JP7170245B2 - UV-Curable Resin Composition, Method for Manufacturing Light-Emitting Device, and Light-Emitting Device - Google Patents

Description

TECHNICAL FIELD The present invention relates to an ultraviolet curable resin composition, a method for manufacturing a light emitting device, and a light emitting device, and more specifically, an ultraviolet curable resin composition containing a photopolymerizable compound and a photopolymerization initiator, and the ultraviolet curable resin composition. The present invention relates to a method for manufacturing a light-emitting device using a material, and a light-emitting device provided with an optical component made of a cured product of an ultraviolet-curable resin composition.

Patent Document 1 contains a polymerizable compound and a polymerization initiator, has a viscosity of 5 to 50 mPa s at 25 ° C., a surface tension of 15 to 35 mN / m at 25 ° C., and a cured product of 40 to A sealing agent for an organic EL display element is disclosed, which has a linear expansion coefficient of 50 to 140 ppm at 50°C.

WO2018/074508

As described in Patent Document 1, when the linear expansion coefficient of a cured product obtained by irradiating a sealant for an organic EL display element with ultraviolet rays is set to 50 to 140 ppm, the crosslink density of the cured product is reduced by irradiation with ultraviolet rays. should be high enough. Therefore, the sealant for organic EL display elements is required to have high reactivity.

However, if the reactivity of the sealant for organic EL display elements is too high, the reaction of the sealant for organic EL display elements may progress during storage, causing an increase in viscosity. In that case, the moldability of the sealant for organic EL display elements deteriorates.

An object of the present invention is to provide an ultraviolet curable resin composition having excellent storage stability, a method for manufacturing a light emitting device using this ultraviolet curable resin composition, and a light emitting device comprising an optical component made from this ultraviolet curable resin composition. It is to provide the equipment.

An ultraviolet curable resin composition according to one aspect of the present invention contains a photopolymerizable compound and a photopolymerization initiator. Obtained by irradiating a coating film having a thickness of 10 μm made from an ultraviolet curable resin composition with light having a peak wavelength of 395 nm under the conditions of an integrated light amount of 800 mJ/cm ² or more and 4000 mJ/cm ² or less in an atmospheric atmosphere at normal temperature and pressure. The DSC curve of the photocured product obtained has a peak with a peak top within the range of 30°C to 260°C.

A method for manufacturing a light-emitting device according to an aspect of the present invention is a method for manufacturing a light-emitting device including a light source and an optical component that transmits light emitted by the light source. The manufacturing method includes molding the ultraviolet-curable resin composition by an inkjet method, and then curing the ultraviolet-curable resin composition by irradiating ultraviolet rays to produce an optical component.

A light-emitting device according to an aspect of the present invention includes a light source and an optical component that transmits light emitted by the light source, and the optical component is made of a cured product of the ultraviolet-curable resin composition.

According to one aspect of the present invention, an ultraviolet curable resin composition having excellent storage stability, a method for manufacturing a light-emitting device using this ultraviolet curable resin composition, and an optical component made from this ultraviolet curable resin composition can be provided.

1 is a schematic cross-sectional view showing a first example of a light emitting device according to one embodiment of the present invention; FIG. FIG. 4 is a schematic cross-sectional view showing a second example of a light emitting device according to one embodiment of the present invention;

An embodiment of the present invention will be described below.

The ultraviolet curable resin composition (hereinafter also referred to as composition (X)) according to this embodiment contains a photopolymerizable compound and a photopolymerization initiator. Under normal temperature and normal pressure (25°C, 1 atm), a 10 μm thick coating film prepared from composition (X) is irradiated with light having a peak wavelength of 395 nm at an integrated light intensity of 800 mJ/cm ² or more and 4000 mJ/cm ² or less. The DSC curve of the cured product obtained by irradiation under the conditions (hereinafter referred to as photocured product) has a peak with a peak top within the range of 30°C to 260°C. In this embodiment, the DSC curve of the photocured product should have the above-described peak when the integrated amount of light is at least one value within the above-described range of 800 mJ/cm ² or more and 4000 mJ/cm ² or less. That is, even if the DSC curve does not have the above-mentioned peak when the integrated light amount is a certain value within the above-mentioned range of 800 mJ/cm ² or more and 4000 mJ/cm ² or less, the integrated light amount is different from the above-mentioned range. The DSC curve should have the aforementioned peak when the value of It is particularly preferable if the DSC curve has the above-described peak regardless of whether the integrated amount of light is any value within the above-described range. It is also preferred that the DSC curve of the photocured product obtained by irradiating the coating film with light having a peak wavelength of 395 nm under the conditions of an irradiation intensity of 3 W/cm ² and an integrated light amount of 1600 mJ/cm ² has the above peak.

Composition (X) is used to produce an optical component that transmits light emitted by a light source. An optical component is a component for transmitting light emitted by a light source such as a light emitting element in a device having an optical system (for example, the light emitting device 1). The optical component is for example the encapsulant 5 for the light emitting element. The optical member is, for example, a thin film, more specifically, a film having a thickness of 2 μm or more and 50 μm or less, or 2 μm or more and 30 μm or less.

According to this embodiment, the curing reaction of the cured product can be further advanced by heating the cured product obtained by irradiating the composition (X) with light. For this reason, the composition (X) can be sufficiently cured by heating after irradiating the composition (X) with light while reducing the photoreactivity of the composition (X). Therefore, the reaction of composition (X) is less likely to proceed during storage of composition (X), and the storage stability of composition (X) can be improved.

In addition, the DSC curve of the photocured product is measured under the conditions shown in Examples described later.

The calorific value calculated from the peak of the DSC curve is preferably 1 J/g or more and 400 J/g or less. In this case, it is particularly easy to obtain the storage stability of the composition (X), and it is particularly easy to cure the composition (X) when the composition (X) is heated after being irradiated with light. The calorific value is more preferably 100 J/g or more and 400 J/g or less.

The coefficient of linear expansion of the primary cured product is preferably 150 ppm/°C or more and 250 ppm/°C or less. The primary cured product is a coating film having a thickness of 100 μm prepared from the composition (X) under an atmospheric atmosphere at normal temperature and pressure, and is irradiated with light having a peak wavelength of 395 nm at an integrated light amount of 1500 mJ/cm ² or more and 7500 mJ/cm ² or less. It is a cured product obtained by irradiation under the following conditions. In the present embodiment, the primary cured product preferably has the above-described linear expansion coefficient when the integrated light amount is at least one value within the above-described range of 1500 mJ/cm ² or more and 7500 mJ/cm ² or less. That is, even if the primary cured product does not have the above linear expansion coefficient when the integrated light amount is a certain value within the above-mentioned range of 1500 mJ/cm ² or more and 7500 mJ/cm ² or less, the integrated light amount is within the above-mentioned range. It is preferable if the primary cured product has the aforementioned coefficient of linear expansion when it is another value within. It is particularly preferable if the primary cured product has the above-described coefficient of linear expansion even if the integrated amount of light is any value within the above-described range. It is also preferred that the primary cured product obtained by irradiating the coating film with light having a peak wavelength of 395 nm under the conditions of an irradiation intensity of 3 W/cm ² and an integrated light quantity of 3000 mJ/cm ² has the aforementioned coefficient of linear expansion.

In the present embodiment, when the cured product obtained by irradiating the composition (X) with light is further heated, the curing reaction proceeds in the cured product, thereby increasing the crosslink density and decreasing the coefficient of linear expansion. do. If the linear expansion coefficient of the primary cured product is 150 ppm/° C. or more and 250 ppm/° C. or less as described above, the linear expansion coefficient of the cured product after heating can be sufficiently reduced. Therefore, even if the light-emitting device 1 including the optical component such as the encapsulant 5 made from the composition (X) is subjected to a thermal load and the optical component thermally expands and contracts, the internal stress in the optical component increases. It is possible to make it difficult for cracks to occur due to

The ratio of the coefficient of linear expansion of the primary cured product to the linear expansion coefficient of the secondary cured product is preferably 1.2 or more. The secondary cured product is a cured product obtained by heating the primary cured product at 100° C. for 5 minutes. In this case, the linear expansion coefficient of the cured product can be sufficiently lowered by further heating the cured product obtained by irradiating the composition (X) with light. As a result, cracks in the optical component are less likely to occur.

The linear expansion coefficient of the secondary cured product obtained by heating the primary cured product at 100°C for 5 minutes is preferably 80 ppm/°C or more and 140 ppm/°C or less. In this case, cracks due to internal stress are particularly unlikely to occur in the optical component produced from the composition (X). The coefficient of linear expansion of the secondary cured product is more preferably 100 ppm/°C or more, and more preferably 130 ppm/°C or less.

Such properties of composition (X) are achievable by the composition of composition (X) described in detail below.

A cured product obtained by irradiating the composition (X) with light and then heating preferably has a glass transition temperature of 80° C. or higher. In this case, the cured product can have good heat resistance. Therefore, for example, when the cured product is subjected to a treatment that involves a temperature rise, the cured product is less likely to deteriorate. The glass transition temperature of the cured product is more preferably 90°C or higher, and even more preferably 100°C or higher.

The viscosity of composition (X) at 25° C. is preferably 1 mPa·s or more and 35 mPa·s or less. In this case, the composition (X) can be applied and molded at room temperature by a casting method, an ink jet method, or the like. This viscosity is more preferably 30 mPa·s or less, further preferably 20 mPa·s or less, and particularly preferably 15 mPa·s or less. The viscosity is preferably 5 mPa·s or more, more preferably 8 mPa·s or more. For example, the viscosity is preferably 8 mPa·s or more and 35 mPa·s or less.

It is also preferable that the composition (X) has a viscosity of 1 mPa·s or more and 35 mPa·s or less at 40°C. In this case, even if the viscosity of the composition (X) at room temperature is any value, the viscosity of the composition (X) can be lowered by slightly heating the composition (X). Therefore, if heated, the composition (X) can be easily molded by a method such as a casting method, and the composition (X) can also be molded by an inkjet method. Moreover, since the viscosity of the composition (X) can be lowered without significantly heating the composition (X), changes in the composition of the composition (X) due to volatilization of the components in the composition (X) can be suppressed. This viscosity is more preferably 30 mPa·s or less, further preferably 20 mPa·s or less, and particularly preferably 15 mPa·s or less. The viscosity is preferably 5 mPa·s or more, more preferably 8 mPa·s or more. For example, the viscosity is preferably 8 mPa·s or more and 35 mPa·s or less.

Such a low viscosity of composition (X) at 25° C. or 40° C. can also be achieved by the composition of composition (X) described in detail below.

When the cured product of composition (X) has a thickness of 10 μm, the total light transmittance is preferably 90% or more. In this case, if the cured product is applied to an optical part such as the sealing material 5 in the light emitting device 1, the extraction efficiency of light transmitted through the optical part and emitted to the outside can be particularly improved. Such optical transparency of the cured product can also be achieved by the composition of composition (X) described in detail below.

It is also preferable that the composition (X) has a surface tension of 20 mN/cm or more and 40 mN/cm or less. In this case, when the composition (X) is applied by an ink jet method, the ejection stability is good, and it is possible to prevent the formation of defective liquid droplets called satellites. A surface tension of 30 mN/cm or more and 40 mN/cm or less is more preferable, and a surface tension of 31 mN/cm or more and 38 mN/cm or less is even more preferable.

The present embodiment will be described in more detail below.

1. Structure of Light Emitting Device First, the structure of the light emitting device 1 will be described. The light emitting device 1 includes a light source and an optical component that transmits light emitted by the light source. For example, the light-emitting device 1 includes a light-emitting element 4 and a sealing material 5 covering the light-emitting element 4 . In this case, the light emitting element 4 is the light source and the sealing material 5 is the optical component. The sealing material 5 may cover the light emitting element 4 while being in direct contact with the light emitting element 4, or may cover the light emitting element 4 while some layer is interposed between the sealing material 5 and the light emitting element 4. good. The light emitting device 1 may be, for example, a lighting device or a display device (display).

Light emitting element 4 includes, for example, a light emitting diode. Light-emitting diodes include, for example, at least one of organic EL elements (organic light-emitting diodes) and micro light-emitting diodes. 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. If the light emitting element 4 comprises a micro light emitting diode, the light emitting device 1 comprising the light emitting element 4 is for example a micro LED display. Note that EL means electroluminescence, and LED means light emitting diode.

