

The zeolite particles having an average particle diameter of 200nm or less can be produced by, for example, pulverizing a general industrial zeolite. In the production of zeolite particles, zeolite may be pulverized and then crystallized by hydrothermal synthesis or the like, and in this case, the zeolite particles may have particularly high hygroscopicity. As a method for producing such nanosized zeolite particles, for example, the methods disclosed in japanese patent application laid-open nos. 2016-69266 and 2013-049602 can be used.

The zeolite particles are preferably produced using a sodium ion-containing zeolite as a raw material, and more preferably at least one selected from a type a zeolite, a type X zeolite, and a type Y zeolite among sodium ion-containing zeolites as a raw material. The zeolite particles are particularly preferably produced from 4A type zeolite among a type zeolite as a raw material. In these cases, the zeolite particles have a crystal structure suitable for adsorption of moisture.

A specific example of a method for producing zeolite particles having an average particle diameter of 200nm or less is shown. First, zeolite powder as a raw material is prepared, and the zeolite powder is physically pulverized. For example, zeolite powder is mixed with water to prepare a slurry, and the slurry is fed to a bead mill pulverizer, whereby the zeolite powder can be physically pulverized.

Next, the zeolite powder was crystallized by hydrothermal synthesis. For example, hydrothermal synthesis can be performed by heating a slurry containing physically pulverized zeolite powder in an autoclave. The hydrothermal synthesis conditions include a heating temperature of 150 to 200 ℃ and a heating time of 15 to 24 hours.

Next, the zeolite powder is dried. The drying temperature is, for example, in the range of 150 to 200 ℃, and the drying time is, for example, in the range of 2 to 3 hours. Next, the dried zeolite powder is pulverized using a mortar or the like, and then sieved, if necessary, to adjust the particle size.

Next, the zeolite powder is subjected to ion exchange treatment as necessary. In particular, when the zeolite powder is a sodium-containing zeolite 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 preparing a mixture by dispersing zeolite powder in an aqueous solution containing magnesium ions, and heating the mixture. More specifically, the ion exchange treatment is performed, for example, as follows. First, zeolite powder, magnesium chloride and water are mixed, and the resulting mixture is stirred while being heated. During this process, the following operations are preferably repeated a plurality of times at appropriate intervals: after the stirring was temporarily stopped, the supernatant of the mixture was discarded, followed by replenishing water to the mixture and then starting the stirring operation. The heating temperature in the treatment is preferably in the range of 40 to 80 ℃, 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 then dried. The drying temperature is, for example, in the range of 150 to 200 ℃, and the drying time is, for example, in the range of 2 to 3 hours. Next, the dried zeolite powder is pulverized using a mortar or the like, and then sieved, if necessary, to adjust the particle size. Thus, zeolite particles having an average particle diameter of 200nm or less can be obtained.

The zeolite powder can also be crystallized in the presence of a silicate and an alkali metal oxide. A specific example of the method for producing zeolite particles having an average particle diameter of 200nm or less in this case will be described. First, zeolite powder is prepared. The zeolite powder preferably has aM1₂O·bSiO₂·Al₂O₃cMe. 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, b is a number in the range of 20 to 80, and c is a number in the range of 0 to 1. The zeolite powder preferably contains a zeolite containing sodium ions, and more preferably contains at least one material selected from the group consisting of a-type zeolite, an X-type zeolite, and a Y-type zeolite among the zeolite containing sodium ions. The zeolite powder particularly preferably contains a 4A type zeolite among a type a zeolites. The zeolite powder is physically crushed. For example, by adding zeolite powder to a bead mill pulverizer, the zeolite powder can be physically pulverized.

Dispersing the physically pulverized zeolite powder in a solvent containing M2₂O、SiO₂And H₂O in solution to prepare a slurry. M2 is an alkali metal, preferably K or Na. M2₂O/H₂The molar ratio of O is, for example, in the range of 0.003 to 0.01，SiO₂/H₂The molar ratio of O is, for example, in the range of 0.006 to 0.025. The amount of zeolite powder is, for example, 0.5 to 10g in 100ml of the solution.

By heating the slurry with an autoclave, the zeolite powder can be crystallized. The conditions are, for example, a heating temperature of 100 to 230 ℃ and a heating time of 1 to 24 hours. Next, after the zeolite powder is washed, it is dried. Thus, zeolite particles having an average particle diameter of 200nm or less can be obtained.