A first example of the structure of the light emitting device 1 will be described with reference to FIG. This 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 on the surface of the support substrate 2 facing the transparent substrate 3 , and the support substrate 2 and the transparent substrate 3 . and a sealing material 5 filled between them. In the first example, the light-emitting device 1 also includes a passivation layer 6 that covers the surface of the support substrate 2 facing the transparent substrate 3 and the light-emitting elements 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 to this. The transparent substrate 3 is made of a translucent material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate. 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 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 laminated in the order described above. Although only one light-emitting element 4 is shown in FIG. good. 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. Elements common to those in the first example shown in FIG. 1 are denoted by the same reference numerals in FIG. 2 as those in FIG. 1, and detailed description thereof will be omitted as appropriate. The light emitting device 1 shown in FIG. 2 is also of the 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 on the surface of the support substrate 2 facing the transparent substrate 3, and a seal covering the light-emitting element 4. Material 5 is provided.

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 between the electrodes 41 and 43, as in 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 laminated in the order described above.

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 element array 9 ) on the support substrate 2 . The element array 9 also comprises partition walls 7 . The partition wall 7 is located on the support substrate 2 and partitions between the two adjacent light emitting elements 4 . The partition wall 7 is produced by molding a photosensitive resin material by photolithography, for example. The element array 9 also includes connection wirings 8 that electrically connect the electrodes 43 and the electron transport layers 424 of the adjacent light emitting elements 4 to each other. The connection wiring 8 is provided on the partition wall 7 .

The light emitting device 1 also comprises a passivation layer 6 covering the light emitting element 4 . Passivation layer 6 is preferably made of silicon nitride or silicon oxide. Passivation layer 6 includes a first passivation layer 61 and a second passivation layer 62 . The first passivation layer 61 covers the light emitting elements 4 by covering the element array 9 while being in direct contact with the element array 9 . The second passivation layer 62 is arranged on the side opposite to the element array 9 with respect to the first passivation layer 61, and a space is provided between the second passivation layer 62 and the first passivation layer 61. ing. A sealing material 5 is filled between the first passivation layer 61 and the second passivation layer 62 . That is, the first passivation layer 61 is interposed between the light emitting element 4 and the sealing material 5 covering the light emitting element 4 .

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

The encapsulant 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 produce the encapsulant 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 manufacturing a light-emitting device.

2. Ultraviolet Curable Resin Composition The composition (X) contains a curable component having ultraviolet curability. The curable component contains, for example, a cationic polymerizable compound (F) and a cationic curing catalyst (photocationic polymerization initiator) (G). The curable component may contain a radically polymerizable compound and a radical photopolymerization initiator (B).

When the curable component contains the radically polymerizable compound and the photoradical polymerization initiator (B), the radically polymerizable compound preferably contains the acrylic compound (A). In this case, when the composition (X) is irradiated with ultraviolet rays, a photoradical polymerization reaction is initiated by the photoradical polymerization initiator (B), and the acrylic compound (A) is cured, whereby a cured product can be produced.

The components of the composition (X) containing the acrylic compound (A) and the radical photopolymerization initiator (B) (hereinafter also referred to as composition (X1)) will be described in more detail.

As described above, composition (X1) contains acrylic compound (A). The acrylic compound (A) has one or more (meth)acryloyl groups in one molecule.

The viscosity of the entire acrylic compound (A) at 25° C. is preferably 50 mPa·s or less. In this case, the acrylic compound (A) can particularly lower the viscosity of the composition (X1). The viscosity of the acrylic compound (A) as a whole is more preferably 30 mPa·s or less, and particularly preferably 20 mPa·s or less. Moreover, the viscosity of the acrylic compound (A) as a whole is, for example, 3 mPa·s or more.

It is also preferable that the viscosity of the entire acrylic compound (A) at 40° C. is 50 mPa·s or less. In this case, the acrylic compound (A) can particularly lower the viscosity of the composition (X1) when heated. The viscosity of the acrylic compound (A) as a whole is more preferably 30 mPa·s or less, and particularly preferably 20 mPa·s or less. Moreover, the viscosity of the acrylic compound (A) as a whole is, for example, 3 mPa·s or more.

A compound that the acrylic compound (A) may contain will be described.

The acrylic compound (A) preferably contains a polyfunctional acrylic compound (A1) having two or more (meth)acryloyl groups in one molecule. In this case, the polyfunctional acrylic compound (A1) can increase the glass transition temperature of the cured product, and therefore can increase the heat resistance of the cured product and the sealing material 5 . The amount of the polyfunctional acrylic compound (A1) is preferably 50% by mass or more and 100% by mass or less based on the total amount of the acrylic compound (A). The acrylic compound (A) may contain only the polyfunctional acrylic compound (A1).

The polyfunctional acrylic compound (A1) includes, for example, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol oligoacrylate, diethylene glycol diacrylate, 1,6-hexanediol oligoacrylate, neopentyl glycol diacrylate, Triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclohexanedimethanol diacrylate, tricyclodecanedimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, pentatriestol tetra Acrylates, propoxylated (2) neopentyl glycol diacrylate, trimethylolpropane triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated (3) trimethylolpropane triacrylate, propoxylated ( 3) glyceryl triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated (4) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, hexadiol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol triacrylate, bispentaerythritol hexaacrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, ethoxylated 1,6-hexanediol diacrylate, polypropylene glycol diacrylate Acrylates, 1,4-butanediol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, neopentyl hydroxypivalate Glycol diacrylate, hydroxypivalic acid trimethylolpropane triacrylate, ethoxylated phosphoric acid triacrylate, ethoxylated tripropylene glycol diacrylate, neopentyl glycol-modified trimethylolpropane diacrylate, stearic acid-modified pentaerythritol diacrylate, tetramethylolpropane triacrylate Chestnut tetramethylolmethane triacrylate, caprolactone-modified trimethylolpropane triacrylate, propoxylate glyceryl triacrylate, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, di Pentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, tripropylene glycol di( It contains at least one compound selected from the group consisting of meth)acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.

The acrylic equivalent of the polyfunctional acrylic compound (A1) is preferably 150 g/eq or less, more preferably 90 g/eq or more and 150 g/eq or less. The weight average molecular weight of the polyfunctional acrylic compound (A1) is, for example, 100 or more and 1000 or less, more preferably 200 or more and 800 or less.

The polyfunctional acrylic compound (A1) preferably has at least one of a benzene ring, an alicyclic ring and a polar group. A polar group is, for example, at least one of an OH group and an NHCO group. In this case, shrinkage during curing of the composition (X1) can be particularly reduced. Furthermore, adhesion between the cured product and inorganic compounds such as silicon nitride and silicon oxide can be enhanced. Polyfunctional acrylic compound (A1) is in particular selected from the group consisting of tricyclodecane dimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, trimethylolpropane triacrylate and pentatriestol tetraacrylate It preferably contains at least one compound. These compounds can particularly reduce shrinkage when the composition (X1) is cured. Furthermore, these compounds can also enhance the adhesion between the cured product and inorganic compounds such as silicon nitride and silicon oxide.

It is also preferred that the polyfunctional acrylic compound (A1) contains a compound (A11) having a structure represented by the following formula (1).

_CH2 =CR1 _- COO-(R3 ^- O) _n -CO-CR2= ^CH2 ( ¹ )
In formula (1), each of R ¹ and R ² is hydrogen or a methyl group, n is an integer of 1 or more, R ³ is an alkylene group having 3 or more carbon atoms, and when n is 2 or more, A plurality of R ³ may be the same or different.

Since the compound (A11) has the structure represented by the formula (1), particularly because the carbon number of R ³ in the formula (1) is 3 or more, it is difficult to increase the affinity of the encapsulant 5 with water. Therefore, the light emitting element 4 is less likely to be deteriorated by water. The carbon number of R ³ is, for example, 3 or more and 15 or less. In addition, the compound (A11) has a structure represented by formula (1), particularly by having two (meth)acryloyl groups in one molecule, so that the glass transition temperature of the cured product can be increased. , the heat resistance of the cured product and the sealing material 5 can be enhanced. Also, n in formula (1) is an integer of 1 or more and 12 or less, for example.

The percentage ratio of compound (A11) to acrylic compound (A) is preferably 50% by mass or more. In this case, it is particularly difficult to increase the affinity of the cured product and the sealing material 5 for water. The percentage ratio of the compound (A11) to the acrylic compound (A) is, for example, 100% by mass or less, or 95% by mass or less, preferably 80% by mass or less.

Compound (A11) preferably contains compound (A12) having a boiling point of 270° C. or higher. That is, the acrylic compound (A) preferably contains a compound (A12) having a structure represented by formula (1) and a boiling point of 270°C or higher. In this case, the acrylic compound (A) is less likely to volatilize from the composition (X) during storage and when the composition (X) is heated. Therefore, the storage stability of composition (X) is less likely to be impaired. Further, even if the compound (A12) remains unreacted in the cured product of the composition (X) and in the sealing material 5, outgassing due to the compound (A12) is generated from the cured product and the sealing material 5. Hateful. Therefore, voids due to outgassing are less likely to occur in the light emitting device 1 . If there is a gap in the light-emitting device 1, moisture may enter the light-emitting element 4 through the gap. The boiling point is the boiling point under normal pressure obtained by converting the boiling point under reduced pressure, and can be determined, for example, by the method shown in Science of Petroleum, Vol. II. P.1281 (1938). More preferably, the boiling point of compound (A12) is 280° C. or higher.

The percentage ratio of compound (A12) to acrylic compound (A) is preferably 50% by mass or more. In this case, the storage stability of the composition (X) is effectively enhanced, the generation of outgassing from the encapsulating material 5 is effectively reduced, and the affinity of the encapsulating material 5 for water is particularly difficult to increase. . The percentage ratio of the compound (A12) to the acrylic compound (A) is, for example, 100% by mass or less, or 95% by mass or less, preferably 80% by mass or less.

The viscosity of compound (A12) at 25° C. is preferably 25 mPa·s or less. In this case, compound (A12) can lower the viscosity of composition (X). The viscosity of compound (A12) at 25° C. is more preferably 25 mPa·s or less, still more preferably 20 mPa·s or less, and particularly preferably 15 mPa·s or less. The viscosity of compound (A12) at 25° C. is, for example, 1 mPa·s or more, preferably 3 mPa·s or more, and more preferably 5 mPa·s or more.

The compound (A12) is, for example, a group consisting of an alkylene glycol di(meth)acrylate, a polyalkylene glycol di(meth)acrylate, and an alkylene oxide-modified alkylene glycol di(meth)acrylate. contains at least one compound selected from

Di(meth)acrylic acid ester of alkylene glycol is a compound in which n is 1 in formula (1). In this case, R ³ in formula (1) preferably has 4 to 12 carbon atoms. R ³ may be linear or branched. In particular, alkylene glycol di(meth)acrylic acid esters are 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9- nonanediol diacrylate, 1,10-decanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9 -nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, and 1,12-dodecanediol dimethacrylate. In addition, the di(meth)acrylic acid ester of alkylene glycol is manufactured by Sartomer, product number SR213, Osaka Organic Chemical Industry Co., Ltd. product number V195, Sartomer product number SR212, Sartomer product number SR247, Kyoei Chemical Industry Co., Ltd. Product name Light acrylate NP-A, product number SR238NS manufactured by Sartomer, product number V230 manufactured by Osaka Organic Chemical Industry Co., Ltd., product number HDDA manufactured by Daicel, product number 1,6HX-A manufactured by Kyoei Chemical Industry Co., Ltd., Osaka Organic Chemical Industry Co., Ltd. product number V260 manufactured by Kyoei Chemical Industry Co., Ltd., product number 1,9-ND-A manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product number A-NOD-A manufactured by Sartomer, product number CD595 manufactured by Sartomer, product number SR214NS manufactured by Sartomer, Shin-Nakamura Product number BD manufactured by Kagaku Kogyo Co., Ltd. Product number SR297 manufactured by Sartomer Co., Ltd. Product number SR248 manufactured by Sartomer Co., Ltd. Product name Light Ester NP manufactured by Kyoei Chemical Industry Co., Ltd. Product number SR239NS manufactured by Sartomer Co., Ltd. Product name Light Ester 1 manufactured by Kyoei Chemical Industry Co., Ltd. , 6HX, product number HD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name Light Ester 1, 9ND manufactured by Kyoei Chemical Industry Co., Ltd., product number NOD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name Light Ester 1 manufactured by Kyoei Chemical Industry Co., Ltd. , 10DC, product number DOD-N manufactured by Shin-Nakamura Chemical Co., Ltd., and product number SR262 manufactured by Sartomer.

Di(meth)acrylic acid ester of polyalkylene glycol is a compound in which n is 2 or more in formula (1). n is, for example, 2 to 10, preferably 2 to 7, more preferably 2 to 6, and more preferably 2 to 3. The carbon number of R ³ is, for example, 2-5. As the number of carbon atoms increases, the hydrophobicity of the cured product and the color resist 1 increases, and the color resist 1 becomes less permeable to moisture. Di(meth)acrylic acid esters of polyalkylene glycols are in particular diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate. It preferably contains at least one compound selected from the group consisting of acrylates, tripropylene glycol dimethacrylate and tritetramethylene glycol diacrylate. In addition, the di(meth)acrylic acid ester of polyalkylene glycol is particularly available from Sartomer under the product number SR230, from Sartomer under the product number SR508NS, from Daicel under the product number DPGDA, from Sartomer under the product number SR306NS, and from Daicel under the product number TPGDA. , Product number V310HP manufactured by Osaka Organic Chemical Industry Co., Ltd. Product number APG200 manufactured by Shin-Nakamura Chemical Industry Co., Ltd. Product name Light acrylate PTMGA-250 manufactured by Kyoei Chemical Industry Co., Ltd. Product number SR231NS manufactured by Sartomer Co., Ltd. Product name Light manufactured by Kyoei Chemical Industry Co., Ltd. Ester 2EG, product number SR205NS manufactured by Sartomer, product name Light Ester 3EG manufactured by Kyoei Chemical Industry, product number SR210NS manufactured by Sartomer, product name Light Ester 4EG manufactured by Kyoei Chemical Industry, product name Acryester HX manufactured by Mitsubishi Chemical Corporation, and new It is preferable to contain at least one compound selected from the group consisting of product number 3PG manufactured by Nakamura Chemical Co., Ltd.

The di(meth)acrylic acid ester of alkylene oxide-modified alkylene glycol contains, for example, propylene oxide-modified neopentyl glycol. Further, the di(meth)acrylic acid ester of alkylene oxide-modified alkylene glycol contains, for example, product number EBECRYL145 manufactured by Daicel.

It is preferable that the percentage of components having a boiling point of 270° C. or higher in the acrylic compound (A) is 80 mass % or higher. When the acrylic compound (A) contains the compound (A12), the percentage of components having a boiling point of 270° C. or higher, including the compound (A12), in the acrylic compound (A) is 80% by mass or more. is preferred. In this case, the storage stability of the composition (X) is particularly unlikely to be impaired, and outgassing from the cured product and the sealing material 5 is particularly unlikely. More preferably, the percentage of components having a boiling point of 280° C. or higher in the acrylic compound (A) is 80 mass % or higher.

Compound (A11) may contain compound (A13) other than compound (A12).

The polyfunctional acrylic compound (A1) may contain a compound (A14) having three or more (meth)acryloyl groups in one molecule. That is, the acrylic compound (A) may contain the compound (A14). In this case, compound (A14) can contain, for example, at least one selected from the group consisting of trimethylolpropane triacrylate and trimethylolpropane trimethacrylate. When the acrylic compound (A) contains the compound (A14), the compound (A14) can particularly increase the glass transition temperature of the cured product, and therefore can particularly increase the heat resistance of the cured product and the color resist 1. can.

When the acrylic compound (A) contains the compound (A14), the percentage of the compound (A14) to the acrylic compound (A) is preferably more than 0% by mass and 25% by mass or less. More preferably, the percentage of compound (A14) is 10% by mass or more. In this case, the glass transition temperature of the cured product can be particularly increased. Further, when the compound (A14) is 25% by mass or less, the increase in viscosity of the composition (X) due to the compound (A14) is less likely to occur. If the percentage of compound (A14) is 20% by mass or less, the increase in viscosity of composition (X) is particularly difficult to occur.

When the acrylic compound (A) contains the compound (A11) having the structure represented by the formula (1), the compound (A11) preferably does not contain compounds in which the value of n in the formula (1) is 5 or more. . When (R ³ —O) _n is a polyethylene glycol skeleton, it is particularly preferred not to include compounds in which the value of n in formula (1) is greater than 5. Even when the compound (A11) contains a compound in the formula (1) in which the value of n is greater than 5, the percentage of the compound in the formula (1) in which the value of n is greater than 5 relative to the acrylic compound (A) is 20. % or less is preferable. Further, even when the compound (A11) contains a compound having a value of n greater than 5 in formula (1), the compound (A11) preferably does not contain a compound having a value of n greater than 9. It is further preferred not to include compounds with a value greater than 7. In these cases, the increase in viscosity of composition (X) is particularly difficult to occur.

The acrylic compound (A) also preferably contains a monofunctional acrylic compound (A2) having only one (meth)acryloyl group in one molecule. The monofunctional acrylic compound (A2) can suppress shrinkage of the composition (X1) during curing.

The amount of the monofunctional acrylic compound (A2) relative to the total amount of the acrylic compound (A) is preferably more than 0% by mass and 50% by mass or less. When the amount of the monofunctional acrylic compound (A2) is more than 0% by mass, the shrinkage of the composition (X1) during curing can be suppressed. In addition, if the amount of the monofunctional acrylic compound (A2) is 50% by mass or less, the amount of the polyfunctional acrylic compound (A1) can be 50% by mass or more, so that the heat resistance of the cured product and the sealing material 5 can be particularly improved. More preferably, the amount of the monofunctional acrylic compound (A2) is 5% by mass or more, and more preferably 30% by mass or less.

Monofunctional acrylic compounds (A2) are, for example, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, 2-methoxyethyl acrylate. , methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydixylethyl acrylate, ethyl diglycol acrylate, cyclic trimethylolpropane formal monoacrylate, imido acrylate, isoamyl acrylate, ethoxylated succinic acid acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, cyclohexyl acrylate, 2-(2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, isodecyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl acrylate, octyl/decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated (4) nylphenol acrylate, methoxypolyethylene glycol (350) monoacrylate, Methoxypolyethylene glycol (550) monoacrylate, phenoxyethyl acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl Acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, ethylene oxide adduct of 2-phenoxyethyl acrylate, propylene oxide adduct of 2-phenoxyethyl acrylate, acryloyl morpholine, isobornyl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1, It contains at least one compound selected from the group consisting of 4-cyclohexanedimethanol monoacrylate, 3-methacryloyloxymethylcyclohexene oxide and 3-acryloyloxymethylcyclohexene oxide.

The monofunctional acrylic compound (A2) may contain at least one compound selected from the group consisting of compounds having an alicyclic structure and compounds having a cyclic ether structure.

Compounds having an alicyclic structure include, for example, phenoxyethyl acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butyl cyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, ethylene oxide adduct of 2-phenoxyethyl acrylate, propylene oxide adduct of 2-phenoxyethyl acrylate, At least one selected from the group consisting of acryloylmorpholine, isobornyl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate contains a compound of

The number of ring members of the cyclic ether structure in the compound having the cyclic ether structure is preferably 3 or more, more preferably 3 or more and 4 or less. The number of carbon atoms contained in the cyclic ether structure is preferably 2 or more and 9 or less, more preferably 2 or more and 6 or less. The compound having a cyclic ether structure contains, for example, at least one compound selected from the group consisting of 3-methacryloyloxymethylcyclohexene oxide and 3-acryloyloxymethylcyclohexene oxide.

The acrylic compound (A) is selected from the group consisting of a compound (A41) having silicon in the molecular skeleton, a compound (A42) having phosphorus in the molecular skeleton, and a compound (A43) having nitrogen in the molecular skeleton. It is preferred to further contain at least one compound. In this case, the adhesion between the cured product/sealing material 5 and the member made of the inorganic material is improved. Therefore, a gap is less likely to occur between the sealing material 5 and the passivation layer 6, and moisture is less likely to enter the light emitting element 4 through this gap.

The compounds (A41), (A42) and (A43) are defined by the types of atoms in the molecular skeleton. Therefore, the compounds contained in each of the polyfunctional acrylic compound (A1) and the monofunctional acrylic compound (A2) overlap with the compounds contained in each of the compound (A41), the compound (A42) and the compound (A43). sell.

The compound (A41) is, for example, 3-(trimethoxysilyl)propyl acrylate (for example, product number KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) and a (meth)acrylic group-containing alkoxysilane oligomer (for example, product number KR-513 manufactured by Shin-Etsu Chemical Co., Ltd. ) contains at least one compound selected from the group consisting of However, since the boiling point of 3-(trimethoxysilyl)propyl acrylate is 260° C., when acrylic compound (A) contains 3-(trimethoxysilyl)propyl acrylate, acrylic acid to acrylic compound (A) The percentage of 3-(trimethoxysilyl)propyl should be 10% by weight or less.

Compound (A42) includes acid phosphooxy (meth)acrylates, such as acid phosphooxy polyoxypropylene glycol monomethacrylate.

Compound (A43) includes, for example, at least one compound selected from the group consisting of acryloylmorpholine, diethylacrylamide, dimethylaminopropylacrylamide and pentamethylpiperidyl methacrylate.

When acrylic compound (A) contains at least one compound selected from the group consisting of compound (A41), compound (A42) and compound (A43), compound (A41) and compound (A42) for acrylic compound (A) ) and compound (A43) is preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less.

It is also preferred that the acrylic compound (A) contains a compound having an isobornyl skeleton. In this case, when the size of the droplets of the composition (X) ejected by the ink jet method is reduced, it is possible to prevent the formation of satellites. That is, it is easy to miniaturize droplets without generating satellites. Therefore, it becomes easy to form small droplets of the composition (X) at high density by an ink jet method, and therefore it is easy to realize thinning of the encapsulating material 5 . When the acrylic compound (A) contains a compound having an isobornyl skeleton, the percentage of the compound having an isobornyl skeleton to the entire acrylic compound (A) is preferably more than 0% by mass and 80% by mass or less. When this percentage is more than 0% by mass, it is particularly easy to reduce the size of droplets. Further, when the percentage is 80% by mass or less, outgassing can be easily reduced. In particular, in order to reduce outgassing, the percentage of the compound having an isobornyl skeleton relative to the total acrylic compound (A) is preferably 40% by mass or less, more preferably 20% by mass or less.

The compound having an isobornyl skeleton can contain, for example, one or more compounds selected from the group consisting of isobornyl acrylate and isobornyl methacrylate.

The acrylic compound (A) preferably contains component (a) comprising at least one compound having a viscosity of 20 mPa·s or less at 25°C. In this case, the component (a) can lower the viscosity of the composition (X1). The compound contained in component (a) may be a compound contained in the polyfunctional acrylic compound (A1) or a compound contained in the monofunctional acrylic compound (A2).

The ratio of component (a) to the total amount of acrylic compound (A) is preferably 50% by mass or more and 100% by mass or less. In this case, the viscosity of the composition (X1) can be particularly lowered, making it particularly easy to apply the composition (X1) by an inkjet method. The proportion of component (a) is more preferably 60% by mass or more, even more preferably 70% by mass or more. Further, the proportion of component (a) is more preferably 95% by mass or less, even more preferably 90% by mass or less.

Component (a) preferably contains a compound having a glass transition temperature of 80° C. or higher. That is, component (a) preferably contains a compound having a viscosity of 20 mPa·s or less at 25°C and a glass transition temperature of 80°C or more. In this case, the component (a) can increase the glass transition temperature of the cured product while reducing the viscosity of the composition (X1). Component (a) more preferably contains a compound having a glass transition temperature of 90°C or higher, and more preferably contains a compound having a glass transition temperature of 100°C or higher. Although the upper limit of the glass transition temperature of the compound contained in component (a) is not limited, it is, for example, 150°C or less.

Component (a) is for example the group consisting of isobornyl acrylate, dicyclopentanyl acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol 200 dimethacrylate and polyethylene glycol 200 diacrylate. can contain at least one compound selected from

Component (a) contains at least one compound selected from the group consisting of isobornyl acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol 200 dimethacrylate and polyethylene glycol 200 diacrylate. preferably. These compounds can particularly reduce the maximum peak value of the composition (X1), so that the maximum peak value of the composition (X1) is 350 mPa s or less, and the ratio of the maximum peak value to the viscosity at 25 ° C. can contribute to achieving 20 or less.

It is particularly preferred if component (a) contains isobornyl acrylate. Isobornyl acrylate can reduce the maximum peak value of the composition (X1), increase the glass transition temperature of the cured product, and reduce shrinkage when the composition (X1) is cured.

The ratio of the total amount of isobornyl acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol 200 dimethacrylate and polyethylene glycol 200 diacrylate to the total amount of acrylic compound (A) is 50% by mass or more. It is preferably 95% by mass or less. In this case, the maximum peak value can be reduced, the glass transition temperature of the cured product can be increased, and shrinkage during curing of the composition (X1) can be reduced. The total amount of these compounds is more preferably 60% by mass or more, and even more preferably 70% by mass or less.

The acrylic compound (A) contains a component (b) consisting of a compound having at least one skeleton selected from the group consisting of a dicyclopentadiene skeleton, a dicyclopentanyl skeleton, a dicyclopentenyl skeleton, and a bisphenol skeleton. good too. Component (b) can improve adhesion between the cured product and inorganic compounds such as silicon nitride and silicon oxide. The compound contained in component (b) may be a compound contained in the polyfunctional acrylic compound (A1) or a compound contained in the monofunctional acrylic compound (A2). The compound contained in component (b) may be the compound contained in component (a).