The pH of the zeolite particles is preferably 7 or more and 10 or less. When the pH of the zeolite particles is 7 or more, the crystals of the zeolite particles are not easily broken, and therefore, the optical member produced from the composition (X) containing zeolite particles can have particularly high hygroscopicity. When the pH of the zeolite particles is 10 or less, the zeolite particles are less likely to inhibit the curing of the composition (X).

The pH of the zeolite particles was measured by heating a dispersion obtained by adding 0.05g of zeolite particles to 99.95g of ion-exchanged water at 90 ℃ for 24 hours and measuring the pH of the supernatant of the dispersion using a pH meter. As the pH meter, for example, a compact pH meter < LAQUAtwin > B-711 manufactured by horiba, Inc. can be used.

In order to set the pH of the zeolite particles to 7 or more and 10 or less, the zeolite particles preferably contain FAU Y-type zeolite having protons as counter cations.

In the process of producing zeolite particles, when hydrothermal synthesis of zeolite is performed, treatment for adjusting pH may be performed. The treatment for adjusting the pH may be performed, for example, before heating the slurry containing the zeolite powder prepared for hydrothermal synthesis, during heating of the slurry, or after heating of the slurry. The pH is adjusted, for example, by adding an acid to the slurry. The acid contains at least one component selected from 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 moisture absorbent (C) is preferably 10nm or more and 200nm or less. When the average particle diameter is 200nm or less, the cured product can have particularly high transparency. When the average particle diameter is 10nm or more, good moisture absorption of the moisture absorbent (C) can be maintained. The average particle diameter is a cumulative 50% diameter (D50) which is a median particle diameter calculated from the measurement results by the dynamic light scattering method. As the measurement device, Nanotrac Wave series by microtrac bel corp.

The average particle diameter of the moisture absorbent (C) is more preferably 150nm or less, and even more preferably 100nm or less, and particularly preferably 70nm or less. The average particle diameter of the moisture absorbent (C) is preferably 20nm or more, and more preferably 50nm or more. In this case, the cured product can have particularly good transparency and moisture absorption.

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

The proportion of the moisture absorbent (C) to the total amount of the composition (X) is preferably 1 mass% or more and 20 mass% or less. When the proportion of the moisture absorbent (C) is 1% by mass or more, the cured product can have particularly high moisture absorption. When the proportion of the moisture absorbent (C) is 20% by mass or less, the viscosity of the composition (X) can be particularly reduced, and the composition (X) may have a sufficiently low viscosity to be ejected by an ink jet method. The proportion of the moisture absorbent (C) is more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The proportion of the moisture absorbent (C) is more preferably 15% by mass or less, and particularly preferably 13% by mass or less.

The composition (X) may further contain an inorganic filler other than the moisture absorbent (C). In particular, the composition (X) preferably contains nano-sized high refractive index particles. Examples of the high refractive index particles include zirconia particles. When the composition (X) contains the high refractive index particles, the refractive index of the cured product can be increased while maintaining good transparency of the cured product. Therefore, when the cured product is applied to an optical member such as the sealing material 5 in the light-emitting device 1, the extraction efficiency of light emitted to the outside through the optical member can be improved. The average particle diameter of the high refractive index particles is preferably in the range of 5 to 30nm, and more preferably in the range of 10 to 20 nm.

The proportion of the high refractive index particles in the composition (X) may be suitably designed so that the cured product has a desired refractive index. In particular, it is preferable that the high refractive index particles are contained in the composition (X) so that the refractive index of the cured product is in the range of 1.45 or more and less than 1.55. In this case, the light extraction efficiency of the light-emitting device 1 is particularly improved.

When the composition (X) contains the moisture absorbent (C), the composition (X) may further contain a dispersant (D). The dispersant (D) is a surfactant that can be adsorbed to the moisture absorbent (C). The dispersant (D) has, for example, an adsorption group (also referred to as an anchor) that can be adsorbed to the particles of the moisture absorbent (C) and a tail portion of a molecular skeleton in a chain or comb shape that is attached to the particles of the moisture absorbent (C) through the adsorption group. The dispersant (D) contains, for example, at least one component selected from an acrylic dispersant having an acrylic molecular chain as a tail, a urethane dispersant having a urethane molecular chain as a tail, and a polyester dispersant having a polyester molecular chain as a tail.

When the composition (X) contains the dispersant (D), the moisture absorbent (C) can be favorably dispersed in the composition (X) and in the cured product. Therefore, even if the cured product and the optical member contain the moisture absorbent (C), the transparency of the cured product and the optical member is not easily lowered by the moisture absorbent (C). The dispersant (D) can effectively suppress aggregation of the moisture absorbent (C) during storage of the composition (X). Therefore, the storage stability of the composition (X) is not easily lowered by the moisture absorbent (C).

Further, the adhesion between the cured product and silicon nitride and silicon oxide is not easily lowered by the dispersant (D). This is presumably because, as described above, the dispersant (D) is likely to adsorb to the moisture absorbent (C), and thus the dispersant (D) is less likely to affect the interface between the cured product and the silicon nitride and silicon oxide. Therefore, the optical member can have high adhesion to a glass substrate. In addition, silicon nitride and silicon oxide are sometimes used as materials of the passivation layer 6 in the light-emitting device 1. Therefore, in the case where the passivation layer 6 is made of silicon nitride or silicon oxide, the optical member such as the sealing material 5 can have high adhesion to the passivation layer 6.

The boiling point of the dispersant (D) is preferably 200 ℃ or higher. In this case, the dispersant (D) is less likely to volatilize from the composition (X), and therefore the storage stability of the composition (X) is further improved.

The dispersant (D) preferably has either or both of a basic polar functional group and an acidic polar functional group as an adsorption group. In this case, the moisture absorbent (C) can be particularly well dispersed in the composition (X) and the cured product. This is presumably because the dispersant (D) has either or both of a basic polar functional group and an acidic polar functional group, and thus is easily adsorbed to the moisture absorbent (C), and the effect of dispersing the moisture absorbent (C) is remarkably exhibited.

The dispersant (D) may contain a polymer. The weight average molecular weight of the polymer is, for example, 1000 or more. The polymer contains at least one component selected from the group consisting of a hydroxyl group-containing carboxylic acid ester, a salt of a long-chain polyaminoamide with a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long-chain polyaminoamide with a polar acid ester, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyacrylate, a polyether ester type anionic activator, a salt of a naphthalenesulfonic acid-formaldehyde condensate, a polyoxyethylene alkyl phosphate, a polyoxyethylene nonylphenyl ether, a polyester polyamine, and stearylamine acetate. When the dispersant (D) contains a polymer, the steric hindrance effect generated when the polymer adsorbs to the particles of the moisture absorbent (C) is improved, and thereby the dispersibility of the moisture absorbent (C) can be improved.

The dispersant (D) may contain, for example, either one or both of the dispersant (F1) having a basic polar functional group and the dispersant (F2) having an acidic polar functional group.

The basic polar functional group in the dispersant (F1) having a basic polar functional group includes, for example, at least one group selected from an amino group, an imino group, an amide group, an imide group, and a nitrogen-containing heterocyclic group. When the dispersant (F1) has a basic polar functional group, the dispersant (F1) is easily adsorbed to the moisture absorbent (C), and therefore, the dispersibility of the moisture absorbent (C) can be improved. The basic polar functional group preferably contains an amino group, because the adsorption capacity of the dispersant (F1) to the moisture absorbent (C) can be particularly improved, the dispersibility of the moisture absorbent (C) can be particularly improved, and the viscosity of the composition (X) can be particularly reduced.

The dispersant (F1) having a basic polar functional group includes, for example, trade names: solsperse 24000 (amine value: 41.6mgKOH/g), trade name: solsperse 32000 (amine number: 31.2mgKOH/g), trade name: solsperse 39000 (amine number: 25.7mgKOH/g), trade name: solsperse J100, trade name: solsperse series manufactured by Lubrizol Corporation of Japan, such as Solsperse J200; trade name: DISPERBYK-108, DISPERBYK-2013, DISPERBYK-180, DISPERBYK-106, DISPERBYK-162 (amine number: 13mgKOH/g), trade name: DISPERBYK-163 (amine value: 10mgKOH/g), trade name: DISPERBYK-168 (amine number: 11mgKOH/g), trade name: DISPERBYK-2050 (amine value: 30.7mgKOH/g), trade name: DISPERBYK series manufactured by BYK-CHEMIE JAPAN, such as DISPERBYK-2150 (amine number: 56.7 mgKOH/g); trade name: BYKJET-9151 (amine number: 17.2mgKOH/g), trade name: BYKJET series manufactured by BYK-CHEMIE JAPAN K.K., BYKJET-9152 (amine value: 27.3 mgKOH/g); and trade name: AJISPER PB821 (amine value: 11.2mgKOH/g), trade name: AJISPER PB822 (amine value: 18.2mgKOH/g), trade name: AJISPER series manufactured by Inc., Ajinomoto Fine-Technio Co., Inc., such as AJISPER PB881 (amine value: 17.4 mgKOH/g).