However, in order to make it difficult for satellites to occur when droplets of the composition (X) ejected by an inkjet method are reduced in size, that is, to reduce the size of droplets without generating satellites, an acrylic compound (A) preferably does not contain a compound having a dicyclopentadiene skeleton.

The ratio of component (b) to the total amount of acrylic compound (A) is preferably 5% by mass or more and 50% by mass or less. When the proportion of component (b) is 5% by mass or more, the adhesiveness of the cured product is further increased. Further, when the proportion of the component (b) is 50% by mass or less, the maximum peak value of the composition (X1) can be lowered, and the viscosity of the composition (X1) can be lowered to obtain the composition (X1). can be easily molded by the inkjet method. The proportion of component (b) is more preferably 30% by mass or more, and even more preferably 40% by mass or less. Incidentally, the acrylic compound (A) may not contain the component (b), in which case the maximum peak value of the composition (X1) can be particularly low.

Component (b) can contain, for example, at least one compound selected from the group consisting of tricyclodecanedimethanol diacrylate, bisphenol A polyethoxy diacrylate and bisphenol F polyethoxy diacrylate.

The acrylic compound (A) is a component (c ) is also preferred. The component (c) can provide the sealing material 5 made from the composition (X) with adhesion to a member made of an inorganic material such as the passivation layer 6 . The compound contained in component (c) may be the compound contained in component (a).

In formula (100), R ⁰ is H or a methyl group. X is a single bond or a divalent hydrocarbon group. Each of R ¹ to R ¹¹ is H, an alkyl group or -R ¹² -OH, R ¹² is an alkylene group and at least one of R ¹ to R ¹¹ is an alkyl group or -R ¹² -OH. R ¹ to R ¹¹ are not chemically bonded to each other.

When X is a divalent hydrocarbon group, X preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Divalent hydrocarbon radicals are, for example, methylene, ethylene or propylene radicals. It is particularly preferred if X is a single bond or a methylene group. In this case, there is an advantage that the compound (A1) has a small molecular weight and a low viscosity.

When at least one of R ¹ to R ¹¹ is an alkyl group, the alkyl group preferably has 1 to 8 carbon atoms. Alkyl is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. The alkyl group may be linear and branched. That is, for example, when the alkyl group is a butyl group, the butyl group may be a t-butyl group, an n-butyl group, or a sec-butyl group. When the alkyl group is a hexyl group, the hexyl group may be a t-hexyl group, an n-butyl group, or a sec-butyl group. If the alkyl group is an octyl group, the octyl group can be, for example, a t-octyl group. It is particularly preferred if the alkyl group is methyl or t-butyl. In this case, there is an advantage that the compound (A1) has a small molecular weight and a low viscosity.

In formula (100), an alkyl group or -R ¹² -OH is preferably connected only to the 4-position of the cyclohexane ring. That is, of R ¹ to R ¹¹ , it is preferred that at least one of R ⁶ and R ⁷ is an alkyl group or -R ¹² -OH and each of the remaining is H. Of R ¹ to R ¹¹ , it is particularly preferred that only R ⁶ is an alkyl group or -R ¹² -OH and each of the remainder is H. In this case, the compound represented by the formula (100) can have good reactivity, and it is particularly easy to provide the sealing material 5 with adhesion to members made of an inorganic material. This is because the cyclohexane ring in the compound represented by formula (100) has a boat-shaped conformation, and the bulky alkyl group or —R ¹² —OH at the 4-position tends to be located at the pseudoequatorial position. it is conceivable that. It is considered that the compound represented by formula (100) having such a structure enhances the reactivity of the (meth)acryloyl group in the compound represented by formula (100). Moreover, when the compound represented by formula (100) has such a structure, the compound represented by formula (1) can increase the free volume in the sealing material 5 . Therefore, it is considered that the interfacial free energy between the sealing material 5 and the member made of the inorganic material tends to decrease, and the adhesion between the sealing material 5 and the member made of the inorganic material tends to increase. The ^{bulkier the alkyl group or —R 12 —OH} , the more likely it is to be positioned in the pseudoequatorial position. From this point of view, the alkyl group or -R ¹² -OH preferably has as many carbon atoms as possible, and the alkyl group or -R ¹² -OH preferably has a branch. For example, an alkyl group or --R ¹² --OH preferably has a t-butyl group.

In formula (100), it is also preferred that an alkyl group or -R ¹² -OH is attached only to each of the 3- and 5-positions of the cyclohexane ring. That is, among R ¹ to R ¹¹ , at least one of R ⁴ and R ⁵ is an alkyl group or -R ¹² -OH, at least one of R ⁸ and R ⁹ is an alkyl group or -R ¹² -OH, It is preferred that each of the remaining is H. Of R ¹ to R ¹¹ , only one of R ⁴ and R ⁵ is an alkyl group or -R ¹² -OH, at least one of R ⁸ and R ⁹ is an alkyl group or -R ¹² -OH, and the remaining More preferably each is H. Of R ¹ to R ¹¹ , at least one of R ⁴ and R ⁵ is an alkyl group or -R ¹² -OH, only one of R ⁸ and R ⁹ is an alkyl group or -R ¹² -OH, and the remaining It is also more preferred that each is H. Also in this case, the compound represented by formula (100) can have good reactivity, and particularly easily imparts adhesion to the sealing material 5 with members made of an inorganic material. This is because the cyclohexane ring in the compound shown in formula (100) has a boat-shaped conformation, and the bulky alkyl groups or —R ¹² —OH at each of the 3- and 5-positions are located in the pseudoequatorial position. This is probably because it is easy. For this reason, the reactivity of the (meth) ^acryloyl group in the compound represented by formula (100) is enhanced, and It is considered that the adhesion between the sealing material 5 and the member made of the inorganic material tends to be high. The ^{bulkier the alkyl group or —R 12 —OH} , the more likely it is to be positioned in the pseudoequatorial position. From this point of view, the alkyl group or -R ¹² -OH preferably has as many carbon atoms as possible, and the alkyl group or -R ¹² -OH preferably has a branch. For example, an alkyl group or --R ¹² --OH is preferably a t-butyl group.

When at least one of R ¹ to R ¹¹ is —R ¹² —OH, R ¹² preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. R ¹² is, for example, methylene, ethylene or propylene. It is particularly preferred if R ¹² is a methylene group. In this case, there is an advantage that the compound (A1) has a small molecular weight and a low viscosity.

In formula (100) it is particularly preferred if each of R ¹ to R ¹¹ is H or an alkyl group and at least one of R ¹ to R ¹¹ is an alkyl group. In this case, the compound of formula (100) can have a particularly low viscosity, so that composition (X) can have a particularly low viscosity. Therefore, the composition (X) can be particularly easily molded by an inkjet method.

Component (c) preferably contains at least one compound selected from the group consisting of compounds represented by the following formula (110), compounds represented by the following formula (120), and compounds represented by the following formula (130). In this case, shrinkage during curing of the composition (X1) can be particularly reduced. Furthermore, these compounds can also particularly enhance the adhesion between the cured product and inorganic compounds such as silicon nitride and silicon oxide.

It is particularly preferable if compound (A1) contains at least one of the compound represented by formula (110) and the compound represented by formula (120). In this case, it is particularly easy to reduce the viscosity of the composition (X), to increase the glass transition temperature of the sealing material 5, and to increase the adhesion between the sealing material 5 and the member made of an inorganic material. In addition, since the compound represented by formula (110) and the compound represented by formula (120) are difficult to volatilize, the storage stability of composition (X) is likely to be improved.

It is also preferred that compound (A1) contains at least one component selected from the group consisting of morpholine acrylate, diethylacrylamide, dimethylaminopropylacrylamide and pentamethylpiperidyl methacrylate. Since these compounds contain nitrogen, they have good affinity with inorganic materials, so that the adhesion between the sealing material 5 and members made of inorganic materials can be particularly easily improved. In addition, these compounds have low viscosities, and are therefore less likely to increase the viscosity of composition (X). Furthermore, since these compounds are difficult to volatilize, the storage stability of the composition (X) can be easily improved.

The amount of compound (A1) is preferably 5% by mass or more and 80% by mass or less with respect to the entire acrylic compound (A). In this case, the sealing material 5 can achieve both a high glass transition temperature and adhesion to members made of an inorganic material. The amount of compound (A1) is more preferably 5% by mass or more and 60% by mass or less, and particularly preferably 5% by mass or more and 50% by mass or less.

When the composition (X1) contains a hygroscopic agent (C) described later, particularly when the hygroscopic agent (C) contains zeolite particles, the acrylic compound (A) contains nitrogen. It is preferable not to contain the compound having Therefore, the acrylic compound (A) preferably does not contain any of the above morpholine acrylate, diethylacrylamide, dimethylaminopropylacrylamide and pentamethylpiperidyl methacrylate. In this case, the composition (X1) is unlikely to increase in viscosity during storage of the composition (X1). This is probably because when the composition (X1) contains the nitrogen-containing compound and the hygroscopic agent (C), the nitrogen-containing compound and the hygroscopic agent (C) are likely to react.

The composition (X1) may further contain a radically polymerizable compound (E) other than the acrylic compound (A). The radically polymerizable compound (E) includes a polyfunctional radically polymerizable compound (E1) having two or more radically polymerizable functional groups per molecule and a monofunctional radically polymerizable compound having only one radically polymerizable functional group per molecule. Either one or both of the radically polymerizable compound (E2) can be contained. The amount of the radically polymerizable compound (E) with respect to the total amount of the acrylic compound (A) and the radically polymerizable compound (E) is, for example, 10% by mass or less. The polyfunctional radically polymerizable compound (E1) is, for example, a group consisting of aromatic urethane oligomers, aliphatic urethane oligomers, epoxy acrylate oligomers, polyester acrylate oligomers and other special oligomers having two or more ethylenic double bonds in one molecule. It may contain at least one compound selected from Monofunctional radically polymerizable compounds (E2) include, for example, N-vinylformamide, vinylcaprolactam, vinylpyrrolidone, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monoxide, 1,2-epoxidedecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene It contains at least one compound selected from the group consisting of oxide, N-vinylpyrrolidone and N-vinylcaprolactam.

The radical photopolymerization initiator (B) is not particularly limited as long as it is a compound that generates radical species when irradiated with ultraviolet rays. Photoradical polymerization initiators (B) include, for example, aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), and hexaarylbiimidazoles. compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

The radical photopolymerization initiator (B) preferably contains a component having photobleaching properties. The component having photobleaching property preferably contains an acylphosphine oxide photoinitiator, and also preferably contains a compound having photobleaching property among oxime ester photoinitiators.

The radical photopolymerization initiator (B) also preferably contains a component having a sensitizer skeleton in the molecule. The sensitizer skeleton includes, for example, at least one of a 9H-thioxanthen-9-one skeleton and an anthracene skeleton. That is, the radical photopolymerization initiator (B) preferably contains a component having at least one of a 9H-thioxanthene-9-one skeleton and an anthracene skeleton.

The radical photopolymerization initiator (B) preferably contains an oxime ester photoinitiator, regardless of the presence or absence of photobleaching properties, from the viewpoint of improving curability and making outgassing less likely to occur from the cured product.

The oxime ester-based photoinitiator has a fragrance in order to make the composition (X) and production equipment less likely to be contaminated by decomposition products from the composition (X), and to further make outgassing from the cured product less likely to occur. It preferably contains a compound having a ring, more preferably contains a compound having a condensed ring containing an aromatic ring, and further preferably contains a compound having a condensed ring containing a benzene ring and a hetero ring.

Oxime ester photoinitiators include, for example, 1,2-octadione-1-[4-(phenylthio)-, 2-(o-benzoyloxime)] and ethanone, 1-[9-ethyl-6-(2- methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), and JP 2000-80068, JP 2001-233842, JP 2010-527339, JP 2010- 527338, JP-A-2013-041153, JP-A-2015-93842, etc. can contain at least one compound selected from the group consisting of oxime ester photoinitiators. The oxime ester-based photoinitiators are commercially available products having a carbazole skeleton, Irgacure OXE-02 (manufactured by BASF), Adeka Arcules NCI-831, N-1919 (manufactured by ADEKA) and TR-PBG-304 (Changzhou Kyokuden Denshi). New Material Co., Ltd.), Irgacure OXE-01 having a diphenyl sulfide skeleton, ADEKA Arkles NCI-930 (ADEKA Co., Ltd.), TR-PBG-345 and TR-PBG-3057 (all of these, Changzhou Tenryu Denshi New Materials Co., Ltd.) , and at least one compound selected from the group consisting of TR-PBG-365 (manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.) and SPI-04 (manufactured by Sanyang) having a fluorene skeleton. In particular, when the oxime ester photoinitiator contains a compound having a diphenyl sulfide skeleton or a fluorene skeleton, it is preferable in that the cured product is less likely to be colored by photobleaching. It is also preferable that the oxime ester-based photoinitiator contains a compound having a carbazole skeleton, since exposure sensitivity tends to increase.

It is also preferred that the oxime ester photoinitiator contains two or more compounds. In this case, for example, the oxime ester photoinitiator contains two or more compounds with different exposure sensitivities, so that the amount of the radical photopolymerization initiator (B) can be reduced while maintaining good exposure sensitivity. Therefore, outgassing from the cured product can be further suppressed.

The amount of the radical photopolymerization initiator (B) relative to the radically polymerizable compound in the composition (X1) is preferably 0.5% by mass or more and less than 4% by mass. When the amount of the radical photopolymerization initiator (B) is 0.5% by mass or more, good photocurability can be imparted to the composition (X1). In addition, since the amount of the photoradical polymerization initiator (B) is less than 4% by mass, the reactivity of the composition (X1) can be moderately moderated, and the DSC curve of the photocured product is from 30 ° C. to 260 ° C. Having an exothermic peak with a peak top within the range is easier to achieve.

The composition (X1) may contain a polymerization accelerator in addition to the radical photopolymerization initiator (B). Polymerization accelerators include, for example, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, butoxy p-dimethylaminobenzoate. Contains amine compounds such as ethyl.

The radical photopolymerization initiator (B) may contain a sensitizer as part of the radical photopolymerization initiator (B). The sensitizer can promote the radical generation reaction of the radical photopolymerization initiator (B), improve the reactivity of radical polymerization, and improve the crosslink density. Sensitizers are, for example, 9,10-dibutoxyanthracene, 9-hydroxymethylanthracene, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, anthraquinone, 1,2- dihydroxyanthraquinone, 2-ethylanthraquinone, 1,4-diethoxynaphthalene, p-dimethylaminoacetophenone, p-diethylaminoacetophenone, p-dimethylaminobenzophenone, p-diethylaminobenzophenone, 4,4′-bis(dimethylamino)benzophenone, It can contain at least one compound selected from the group consisting of 4,4'-bis(diethylamino)benzophenone, p-dimethylaminobenzaldehyde, and p-diethylaminobenzaldehyde.

The content of the sensitizer in the composition (X1) is, for example, 0.1 parts by mass or more and 5 parts by mass or less, preferably 0.1 parts by mass, relative to 100 parts by mass of the solid content of the composition (X1). part or more and 3 parts by mass or less. If the content of the sensitizer is within this range, the composition (X1) can be cured in the air, and it is necessary to cure the composition (X1) in an inert atmosphere such as a nitrogen atmosphere. Gone.

The composition (X1) may contain a polymerization accelerator in addition to the radical photopolymerization initiator (B). Polymerization accelerators include, for example, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, butoxy p-dimethylaminobenzoate. Contains amine compounds such as ethyl.

Components of composition (X) (hereinafter also referred to as composition (X2)) when the curable component in composition (X) contains cationic polymerizable compound (F) and cationic curing catalyst (G) will be explained.

The cationically polymerizable compound (F) in the composition (X2) contains, for example, at least one of a polyfunctional cationically polymerizable compound (F1) and a monofunctional cationically polymerizable compound (F2).

The polyfunctional cationically polymerizable compound (F1) is one or both of a polyfunctional cationically polymerizable compound (F11) having no siloxane skeleton and a polyfunctional cationically polymerizable compound (F12) having a siloxane skeleton. can contain

The polyfunctional cationically polymerizable compound (F11) does not have a siloxane skeleton and has two or more cationically polymerizable functional groups per molecule. The number of cationically polymerizable functional groups per molecule of the polyfunctional cationically polymerizable compound (F11) is preferably 2 to 4, more preferably 2 to 3.

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

The polyfunctional cationically polymerizable compound (F11) is, for example, from the group consisting of polyfunctional alicyclic epoxy compounds, polyfunctional heterocyclic epoxy compounds, polyfunctional oxetane compounds, alkylene glycol diglycidyl ethers, and alkylene glycol monovinyl monoglycidyl ethers. It contains at least one selected compound.

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

In formula (1), each of R ¹ to R ¹⁸ is independently a hydrogen atom, a halogen atom, or a hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably within the range of 1-20. The hydrocarbon group is, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, or a propyl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group or an allyl group; or an ethylidene group or a propylidene group. 20 alkylidene groups. The hydrocarbon group may contain an oxygen atom or a halogen atom. each of R ¹ to R ¹⁸ is independently a hydrogen atom or a C 1-2
0 is preferably a hydrocarbon group, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

In formula (1), X is a single bond or a _divalent organic group, and the organic group is, for example, --CO--O--CH.sub.2--.

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

In formula (20), each of R ¹ to R ¹² is independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. Halogen is, for example, fluorine, chlorine, bromine or iodine. 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 and a propyl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group and an allyl group; or an ethylidene group and a propylidene group. It is an alkylidene group having 2 to 20 carbon atoms such as a group. The hydrocarbon group having 1 to 20 carbon atoms may contain an oxygen atom or a halogen atom.

Each of R ¹ to R ¹² is independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.

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

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

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

Alkylene glycol diglycidyl ether contains, for example, at least one compound selected from the group consisting of compounds represented by the following formulas (4) to (7).

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

More specifically, the polyfunctional cationic polymerizable compound (F11) is, for example, Daicel Celoxide 2021P and Celoxide 8010, Nissan Chemical TEPIC-VL, Toagosei OXT-221, and Yokkaichi Gosei 1, It can contain at least one component selected from the group consisting of 3-PD-DEP, 1,4-BG-DEP, 1,6-HD-DEP, NPG-DEP and butylene glycol monovinyl monoglycidyl ether.

The polyfunctional cationically polymerizable compound (F11) also preferably contains a polyfunctional alicyclic epoxy compound. In this case, the composition (X2) can have a particularly high cationic polymerization reactivity.

The polyfunctional alicyclic epoxy compound 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 (X2) can have higher cationic polymerization reactivity.

When the polyfunctional alicyclic epoxy compound contains the compound represented by formula (1), the compound represented by formula (1) preferably contains the compound represented by formula (1a). In this case, the composition (X2) can have a higher cationic polymerization reactivity and a particularly low viscosity.

In addition, in particular, the compound represented by formula (20) has a low viscosity, so when the compound represented by formula (20) is contained, the composition (X2) can have good ultraviolet curability, and in particular It can have a low viscosity. Furthermore, the compound represented by formula (20) has a property of being difficult to volatilize in spite of having a low viscosity. Therefore, even if the composition (X2) contains the compound represented by the formula (20), the composition (X2) is unlikely to change in composition due to volatilization of the compound represented by the formula (20). Therefore, the composition (X2) containing the compound represented by the formula (20) can have a low viscosity without impairing the storage stability.

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

The compound of formula (20) can contain four stereoisomers based on the configuration of the two epoxy rings. Compounds of formula (20) may include any of the four stereoisomers. That is, the compound represented by formula (20) can contain at least one component selected from the group consisting of four stereoisomers. In the compound represented by the formula (20), the ratio of the total amount of the exo-endo form and the endo-endo form among the four stereoisomers is 10% by mass or less with respect to the entire epoxy compound (A1). is preferred, and 5% by mass or less is more preferred. In this case, the heat resistance of the cured product can be improved. The proportion of a 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 amounts of the exo-endo form and the endo-endo form in the compound represented by the formula (20), a method of precision distillation of the compound represented by the formula (20), column chromatography using silica gel or the like as a packing material Any suitable method can be applied, such as a method applying graphics.

When the composition (X2) contains the polyfunctional cationically polymerizable compound (F11), the ratio of the polyfunctional cationically polymerizable compound (F11) to the total amount of the resin component is preferably in the range of 5 to 95% by mass. . The resin component refers to a cationically polymerizable compound in the composition (X2), including the polyfunctional cationically polymerizable compound (F1) and the monofunctional cationically polymerizable compound (F2). If the proportion of the polyfunctional cationically polymerizable compound (F11) is 5% by mass or more, the composition (X2) can have particularly excellent reactivity during the cationic photopolymerization reaction, and thereby the cured product has high strength. (hardness). Further, if the proportion of the polyfunctional cationically polymerizable compound (F11) is 95% by mass or less, when the composition (X2) contains the moisture absorbent (C), the moisture absorbent (C ) can be particularly easily dispersed uniformly. The proportion of the polyfunctional cationically polymerizable compound (F11) is more preferably 12% by mass or more, still more preferably 15% by mass or more, even more preferably 20% by mass or more, even if it is 25% by mass or more. is particularly preferred. The proportion of this polyfunctional cationically polymerizable compound (F11) is more preferably 85% by mass or less, and even more preferably 60% by mass or less. For example, it is preferable that the proportion of the polyfunctional cationic polymerizable compound (F11) is within the range of 20 to 60% by mass.

When the polyfunctional cationically polymerizable compound (F11) contains a polyfunctional alicyclic epoxy compound, the polyfunctional alicyclic epoxy compound may be part or all of the polyfunctional cationically polymerizable compound (F11). may be The ratio of the polyfunctional alicyclic epoxy compound to the polyfunctional cationically polymerizable compound (F11) is preferably within the range of 15 to 100% by mass. When this proportion is 15% by mass or more, the polyfunctional alicyclic epoxy compound can particularly contribute to improving the ultraviolet curability of the composition (X2).

The polyfunctional cationically polymerizable compound (F12) has a siloxane skeleton and two or more cationically polymerizable functional groups per molecule. The number of cationically polymerizable functional groups per molecule of the polyfunctional cationically polymerizable compound (F12) is preferably 2 to 6, more preferably 2 to 4. The polyfunctional cationically polymerizable compound (F12) can contribute to improving the cationic polymerization reactivity of the composition (X2), and can contribute to improving the resistance to heat discoloration of the cured product and the sealing material 5 . When the sealing material 5 has high resistance to heat discoloration, it is possible to suppress deterioration of the emission intensity over time and change in emission color over time of the light emitting device 1 including the sealing material 5 . In addition, the polyfunctional cationically polymerizable compound (F12) can also contribute to lowering the elastic modulus of the cured product and the encapsulant 5, and thus imparts flexibility to the light-emitting device 1 including the encapsulant 5. is also possible. Moreover, when the composition (X2) contains a moisture absorbent, the polyfunctional cationic polymerizable compound (F12) can contribute to improving the dispersibility of the moisture absorbent in the composition (X2) and in the cured product. Therefore, even if the hygroscopic agent is not subjected to a surface treatment or the like for improving dispersibility, the hygroscopic agent can be well dispersed in the composition (X2) and the cured product.

The polyfunctional cationic polymerizable compound (F12) is preferably liquid at 25°C. In particular, the viscosity at 25° C. of the polyfunctional cationic polymerizable compound (F12) is preferably in the range of 10 to 300 mPa·s. In this case, an increase in viscosity of the composition (X2) can be suppressed.

The cationically polymerizable functional group possessed by the polyfunctional cationically polymerizable compound (F12) is, for example, at least one group selected from the group consisting of an epoxy group, an oxetane group and a vinyl ether group.

The siloxane skeleton of the polyfunctional cationically polymerizable compound (F12) may be linear, branched, or cyclic. The number of Si atoms in the siloxane skeleton is preferably within the range of 2-14. In this case, composition (X2) can have a particularly low viscosity. The number of Si atoms is more preferably within the range of 2-10, more preferably within the range of 2-7, and particularly preferably within the range of 3-6.

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

R in each of formulas (10) and (11) is a single bond or a divalent organic group, preferably an alkylene group. Y is a siloxane skeleton, which may be linear, branched, or cyclic, and the number of Si atoms is preferably within the range of 2 to 14, preferably within the range of 2 to 10. is more preferable, 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 2-4.

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

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

The compound represented by formula (10a) preferably contains a compound represented by formula (30) below. That is, the polyfunctional cationically polymerizable compound (F12) preferably contains a compound represented by the following formula (30).

In formula (30), n is an integer of 0 or more, preferably in the range of 0 to 12, more preferably in the range of 0 to 8, and further if in the range of 0 to 5 Preferably, it is in the range of 1 to 4, particularly preferably.

Examples of compounds represented by formula (30) include compounds represented by formula (10a-1) below.

The polyfunctional cationically polymerizable compound (F12) is represented by the following formulas (10b) to (10d) and (11a) to (11b) in place of the compound represented by the formula (10a) or together with the compound represented by the formula (10a). It may contain at least one compound among the compounds shown in .