The amine value of the dispersant (F1) is preferably not less than 10mgKOH/g, more preferably not less than 10mgKOH/g and not more than 30mgKOH/g, and still more preferably not less than 15mgKOH/g and not more than 30 mgKOH/g. In addition, the dispersant (F1) preferably has no phosphoric acid group. When the dispersant (F1) has a phosphate group, the acid value derived from the phosphate group is preferably equal to or less than the amine value. In this case, the dispersant (F1) can disperse the moisture absorbent (C) particularly well, can improve the storage stability of the composition (X), can improve the transparency of the cured product, and can improve the adhesion between the cured product and silicon nitride and silicon oxide. Among the components that can be contained in the dispersant (F1), examples of dispersants having an amino group and no phosphoric acid group include DISPERBYK-108 manufactured by BYK-CHEMIE. Examples of the dispersant having an amino group and a phosphoric acid group and having an acid value derived from the phosphoric acid group of not more than an amine value include DISPERBYK-2013 manufactured by BYK-CHEMIE and DISPERBYK-180 manufactured by BYK-CHEMIE.

The acidic polar functional group in the dispersant (F2) having an acidic polar functional group is, for example, a carboxyl group. The dispersant (F2) may, for example, be DISPERBYK-P105 manufactured by BYK-CHEMIE.

The amount of the dispersant (D) is preferably 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the moisture absorbent (C). When the amount of the dispersant (D) is 5 parts by mass or more, the advantages of the dispersant (D) can be particularly exerted. When the amount of the dispersant (D) is 60 parts by mass or less, the adhesion between the cured product and silicon nitride and silicon oxide can be further improved. The amount of the dispersant (D) is more preferably 15 parts by mass or more. The amount of the dispersant (D) is more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less.

The composition (X) preferably contains no solvent or contains a solvent in an amount of 1% by mass or less. In this case, it is not necessary to evaporate the solvent by drying the composition (X) when preparing a cured product from the composition (X). Further, the storage stability of the composition (X) is further improved. The content of the solvent is more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. It is particularly preferable that the composition (X) contains no solvent or only an inevitably mixed solvent.

The composition (X) can be prepared by mixing the above components. Preferably, the composition (X) is in liquid form at 25 ℃.

3. Method for producing sealing material and method for producing light-emitting device

A method for producing the sealing material 5 using the composition (X) and a method for producing the light-emitting device 1 will be described.

In the present embodiment, it is preferable that: the sealing material 5 is produced by forming a coating film on an object by discharging the composition (X) by an ink jet method, irradiating the coating film with ultraviolet rays, and then heating the coating film. In the present embodiment, the composition (X) is ejected from the inkjet head, whereby a coating film can be formed by being applied to an object.

When the composition (X) is ejected by an ink jet method and applied to an object, when the composition (X) has a sufficiently low viscosity at room temperature, for example, when the viscosity at 25 ℃ is 30mPa · s or less, particularly 15mPa · s or less, the composition (X) can be ejected by an ink jet method and applied to the object without heating the composition (X).

When the composition (X) has a property of being heated to lower the viscosity, the composition (X) may be heated and then ejected by an ink jet method to be applied to an object. When the viscosity of the composition (X) is 30mPa · s or less, particularly 15mPa · s or less at 40 ℃, the viscosity of the composition (X) can be reduced by slightly heating the composition (X), and the reduced viscosity composition (X) can be ejected by an ink jet method. The heating temperature of the composition (X) is, for example, 20 ℃ or more and 50 ℃ or less.