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

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

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

More specifically, the polyfunctional cationic polymerizable compound (F12) is, for example, Shin-Etsu Chemical Co., Ltd. product numbers X-40-2669, X-40-2670, X-40-2715, X-40-2732, X -Containing at least one component selected from the group consisting of 22-169AS, X-22-169B, X-22-2046, X-22-343, X-22-163, and X-22-163B is preferred.

The polyfunctional cationically polymerizable compound (F12) preferably has an alicyclic epoxy structure, and it is particularly preferable if the polyfunctional cationically polymerizable compound (F12) contains a compound represented by formula (10a). The compound represented by the formula (10a) can particularly contribute to improving the cationic polymerization reactivity and lowering the viscosity of the composition (X2), and also improving the resistance to heat discoloration and lowering the elastic modulus of the cured product and the sealing material 5. can contribute in particular to When the composition (X2) contains the moisture absorbent (C), it can particularly contribute to improving the dispersibility of the moisture absorbent (C) in the composition (X2).

When the composition (X2) contains the polyfunctional cationically polymerizable compound (F12), the ratio of the polyfunctional cationically polymerizable compound (F12) to the total amount of the resin component is preferably in the range of 5 to 95% by mass. . If the proportion of the polyfunctional cationically polymerizable compound (F12) is 5% by mass or more, especially when the composition (X2) contains the moisture absorbent (C), the composition (X2) and the cured product By particularly improving the dispersibility of the moisture absorbent (C), the transparency of the cured product is particularly improved. Further, when the proportion of the polyfunctional cationically polymerizable compound (F12) is 95% by mass or less, the composition (X2) can have a particularly high cationic photopolymerization reactivity, so that the cured product has a particularly high strength ( hardness). The proportion of the polyfunctional cationically polymerizable compound (F12) is more preferably 6% by mass or more, further preferably 13% by mass or more, and particularly preferably 20% by mass or more. Further, the proportion of this polyfunctional cationically polymerizable compound (F12) is more preferably 70% by mass or less, in which case the refractive index of the cured product can be increased. More preferably, the proportion of the polyfunctional cationic polymerizable compound (F12) is 45% by mass or less. For example, it is preferable that the proportion of the polyfunctional cationic polymerizable compound (F12) is within the range of 20 to 70% by mass.

The monofunctional cationically polymerizable compound (F2) has only one cationically polymerizable functional group per molecule. The cationic polymerizable functional group is, for example, at least one group selected from the group consisting of epoxy group, oxetane group and vinyl ether group.

The viscosity of the monofunctional cationic polymerizable compound (F2) at 25° C. is preferably 8 mPa·s or less. In this case, even if the composition (X2) does not contain a solvent, the monofunctional cationic polymerizable compound (F2) can reduce the viscosity of the composition (X2). In particular, the viscosity at 25° C. of the monofunctional cationic polymerizable compound (F2) is preferably in the range of 0.1 to 8 mPa·s.

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

The ratio of the monofunctional cationically polymerizable compound (F2) to the total amount of the resin component is preferably in the range of 5-50% by mass. If the ratio of the monofunctional cationically polymerizable compound (F2) is 5% by mass or more, the viscosity of the composition (X2) can be particularly reduced. Further, when the proportion of the monofunctional cationically polymerizable compound (F2) is 50% by mass or less, the composition (X2) can have particularly excellent reactivity during the cationic photopolymerization reaction, and thereby the cured product can have high strength (hardness). The proportion of the monofunctional cationically polymerizable compound (F2) is more preferably 10% by mass or more, and even more preferably 15% by mass or more. The proportion of the monofunctional cationically polymerizable compound (F2) is more preferably 40% by mass or less, even more preferably 35% by mass or less, and particularly preferably 30% by mass or less. If the ratio of the monofunctional cationically polymerizable compound (F2) is particularly 35% by mass or less, the amount of volatilization of the components in the composition (X2) during storage of the composition (X2) can be effectively reduced. Therefore, even if the composition (X2) is stored for a long period of time, the properties of the composition (X2) are unlikely to be impaired. Furthermore, it is possible to particularly suppress the generation of tack in the cured product. For example, it is preferable that the proportion of the monofunctional cationic polymerizable compound (F2) is within the range of 10 to 35% by mass.

Further, particularly when the composition (X2) contains a polyfunctional cationically polymerizable compound (F11) and a polyfunctional cationically polymerizable compound (F12), the polyfunctional cationically polymerizable compound (F11) is is in the range of 30 to 60% by mass, the ratio of the polyfunctional cationically polymerizable compound (F12) is in the range of 15 to 30% by mass, and the ratio of the monofunctional cationically polymerizable compound (F2) is in the range of 15 to 40% by mass. % is preferred. In this case, good storage stability, low viscosity, and good cationic polymerization reactivity of the composition (X2) can be achieved in a well-balanced manner. well achievable.

The cationic polymerizable compound (F) preferably contains a compound having an oxetane group. In this case, the progress of the curing reaction when producing a photocured product from the composition (X2) tends to be moderately moderate, so that the DSC curve of the photocured product has a peak top within the range of 30 ° C. to 260 ° C. Having a certain peak is likely to be realized.

The amount of the compound having an oxetane group is preferably 25% by mass or more and 80% by mass or less with respect to the total amount of the resin component. When the amount of the compound having an oxetane group is 25% by mass or more, the storage stability of composition (X) is particularly likely to be improved. Further, when the amount of the compound having an oxetane group is 80% by mass or less, when the composition (X) is cured by heating after being irradiated with ultraviolet rays, the reaction can be sufficiently progressed easily. Thereby, for example, the glass transition temperature of the cured product can be easily increased, and the linear expansion coefficient of the cured product can be easily decreased. More preferably, the amount of the compound having an oxetane group is 30% by mass or more and 70% by mass or less, and even more preferably 30% by mass or more and 65% by mass or less.

The compound having an oxetane group preferably contains at least one of the compound represented by formula (3) and the compound represented by formula (16). That is, the cationic polymerizable compound (F) preferably contains at least one of the compound represented by formula (3) and the compound represented by formula (16). In this case, the progress of the curing reaction when producing a photocured product from the composition (X2) tends to be moderately moderate. Among these, the compound represented by the formula (16) has a slightly higher reactivity than the compound represented by the formula (3), but tends to lower the viscosity of the composition (X2), and furthermore, the monofunctional cationic polymerizable compound ( Among the components that F2) may contain, it has a high boiling point and a low volatility. Therefore, the compound represented by formula (16) can effectively suppress the increase in the viscosity of composition (X2) over time. Therefore, the composition (X2) can have good applicability even when stored for a long period of time, and can maintain good inkjet applicability.

If the cationic polymerizable compound (F) contains the compound represented by the formula (3) and the compound represented by the formula (16), a photocured product can be produced from the composition (X2) by adjusting the ratio of the two. It is possible to realize a low viscosity and an improvement in storage stability of the composition (X2) while appropriately adjusting the easiness of progress of the curing reaction in the case of using the composition (X2).

The amount of the compound represented by formula (16) is appropriately adjusted so that the composition (X2) has the properties described above. For example, the amount of the compound represented by formula (16) is preferably 10% by mass or more and 40% by mass or less with respect to the total amount of the resin component.

The cationic curing catalyst (G) is not particularly limited as long as it is a catalyst that generates protonic acid or Lewis acid upon receiving light irradiation. The cationic curing catalyst (G) can contain at least one of an ionic photoacid-generating cationic curing catalyst and a nonionic photoacid-generating cationic curing catalyst.

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

The cationic curing catalyst of the nonionic photoacid generator is, for example, at least one selected from the group consisting of nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinones, and N-hydroxyimide phosphonates. can contain the components of

More specific examples of compounds that can be contained in the cationic curing catalyst (G) include Midori Chemical 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-100, NB series (101, 201, etc.), NAI series (100, 1002, 1003, 1004, 101, 105, 106) , 109, etc.), TAZ series (100, 101, 102, 103, 104, 107, 108, 109, 110, 113, 114, 118, 122, 123, 203, 204, etc.), NBC-101, ANC-101, TPS-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, USA;
Irgacure 250, Irgacure 261 and Irgacure 264 from BASF;
CG-24-61 manufactured by Ciba-Geigy;
Adeka Optomer SP-150, Adeka Optomer SP-151, Adeka Optomer SP-170 and Adeka Optomer SP-171 manufactured by ADEKA Corporation;
DAICAT II manufactured by Daicel Corporation;
UVAC1590 and UVAC1591 manufactured by Daicel Cytec Co., Ltd.;
CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758, and CIT-1682 manufactured by Nippon Soda Co., Ltd;
PI-2074, a tetrakis(pentafluorophenyl)borate toluyl cumyl iodonium salt from Rhodia;
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 from Sun-Apro Corporation; and UVI-6992 and UVI-6976 from The Dow Chemical Company. The cationic curing catalyst (G) can contain at least one compound selected from the group consisting of these compounds.

The ratio of the cationic curing catalyst (G) to the total amount of the resin component is preferably 1% by mass or more and 4% by mass or less. When this proportion is 1% by mass or more, the composition (X2) can have particularly good cationic polymerization reactivity. In addition, when this ratio is 4% by mass or less, the composition (X2) can have good storage stability, and since it does not contain an excessive amount of the cationic curing catalyst (G), it is possible to reduce the production cost. is. It is also preferable that the ratio of the cationic curing catalyst (G) to the total amount of the resin component is 0.5% by mass or more and 3% by mass or less. In this case, the reactivity of the composition (X2) can be made moderately moderate, and it becomes easy to realize that the DSC curve of the photocured product has a peak top within the range of 30°C to 260°C.

Composition (X2) may contain a sensitizer (H). Sensitizer (H) contains, for example, one or both of 9,10-dibutoxyanthracene and 9,10-diethoxyanthracene. The ratio of the sensitizer (H) to the total amount of the resin component is preferably in the range of more than 0% by mass and 1% by mass or less. In this case, the sensitizer (H) is less likely to impair the transparency of the cured product, so that the cured product can have good transparency. More preferably, the amount of the sensitizer (H) is more than 0% by mass and 0.8% by mass or less with respect to the total amount of the resin component. In this case, the reactivity of the composition (X2) can be made moderately moderate, and it becomes easy to realize that the DSC curve of the photocured product has a peak top within the range of 30°C to 260°C.

When composition (X) contains any curable component, composition (X) may further contain a moisture absorbent (C). That is, the composition (X1) may further contain the moisture absorbent (C), and the composition (X2) may further contain the moisture absorbent (C). When the composition (X) contains the hygroscopic agent (C), the cured product can have excellent hygroscopicity. It is preferable that the average particle size of the moisture absorbent (C) is 200 nm or less. In this case, the cured product can have high transparency in spite of containing the moisture absorbent (C). Moreover, especially when the composition (X) is applied by an inkjet method, if the average particle size of the moisture absorbent (C) is 200 nm or less, there is an advantage that the composition (X) is less likely to clog nozzles. Furthermore, when the average particle size of the moisture absorbent (C) is 200 nm or less, the moisture absorbent (C) does not easily impair the smoothness of the surface of the sealing material produced from the composition (X). Therefore, the surface of the sealing material can have good smoothness.

As described above, the hygroscopic agent (C) enables the cured product to have high hygroscopicity. 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. Incidentally, the moisture absorption rate is obtained by the following method. A film having a thickness of 10 μm is produced by applying the composition (X) in an argon atmosphere and then irradiating it with ultraviolet rays. The ultraviolet irradiation conditions are, for example, an ultraviolet peak wavelength of 365 nm, an ultraviolet intensity of 3000 mW/cm ² , and an ultraviolet irradiation time of 10 seconds. This film is vacuum-dried using, for example, a vacuum dryer under conditions of a heating temperature of 120° C. and a heating time of 3 hours. Measure the mass of the film after drying. Let this measurement result be the initial mass (M ₀ ). Subsequently, the film is sufficiently moisture-absorbed. For this purpose, for example, the film is exposed to conditions of 85° C. and 85% RH for 24 hours. Measure the mass of the film after moisture absorption. The result of this measurement is called mass after moisture absorption (M). From these initial mass (M ₀ ) and mass after moisture absorption (M), the moisture absorption rate can be calculated by the formula (M−M ₀ )/M ₀ ×100 (% by mass).

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

Zeolite particles having an average particle size of 200 nm or less can be produced, for example, by pulverizing general industrial zeolite. In producing the zeolite particles, the zeolite may be pulverized and then crystallized by hydrothermal synthesis or the like. In this case, the zeolite particles can have particularly high hygroscopicity. Methods for producing such zeolite particles are known from JP-A-2016-69266, JP-A-2013-049602, and the like.

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

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

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

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

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

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

After the ion exchange treatment, the zeolite powder is dried. The drying temperature is, for example, in the range of 150-200° C., and the drying time is, for example, in the range of 2-3 hours. Subsequently, if necessary, the dried zeolite powder is pulverized using a mortar or the like, and then sieved to adjust the particle size. Thereby, zeolite particles having an average particle size of 200 nm or less can be obtained.

Crystallization of zeolite powder can also be carried out in the presence of silicates and alkali metal oxides. A specific example of a method for producing zeolite particles having an average particle size of 200 nm or less in that case will be shown. First, zeolite powder is prepared. _{The zeolite} powder preferably has a _composition of _{aM12O.bSiO2.Al2O3.cMe} . M1 is an alkali metal, proton, or ammonium ion (NH ₄ ⁺ ), Me is an alkaline earth metal, a is a number in the range of 0.01 to 1, and b is in the range of 20 to 80 and c is a number in the range of 0-1. The zeolite powder preferably contains zeolite containing sodium ions, and may contain at least one material selected from the group consisting of A-type zeolite, X-type zeolite and Y-type zeolite among zeolites containing sodium ions. more preferred. It is particularly preferred that the zeolite powder contains 4A-type zeolite among the A-type zeolites. This zeolite powder is physically pulverized. For example, zeolite powder can be physically pulverized by using a bead mill pulverizer.

The physically pulverized zeolite powder is dispersed in a solution containing M2 ₂ O, SiO ₂ and H ₂ O to prepare a slurry. M2 is an alkali metal, preferably K or Na. The M2 ₂ O/H ₂ O molar ratio is, for example, in the range from 0.003 to 0.01, and the SiO2/H2O molar ratio is, for example, in the range from 0.006 to 0.025. The amount of zeolite powder is, for example, 0.5-10 g per 100 ml of solution.

Zeolite powder can be crystallized by heating this slurry in an autoclave. The conditions are, for example, a heating temperature range of 100 to 230° C. and a heating time range of 1 to 24 hours. Subsequently, the zeolite powder is washed and then dried. Thereby, zeolite particles having an average particle size of 200 nm 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 higher, the crystals of the zeolite particles are less likely to be broken, so that the sealing material produced from the composition (X) containing the zeolite particles can have particularly high hygroscopicity. Further, when the pH of the zeolite particles is 10 or less, the zeolite particles are less likely to inhibit curing when the composition (X) is cured.

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

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

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

The average particle size of the moisture absorbent (C) is preferably 10 nm or more and 200 nm or less. If this average particle diameter is 200 nm or less, the cured product can have particularly high transparency. Moreover, when the average particle diameter is 10 nm or more, the moisture absorbent (C) can maintain good moisture absorption. The average particle diameter is the median diameter calculated from the measurement result by the dynamic light scattering method, that is, the cumulative 50% diameter (D50). As a measuring device, Nanotrac Wave series manufactured by Microtrac Bell Co., Ltd. can be used.

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

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

The ratio of the moisture absorbent (C) to the total amount of the composition (X) is preferably 1% by mass or more and 20% by mass or less. If the proportion of the hygroscopic agent (C) is 1% by mass or more, the cured product can have particularly high hygroscopicity. In addition, if 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) must have a sufficiently low viscosity to the extent that it can be applied by an inkjet method. can also The proportion of the moisture absorbent (C) is more preferably 3% by mass or more, and particularly preferably 5% by mass or more. Moreover, 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 high refractive index particles include zirconia particles. When the composition (X) contains high refractive index particles, the cured product can have a high refractive index while maintaining good transparency of the cured product. Therefore, when the cured product is applied to the sealing material 5 in the light-emitting device 1, the extraction efficiency of the light that passes through the sealing material 5 and is emitted to the outside can be improved. The average particle size of the high refractive index particles is preferably in the range of 5 to 30 nm, more preferably in the range of 10 to 20 nm.

The proportion of the high refractive index particles in composition (X) is appropriately designed so that the cured product has a desired refractive index. In particular, the high refractive index particles are preferably contained in the composition (X) so that the cured product has a refractive index 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 a moisture absorbent (C), the composition (X) may further contain a dispersant (D). The dispersant (D) is a surfactant that can be adsorbed on the hygroscopic agent (C). The dispersing agent (D) includes, for example, an adsorbing group (also referred to as an anchor) that can adsorb to the particles of the moisture absorbent (C), and a chain-like adsorbing group that attaches to the particles of the moisture absorbent (C) by adsorbing the particles. or a tail, which is a comb-shaped molecular skeleton. The dispersant (D) includes, for example, an acrylic dispersant whose tail is an acrylic molecular chain, a urethane dispersant whose tail is a urethane molecular chain, and a polyester dispersant whose tail is a polyester molecular chain. It contains at least one component selected from the group consisting of agents.

When the composition (X) contains the dispersant (D), the moisture absorbent (C) can be well dispersed in the composition (X) and in the cured product. Therefore, although the cured product and the sealing material 5 contain the moisture absorbent (C), the transparency of the cured product and the sealing material 5 is less likely to be lowered by the moisture absorbent (C). In addition, 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 less likely to be lowered by the moisture absorbent (C).

Furthermore, the adhesion between the cured product and silicon nitride or silicon oxide is less likely to be reduced by the dispersant (D). This is because the dispersant (D) is easily adsorbed by the moisture absorbent (C) as described above, and thus the dispersant (D) hardly affects the interface between the cured product and the silicon nitride and silicon oxide. It is believed that there is. For this reason, the sealing material 5 can have high adhesion to the base material made of glass. Also, silicon nitride and silicon oxide are sometimes used as materials for the passivation layer 6 in the light emitting device 1 . Therefore, when the passivation layer 6 is made of silicon nitride or silicon oxide, the sealing material 5 can have high adhesion to the passivation layer 6 .

The boiling point of the dispersant (D) is preferably 200°C or higher. In this case, since the dispersant (D) is difficult to volatilize from the composition (X), the storage stability of the composition (X) is further improved.

It is preferable that the dispersant (D) has one or both of a basic polar functional group and an acidic polar functional group as an adsorptive group. In this case, the moisture absorbent (C) can be dispersed particularly well in the composition (X) and in the cured product. This is because the dispersant (D) has one or both of a basic polar functional group and an acidic polar functional group, so that it easily adsorbs to the hygroscopic agent (C), so that the hygroscopic agent (C) It is considered that the effect of dispersing is remarkably expressed.

Dispersant (D) may comprise a polymer. The weight average molecular weight of the polymer is, for example, 1000 or more. Polymers include, for example, hydroxyl-containing carboxylic acid esters, salts of long-chain polyaminoamides and high-molecular-weight acid esters, salts of high-molecular-weight polycarboxylic acids, salts of long-chain polyaminoamides and polar acid esters, and high-molecular-weight unsaturated acid esters. , modified polyurethane, modified polyacrylate, polyether ester type anionic surfactant, naphthalene sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate, polyoxyethylene nonylphenyl ether, polyester polyamine, and stearylamine acetate It contains at least one component selected from the group. When the dispersant (D) contains a polymer, the steric hindrance effect generated when the polymer is adsorbed to the particles of the moisture absorbent (C) can be improved, thereby improving the dispersibility of the moisture absorbent (C).

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

The basic polar functional group in the dispersant (F1) having a basic polar functional group is, for example, at least one selected from the group consisting of an amino group, an imino group, an amide group, an imide group, and a nitrogen-containing heterocyclic group. Including the group of When the dispersant (F1) has a basic polar functional group, the dispersant (F1) easily adsorbs to the moisture absorbent (C), and thus the dispersibility of the moisture absorbent (C) can be improved. The basic polar functional group can particularly enhance the adsorption ability of the dispersant (F1) to the moisture absorbent (C), can particularly improve the dispersibility of the moisture absorbent (C), and can improve the composition (X). It preferably contains an amino group, since it can particularly reduce the viscosity.

The dispersant (F1) having a basic polar functional group is, for example, trade name: Solsperse 24000 (amine value: 41.6 mgKOH/g), trade name: Solsperse 32000 (amine value: 31.2 mgKOH/g), trade name : Solsperse 39000 (amine value: 25.7 mgKOH/g), trade name: Solsperse J100, trade name: Solsperse series manufactured by Nihon Luvre Resol Co., Ltd. such as Solsperse J200; trade names: DISPERBYK-108, DISPERBYK-2013, DISPERBYK -180, DISPERBYK-106, DISPERBYK-162 (amine value: 13 mgKOH/g), product name: DISPERBYK-163 (amine value: 10 mgKOH/g), product name: DISPERBYK-168 (amine value: 11 mgKOH/g), product Name: DISPERBYK-2050 (amine value: 30.7 mgKOH/g), trade name: DISPERBYK-2150 (amine value: 56.7 mgKOH/g), etc. DISPERBYK series manufactured by BYK-Chemie Japan Co., Ltd.; trade name: BYKJET-9151 (amine value: 17.2 mgKOH / g), trade name: BYKJET-9152 (amine value: 27.3 mgKOH / g) BYKJET series manufactured by BYK Chemie Japan Co., Ltd.; and trade name: Ajisper PB821 (amine value: 11.2 mg KOH / g), trade name: Ajisper PB822 (amine value: 18.2 mg KOH / g), trade name: Ajisper PB881 (amine value: 17.4 mg KOH / g) Ajinomoto Fine-Techno Co., Ltd. Ajisper series including.

The amine value of the dispersant (F1) is preferably 10 mgKOH/g or more, more preferably 10 mgKOH/g or more and 30 mgKOH/g or less, and still more preferably 15 mgKOH/g or more and 30 mgKOH/g or less. Moreover, it is preferable that the dispersant (F1) does not have a phosphate group. When the dispersant (F1) has a phosphoric acid group, the acid value derived from the phosphoric acid 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 particularly enhance the storage stability of the composition (X), and can particularly enhance the transparency of the cured product. Furthermore, the adhesion between the cured product and silicon nitride and silicon oxide can be particularly enhanced. Among the components that can be contained in the dispersant (F1), an example of a dispersant having an amino group and no phosphoric acid group includes DISPERBYK-108 manufactured by BYK-Chemie. Examples of dispersants having an amino group and a phosphate group and having an acid value derived from the phosphate group equal to or less than the 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. Dispersant (F2) contains, for example, 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 exhibited. If the amount of the dispersant (D) is 60 parts by mass or less, the adhesion between the cured product and silicon nitride or silicon oxide can be further enhanced. More preferably, the amount of the dispersant (D) is 15 parts by mass or more. The amount of the dispersant (D) is more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less.

It is preferable that the composition (X) does not contain a solvent or has a solvent content of 1% by mass or less. In this case, there is no need to dry the composition (X) to volatilize the solvent when producing a cured product from the composition (X). Moreover, the storage stability of the composition (X) is further enhanced. The solvent content is more preferably 0.5% by mass or less, even more preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. It is particularly preferred that the composition (X) contains no solvent or only unavoidably mixed solvents.

Composition (X) can be prepared by mixing the above components. Composition (X) is preferably liquid at 25°C.

3. Method for Producing Encapsulating Material and Method for Producing Light Emitting Device A method for producing the encapsulating material 5 using the composition (X) and a method for producing the light emitting device 1 will be described.

In the present embodiment, the composition (X) is molded by an inkjet method to form a coating film, and then the composition (X) is irradiated with ultraviolet rays to the coating film, followed by heating to obtain the sealing material 5. is preferably made. In this embodiment, the composition (X) can be applied and molded by an inkjet method.

When applying the composition (X) by an inkjet method, when the composition (X) has a sufficiently low viscosity at room temperature, for example, when the viscosity at 25° C. is 30 mPa·s or less, particularly 15 mPa·s or less. can be molded by applying the composition (X) by an inkjet method without heating.

In the case where the composition (X) has the property of reducing the viscosity when heated, the composition (X) may be heated and then applied by an ink jet method for molding. When the viscosity of the composition (X) at 40° C. is 30 mPa·s or less, particularly 15 mPa·s or less, the viscosity of the composition (X) can be lowered by only slightly heating the composition (X). Composition (X) can be discharged by an inkjet method. The heating temperature of the composition (X) is, for example, 20°C or higher and 50°C or lower.

When the coating film obtained by molding the composition (X) is irradiated with light to be cured, the light with which the coating film is irradiated is, for example, ultraviolet rays. Ultraviolet light means light having a wavelength in the range of 200 nm or more and 410 nm or less. The wavelength of the light with which the coating film is irradiated is preferably in the range of 350 nm or more and 410 nm or less, more preferably 385 nm or more and 405 nm or less. Light with a wavelength of 395 nm is a representative example of the light with which the coating film is irradiated. The wavelength of the light with which the coating film is irradiated is not limited to the above description as long as the coating film can be cured.

The irradiation intensity of the light with which the coating film is irradiated is preferably 20 mW/m ² or more and 20 W/cm ² or less. The irradiation intensity of light is not limited to the above description as long as the coating film can be cured.