When the coating film obtained by molding the composition (X) is cured by irradiating light, the light irradiated to the coating film is, for example, ultraviolet light. The ultraviolet ray is a light ray having a wavelength of 200nm to 410 nm. The wavelength of light irradiated to the coating film is preferably in the range of 350nm to 410nm, more preferably 385nm to 405 nm. As a typical example of the light to be irradiated to the coating film, a light having a wavelength of 395nm is cited. The wavelength of light to be irradiated to the coating film is not limited to the above description as long as it is a wavelength that can cure the coating film.

The irradiation intensity of light with which the coating film is irradiated is preferably 20mW/m²Above 20W/cm²The following. The irradiation intensity of light is not limited to the above description as long as it is an intensity that can cure the coating film.

The shape of the portion to which light is irradiated when the coating film is irradiated may be a region type having a certain area or a line type. In the case of the line type, the entire coating film can be irradiated with light by moving the coating film with respect to the light source or by moving the light source with respect to the coating film. In this case, the time for irradiating the coating film with light can be easily adjusted, and the cumulative light amount can be easily adjusted by adjusting the time.

The heating temperature when the cured coating film is further heated is preferably 90 ℃ or higher. In this case, the linear expansion coefficient of the sealing material 5 is easily reduced by further curing the coating film, and thus the linear expansion coefficient of the sealing material 5 is easily made to be 100 ppm/DEG C or more and 130 ppm/DEG C or less. The heating temperature is preferably 150 ℃ or lower. In this case, the organic EL element or the like as the light emitting element 4 may be less likely to be deteriorated by heat.

More specifically, for example, the support substrate 2 is first prepared. Partition walls are formed on one surface of the support substrate 2 by photolithography using, for example, a photosensitive resin material. Next, a plurality of organic EL elements or the like as the light emitting elements 4 are provided on one surface of the supporting substrate 2. The organic EL element or the like as the light-emitting element 4 can be produced by an appropriate method such as a vapor deposition method or a coating method. In particular, it is preferable to fabricate an organic EL element or the like as the light-emitting element 4 by an application method such as an ink-jet method, as in the case of the composition (X). 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 formed by an evaporation method such as a plasma CVD method, for example.

Next, the composition (X) is discharged on the first passivation layer 61 by, for example, an ink jet method to form a coating film. If the ink jet method is applied to both formation of the organic EL element or the like as the light emitting element 4 and application of the composition (X), the manufacturing efficiency of the light emitting device 1 can be particularly improved. Next, the coating film is irradiated with ultraviolet rays and cured to produce the sealing material 5. The thickness of the sealing material 5 is, for example, 2 μm or more and 50 μm or less.

The thickness of the sealing material 5 is preferably 2 μm or more and 30 μm or less, and more preferably 2 μm or more and 15 μm or less. As described above, in the present embodiment, since it is easy to form small droplets of the composition (X) at high density by the ink jet method, it is easy to realize the thin sealing material 5 having a thickness of 2 μm or more and 15 μm or less. When the sealing member 5 is thinned as described above, the sealing member 5 is less likely to generate tensile stress and compressive stress in the light-emitting device 1. Therefore, the flexible light emitting device 1 is easily realized.

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

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 superimposed 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 to 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 to produce the second sealing material 52.

As described above, the sealing material 5 including the cured product of the composition (X) can have good heat resistance. Therefore, when the passivation layer 6 (second passivation layer 62) is formed by a vapor deposition method such as a plasma CVD method while being superimposed on the sealing material 5, the sealing material 5 is less likely to be deteriorated even if the temperature of the sealing material 5 increases. In addition, even if the temperature of the light-emitting device 1 rises during use of the light-emitting device 1, the sealing material 5 is less likely to deteriorate. As described above, the light-emitting element 4 is, for example, an organic EL element, but the light-emitting element 4 may be a micro light-emitting diode or the like.

The optical member is not limited to the sealing material 5 for the light emitting element 4. The composition (X) can be used for producing various optical parts. For example, the optical component may be a colored photoresist (force ラ - レジスト). In this case, for example, a phosphor is contained in the composition (X), and a color resist in a color filter is produced from the composition (X). In this case, the color resist in the color filter can be easily manufactured with high density and high accuracy. The color filter may be provided in a display device such as an organic EL display, a micro LED display, or the like.

Examples

Specific examples of the present application will be described below. However, the present application is not limited to the following examples.

1. Preparation of the composition

The compositions of examples and comparative examples were prepared by mixing the components shown in the following table.

The components shown in the table are described in detail below. The viscosity of the following components was measured at 25 ℃ and a shear rate of 1000s using a rheometer (model DHR-2 manufactured by Anton Paar Japan, Ltd.)^-1The value measured under the conditions of (1).

(1) Cationically polymerizable compound

■ Phenylmethyloxirane: a boiling point of 235 ℃ and a viscosity of 6 mPas at 25 ℃.

■ 4-fluorophenyl oxirane: a boiling point of 220 ℃ and a viscosity of 8 mPas at 25 ℃.

■ styrene oxide: a boiling point of 200 ℃ and a viscosity of 4 mPas at 25 ℃.

■ BATG: a polyfunctional aromatic epoxy compound, SHOWA DENKO, model BATG, having a boiling point of 300 ℃ or higher and a viscosity of 10000 mPas at 25 ℃.

■ 2 boiling point of the 2-glycidyl-phenyl oxirane is 300 ℃ or higher, and viscosity at 25 ℃ is 17 mPaS.

■ OXT-221: a compound represented by the formula (3) and having a boiling point of 275 ℃, a surface tension of 33mN/cm and a viscosity of 11 mPas, which is manufactured by Toyo Synthesis.

■ OXT-212: a compound represented by the formula (12) and having a boiling point of 277 ℃, a surface tension of 35mN/cm and a viscosity of 4 mPas, which is manufactured by Toyo Synthesis.

■ AL-EOX: a compound represented by the formula (16) and synthesized in the product of four-day market, model AL-EOX, boiling point 200 ℃, surface tension 27mN/cm, and viscosity 2 mPas.

■ CELLOXIDE 8010: a compound represented by the formula (1a) and made of cellosolve, having a boiling point of 265 ℃, a surface tension of 43mN/cm and a viscosity of 60 mPas at 25 ℃.

■ CELLOXIDE 8010 (heat treated article): the treated product obtained by subjecting CELLOXIDE 8010 to heat treatment at 100 ℃ for 30 minutes in an atmospheric atmosphere has a boiling point of 265 ℃, a surface tension of 43mN/cm and a viscosity of 60 mPas at 25 ℃.

■ 1, 2, 7, 8-octane diepoxide: a boiling point of 230 ℃, a surface tension of 37mN/cm, and a viscosity of 3 mPas at 25 ℃.

(2) Cationic curing catalysts

■ CPI-310B: triaryl sulfonium salt type photoacid generator manufactured by San-Apro corporation, anion seed B (C)₆F₅)₄ ^-Model CPI-310B.

CPI-210S: triaryl sulfonium salt type photoacid generator manufactured by San-Apro corporation, anion seed (Rf)_nPF_6-n ^-Model CPI-310B.

IK-1: diaryl iodonium salt type photoacid generator manufactured by San-Apro corporation, anion seed (Rf)_nPF_6-nType IK-1.

CPI-110P: triaryl sulfonium salt type photoacid generator manufactured by San-Apro corporation, anion seed PF₆ ^-Model CPI-110P.

IRGACURE 250: diaryl iodonium salt type photoacid generator manufactured by BASF corporation, anion seed PF₆ ^-Model IRGACURE 250.

(3) Sensitizers

UVS 1331: 9, model UVS1331 made by Kawasaki Kazaki Kaisha.

DETX-s: 2, 4-Diethylthioxanthen-9-one, manufactured by Nippon Chemicals, Inc., model DETX-s.

(4) Additive agent

BYK 333: a leveling agent, BYK-CHEMIE company, and polyether modified polydimethylsiloxane as an active ingredient.

2. Evaluation test

The following evaluation tests were carried out for examples and comparative examples. The results are shown in the table.

2.1. Curing Properties

The composition was applied to a glass slide, and then the composition was irradiated with an LED-UV irradiator manufactured by CCS corporation at the peak wavelength395nm and output power of 1W/cm²Under the condition of (1) to reach 1.5J/cm²By irradiating the light with the light of (1), the light is cured. The atmosphere was set to a dry atmosphere containing oxygen. Thus, a film having a thickness of 10 μm was produced. The tester touches the surface of the film with a finger to determine the presence or absence of stickiness. As a result, the case where the test person did not feel sticky was evaluated as "a", the case where the test person did not adhere to the finger but felt sticky was evaluated as "B", and the case where the test person felt sticky and a part of the film adhered to the finger was evaluated as "C".

2.2. Transmittance of light

The composition was coated on a smooth table, and then an LED-UV irradiator manufactured by CCS was used in a dry atmosphere, and the peak wavelength was 395nm, and the output was 1W/cm²Cumulative light quantity of 1.5J/cm²By irradiating it with light under the conditions of (1), thereby photocuring it. Thus, a film having a thickness of 15 μm was produced. The transmittance of the film was measured for light having a wavelength of 430 nm. A spectrophotometer (U-4100, Hitachi, Ltd.) was used for the measurement. In the case of comparative example 3, the composition could not be sufficiently photo-cured, and thus, evaluation was impossible.

2.3. Viscosity of the oil

The shear rate was 1000 seconds at 25 ℃ using a rheometer (model DHR-2 manufactured by Anton Paar Japan K.K.)^-1The viscosity of the composition was measured under the conditions of (1).

2.4. Surface tension

The surface tension of the composition was measured by the Wilhelmy method. For the measurement, a surface tension meter (manufactured by Kyodo interfacial Co., Ltd.; type: CBVP-Z) was used, and the measurement was carried out at a measurement temperature of 25 ℃ using a platinum plate.

2.5. Storage stability

The composition was left at a temperature of 60 ℃ for 2 weeks. The viscosity of the composition before and after the test was measured by a rheometer, and the case where the viscosity change rate was less than 10% was evaluated as "a", the case where the viscosity change rate was 10% or more and gelation of the composition was not observed after the test was evaluated as "B", and the case where gelation of the composition was observed after the test was evaluated as "C".

2.6. Ink-jet property

2.6.1. With or without satellite drip

The composition was put into an ink cartridge of an ink jet printer (manufactured by RICOH, "MH 2420"), and after confirming that the resin composition in the ink cartridge could be ejected from the nozzle of the ink jet printer, the resin composition was ejected from the nozzle to print test patterns continuously. A high-speed camera photographs the droplet discharged from the nozzle, and it is checked whether the droplet is separated and a satellite is generated. As a result, the case where the droplet was not separated was evaluated as "a"; a case where the satellite droplet was separated from the original droplet and integrated with the original droplet to become one droplet again was evaluated as "B"; the satellite droplets were separated from the original droplets and were not integrated, and evaluated as "C".

2.6.2. Ink jet speed (initial)

In the test of "2.6.1. presence or absence of satellite", the ejection speed of the droplet was changed to confirm that: the maximum ejection speed in the case where the droplet is not separated or the satellite is separated from the original droplet and then the satellite and the original droplet are integrated and become one droplet again.

2.6.3. Ink jet speed (after storage)

The composition was stored at 60 ℃ for 2 weeks. Next, the same test as the above "2.6.2. ink ejection speed (initial)" was performed.

2.6.4. Maintenance rate

The percentage of the result of the "2.6.3 ink ejection speed (after storage)" to the result of the "2.6.2 ink ejection speed (initial)" was calculated as a maintenance ratio.

2.7. Barrier film suitability

A500 nm thick SiN film was formed on a glass slide, and a 10 μm thick SiN film was formed on the SiN film under the same conditions as in the case of "2.1. curability". The film was stored in a constant temperature and humidity chamber at 85 ℃ and 85% RH for 168 hours, and then the surface of the film was observed by SEM. As a result, the case where no change was found in the film was evaluated as "a"; the case where swelling or surface roughness was generated on the film but no crack was found was evaluated as "B"; the case where the breakage occurred on the film was evaluated as "C".

2.8. Glass transition temperature

A coating film was formed by coating the composition, and the coating film had a peak wavelength of 395nm and an output of 1W/cm using an LED-UV irradiator manufactured by CCS²The cumulative light quantity was 10J/cm²The coating film was irradiated with light under the conditions described above, whereby a film having a thickness of 200 μm was produced. The glass transition temperature of a sample cut out from the film was measured using a viscoelasticity measuring apparatus (model DMA7100 manufactured by Hitachi High-Tech Science Corporation). In the case of comparative example 3, the coating film could not be sufficiently cured, and thus, evaluation was impossible.

2.9. Evaluation of outgassing

The outgas when a cured product of the composition was heated was measured by the following method. A headspace vial was charged with 100mg of the composition, and the composition was irradiated with an LED-UV irradiator manufactured by CCS at a peak wavelength of 395nm and a concentration of about 100mW/cm²The composition was cured by light irradiation under the conditions of (1), then the vial was sealed and heated at 80 ℃ for 30 minutes, and then the gas phase portion in the vial was introduced into a gas chromatograph for analysis. From the results, the mass ratio of the generated gas to the composition was determined. In order to prevent the occurrence of outgas, the result is preferably 200ppm or less, more preferably 100ppm or less, still more preferably 50ppm or less, and particularly preferably 25ppm or less.

[ Table 1]

[ Table 2]

[ Table 3]

Claims

1. An ultraviolet-curable resin composition for producing an optical component through which light emitted from a light source is transmitted,

the ultraviolet-curable resin composition contains a cationically polymerizable compound (F) and a cationic curing catalyst (G),

the cationically polymerizable compound (F) contains an epoxy compound (F1) and a compound (F22) having an oxyalkylene group and an oxetanyl group.

2. The ultraviolet-curable resin composition according to claim 1,

the proportion of the compound (F22) to the cationically polymerizable compound (F) is 10% by mass or more.

3. The ultraviolet-curable resin composition according to claim 1 or 2,

the epoxy compound (f1) contains a compound (f11) represented by the following formula (30),

in the formula (30), X is at least one selected from the group consisting of halogen, H, a hydrocarbon group and an alkylene glycol group, and when a plurality of X are present in one molecule, X may be the same or different from each other,

r is a single bond or a divalent organic group,

n is any number from 1 to 3.

4. The ultraviolet-curable resin composition according to claim 3,

the proportion of the compound (F11) to the entire cationically polymerizable compound (F) is 10% by mass or more and 90% by mass or less.

5. The ultraviolet-curable resin composition according to claim 3 or 4,

the total amount of the compound (F11) and the compound (F22) is 55% by mass or more relative to the cationically polymerizable compound (F).

6. The ultraviolet-curable resin composition according to any one of claims 1 to 5,

the cationic curing catalyst (G) contains a plurality of ionic photoacid generators having different strengths of conjugate acids of anionic species from each other.

7. The ultraviolet-curable resin composition according to claim 6,

the cationic curing catalyst (G) contains a first agent (G1) and a second agent (G2), the first agent (G1) comprising a compound selected from the group consisting of (Rf)_nPF_6-n ^-The ionic photoacid generator of (1) and a compound having (Rx)_nBX_4-n ^-At least one ionic photoacid generator of (a), the second agent (g2) comprising a compound selected from the group consisting of compounds having a PF₆ ^-An ionic photoacid generator having BF₄ ^-The ionic photoacid generator of (5) having (Rf) SO₃ ^-At least one ionic photoacid generator selected from the ionic photoacid generators of (1) and the ionic photoacid generators having sulfite ions,

said Rf are all perfluoroalkyl groups, said (Rf)_nPF_6-n ^-Wherein n is an arbitrary number of 1 to 5, Rx is a phenyl group in which a hydrogen atom is partially substituted with a halogen atom or an electron-withdrawing substituent, X is a halogen atom, and (Rx)_nBX_4-n ^-N in (1) to (4).

8. The ultraviolet-curable resin composition according to claim 7,

the proportion of the first agent (g1) to the total amount of the first agent (g1) and the second agent (g2) is 50% by mass or more.

9. The ultraviolet-curable resin composition according to any one of claims 1 to 8, which contains no solvent or contains 1% by mass or less of a solvent.

10. The ultraviolet-curable resin composition according to any one of claims 1 to 9, having a viscosity of 8 to 40 mPas at 25 ℃.

11. The ultraviolet-curable resin composition according to any one of claims 1 to 10, having a viscosity of 8 to 40 mPas at 40 ℃.

12. The ultraviolet-curable resin composition according to any one of claims 1 to 11, which can be ejected by an ink jet method.

13. A method for manufacturing a light-emitting device including a light source and an optical member for transmitting light emitted from the light source, the method comprising:

an optical component is produced by ejecting the ultraviolet-curable resin composition according to any one of claims 1 to 12 to a position through which light emitted from the light source passes by an ink jet method to produce a coating film, and irradiating the coating film with ultraviolet light.

14. A light-emitting device comprising a light source and an optical member for transmitting light emitted from the light source, wherein the optical member comprises a cured product of the ultraviolet-curable resin composition according to any one of claims 1 to 12.