The shape of the portion irradiated with light when the coating film is irradiated with light may be an area type having a certain area, or may be 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, it is easy to adjust the time during which the coating film is irradiated with light, and by adjusting this time, it is easy to adjust the integrated amount of light.

When the cured coating film is further heated, the heating temperature is preferably 90° C. or higher. In this case, the curing of the coating film is further advanced, and the coefficient of linear expansion of the sealing material 5 can be easily lowered, thereby realizing that the coefficient of linear expansion of the sealing material 5 is 100 ppm/° C. or more and 130 ppm/° C. or less. It's easy to do. The heating temperature is preferably 150° C. or lower. In this case, the light emitting element 4 is less likely to deteriorate due to heat.

More specifically, for example, first, the support substrate 2 is prepared. A partition wall is formed on one surface of the support substrate 2 by photolithography using, for example, a photosensitive resin material. Subsequently, a plurality of light emitting elements 4 are provided on one surface of the support substrate 2 . 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 the light-emitting element 4 by a coating method such as an inkjet method. Thus, an element array 9 is produced on the support substrate 2 .

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

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

The thickness of the sealing material 5 is preferably 4 μm or more and 50 μm or less, more preferably 4 μm or more and 15 μm or less. As described above, in the present embodiment, it is easy to form small droplets of the composition (X) at a high density by an ink jet method, so it is easy to realize a thin encapsulant 5 having a thickness of 4 μm or more and 15 μm or less. When the encapsulating material 5 is thinned in this way, tensile stress and compressive stress are less likely to occur in the encapsulating material 5 within the light emitting device 1 . Therefore, it becomes easier to realize a flexible light emitting device 1 .

Next, a second passivation layer 62 is provided on the encapsulant 5 . The second passivation layer 62 can be produced by a vapor deposition method such as a plasma CVD method.

Next, an ultraviolet curable resin material is provided on one surface of the support substrate 2 so as to cover the second passivation layer 62, and the transparent substrate 3 is placed on this resin material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate.

Next, the transparent substrate 3 is irradiated with ultraviolet rays from the outside. Ultraviolet rays pass through the transparent substrate 3 and reach the ultraviolet curable resin material. Thereby, the ultraviolet curable resin material is cured, and the second sealing material 52 is produced.

As described above, the sealing material 5 made of the cured composition (X) can have good heat resistance. Therefore, when the passivation layer 6 (second passivation layer 62) is formed over the sealing material 5 by vapor deposition such as plasma CVD, even if the temperature of the sealing material 5 rises, the sealing material 5 deteriorates. hard to do. Moreover, even if the temperature of the organic EL light-emitting device rises during use of the organic EL light-emitting device, the encapsulant 5 is less likely to deteriorate.

Note that the application of the composition (X) according to this embodiment is not limited to the production of the encapsulant 5 for the light emitting element 4 . Composition (X) can be used to produce various optical components that transmit light emitted by a light source. For example, the optical component may be a color resist. That is, for example, the composition (X) may contain a phosphor, and a color resist for a color filter may be produced from the composition (X). In this case, particularly by using the ink jet method, it is easy to form the color resist in the color filter with high density and accuracy. This color filter can be provided, for example, in a display device such as an organic EL display or a micro LED display, which are light emitting devices.

Specific examples of the present invention are presented below. However, the present invention is not limited only to the following examples.

1. Preparation of Composition Compositions of Examples and Comparative Examples were prepared by mixing the components shown in the "Composition" column of the table below.

The details of the components shown in the table are as follows. The viscosities of the following components are values measured using a rheometer (manufactured by Anton Paar Japan, Model No. DHR-2) under conditions of a temperature of 25° C. and a shear rate of 1000 s ⁻¹ .

Also, the glass transition temperature of the following acrylic compound was measured by the following method. A mixture was obtained by mixing an acrylic compound with a photoinitiator (Irgacure 184) in a percentage of 5% by weight relative to the acrylic compound. A molded product obtained by molding this mixture into a film is irradiated with ultraviolet rays from a high-pressure mercury lamp under the conditions of a maximum illuminance of 200 mW/cm ² and an integrated light intensity of 1500 mJ/cm ² , thereby polymerizing the acrylic compound and increasing the thickness. A 10 μm film was produced. Differential scanning calorimetry analysis of this film was performed using a viscoelastic spectrometer "DMS100" manufactured by Seiko Instruments Inc. at a temperature increase rate of 5 ° C./min. It was taken as the glass transition temperature of the compound.

(1) Radically polymerizable compound Polyethylene glycol 200 dimethacrylate: manufactured by Shin-Nakamura Chemical Co., Ltd., viscosity 14 mPa·s (25°C), glass transition temperature 41°C.
- Pentatriestol tetraacrylate: Shin-Nakamura Chemical Co., Ltd., viscosity 200 mPa·s (40°C), glass transition temperature 103°C.

(2) Polyfunctional cationic polymerizable compound Celoxide 8010: manufactured by Daicel, product name Celoxide 8010, compound represented by formula (1a), specific gravity 1.11, viscosity 60 mPa·s, refractive index 1.5071.
OXT-221: manufactured by Toagosei, product number OXT-221, compound represented by formula (3), specific gravity 0.998, viscosity 10 mPa·s, refractive index 1.4538.
• Celoxide 2021P: manufactured by Daicel, trade name Celoxide 2021P, compound represented by formula (1b), viscosity 200 mP·s.
· X-40-2669: manufactured by Shin-Etsu Chemical Co., Ltd., product number X-40-2669, compound represented by formula (10a-1), viscosity 45 mP·s.

(3) Monofunctional cationic polymerizable compound AL-EOX: manufactured by Yokkaichi Gosei, product name AL-EOX, compound represented by formula (16) (3-allyloxymethyl-3-ethyloxetane), viscosity 2 mPa·s.

(4) Photoradical polymerization initiator Irgacure TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, product number Irgacure TPO.

(5) Cationic Photopolymerization Initiator CPI-210S: Photocationic initiator (sulfonium salt) manufactured by San-Apro Co., Ltd., product number CPI-210S.

(6) Sensitizer DETX-s: 2,4-diethylthioxanthen-9-one, manufactured by Nippon Kayaku Co., Ltd., product number DETX-s.
- UVS1331: 9,10-dibutoxyanthracene, manufactured by Kawasaki Kasei Co., Ltd., product number UVS1331.

2. Evaluation Tests The following evaluation tests were conducted for Examples and Comparative Examples. The results are shown in the table.

(1) Transmittance The composition was applied to prepare a coating film with a thickness of 10 μm, and this coating film was irradiated with an LED-UV irradiator (model number E075IIHD, peak wavelength 395 nm) manufactured by Ushio Co., Ltd. in the atmosphere. , UV irradiation intensity of 3 W/cm ² for 5.3 seconds, followed by heating at 100° C. for 5 minutes to prepare a film. The total light transmittance of this film was measured according to JIS K7361-1.

(2) Viscosity The viscosity of the composition was measured using a rheometer (manufactured by Anton Paar Japan, Model No. DHR-2) under conditions of a temperature of 25° C. and a shear rate of 1000 s ⁻¹ .

(3) DSC evaluation of photocured product The composition was applied to prepare a coating film having a thickness of 10 μm, and this coating film was irradiated with an LED-UV irradiator (peak wavelength 395 nm) manufactured by Ushio Co., Ltd. in an atmospheric environment. A photocured material having a thickness of 10 μm was produced by irradiating with ultraviolet rays under the conditions of an irradiation intensity of 3 W/cm ² and an accumulated light amount of 1600 mJ/cm ² . The values of irradiation intensity are based on the results of measurement using UV Power Puck (registered trademark) II, UVV manufactured by Heraeus.

A sample obtained by scraping a part of the photocured product with a spatula is measured using a DSC device (Diamond DSC manufactured by PerkinElmer) under a nitrogen atmosphere at a temperature increase rate of 10 ° C./min and a measurement temperature range of 30 to 270 ° C. Differential scanning calorimetry was performed under the conditions of It was confirmed whether or not the DSC curve thus obtained had a peak with a peak top within the range of 30°C to 260°C. When there was a peak, the temperature indicating the peak top was confirmed, and the calorific value was calculated from the peak.

(4) Linear expansion coefficient of primary cured product The composition was applied to prepare a coating film having a thickness of 100 μm, and this coating film was irradiated with an LED-UV irradiator (peak wavelength: 395 nm) manufactured by Ushio Corporation. A primary cured product having a thickness of 10 μm was produced by irradiating ultraviolet rays under the conditions of an irradiation intensity of 3 W/cm ² and an accumulated light amount of 3000 mJ/cm ² in an atmosphere. The values of irradiation intensity are based on the results of measurement using UV Power Puck (registered trademark) II, UVV manufactured by Heraeus.

The coefficient of linear expansion of this primary cured product in the range from 40 ° C. to 50 ° C. was measured by TMA (Thermomechanical Analysis, thermomechanical analysis) with a load of 0.1 N, a measurement temperature range of 30 ° C. to 240 ° C., and a heating rate of 5. Measured under the conditions of °C/min. As a measuring device, Model No. Q400EM manufactured by TA Instruments was used.

(5) Coefficient of linear expansion of the secondary cured product By heating the primary cured product under the same conditions as in the above “(4) Linear expansion coefficient of the primary cured product” at 100 ° C. for 5 minutes in a dryer, A secondary cured product was obtained. The coefficient of linear expansion of this secondary cured product was measured under the same conditions as in the above-mentioned "(4) Coefficient of linear expansion of primary cured product".

Also, the value of the ratio of the linear expansion coefficient of the primary cured product to the linear expansion coefficient of the secondary cured product was calculated.

(6) Storage properties Using an inkjet head "MH5421F/5421MF" manufactured by Ricoh Co., Ltd., a composition circulation test was performed at a flow rate of 10 ml/min, and the results were evaluated according to the following criteria.
A: The ink (composition) can be ejected continuously for 10 minutes without any problem, and the ink (composition) adheres to the inkjet head in a small amount.
B: The ink (composition) can be ejected continuously for 10 minutes without any problem, and much ink (composition) adheres to the inkjet head.
C: A hole occurs in the ink-jet head that prevents ejection for 10 consecutive minutes.

Claims (13)

Containing a photopolymerizable compound and a photopolymerization initiator,
The photopolymerizable compound contains a radically polymerizable compound,
The photopolymerization initiator contains a photoradical polymerization initiator,
The radically polymerizable compound contains an acrylic compound (A), and the acrylic compound (A) contains a di(meth)acrylic acid ester of polyalkylene glycol having a boiling point of 270° C. or higher,
The DSC curve of a photocured product obtained by irradiating a coating film having a thickness of 10 μm with a peak wavelength of 395 nm under the conditions of an integrated light amount of 800 mJ/cm ² or more and 4000 mJ/cm ² or less in an air atmosphere at normal temperature and pressure is 210 ° C. has a peak with a peak top within the range of from to 240 ° C,
Molded by the inkjet method,
UV curable resin composition. Containing a photopolymerizable compound and a photopolymerization initiator,
The photopolymerizable compound contains a cationically polymerizable compound, the cationically polymerizable compound contains a compound having an oxetane group,
The photoinitiator contains a cationic curing catalyst,
The DSC curve of a photocured product obtained by irradiating a coating film having a thickness of 10 μm with a peak wavelength of 395 nm under the conditions of an integrated light amount of 800 mJ/cm ² or more and 4000 mJ/cm ² or less in an air atmosphere at normal temperature and pressure is 210 ° C. having a peak with a peak top within the range of from to 240 ° C.,
UV curable resin composition. Molded by the inkjet method,
The ultraviolet curable resin composition according to claim 2. The DSC curve of the photocured product obtained by irradiating the coating film having a thickness of 10 μm under the conditions of an irradiation intensity of 3 W/cm ² and an integrated light amount of 1600 mJ/cm ² with a peak wavelength of 395 nm in an air atmosphere at normal temperature and pressure is , having a peak with a peak top within the range of 30° C. to 260° C.,
The ultraviolet curable resin composition according to any one of claims 1 to 3. The calorific value calculated from the peak is 1 J / g or more and 400 J / g or less.
The ultraviolet curable resin composition according to any one of claims 1 to 4. The linear expansion coefficient of the primary cured product obtained by irradiating a coating film having a thickness of 100 μm in an atmospheric atmosphere at normal temperature and pressure with light having a peak wavelength of 395 nm under the conditions of an integrated light amount of 1500 mJ/cm ² or more and 7500 mJ/cm ² or less is 150 ppm. / ° C. or more and 250 ppm / ° C. or less,
The ultraviolet curable resin composition according to any one of claims 1 to 5. The coefficient of linear expansion of the primary cured product obtained by irradiating the coating film having a thickness of 100 μm under the conditions of an irradiation intensity of 3 W/cm ² and an integrated light amount of 3000 mJ/cm ² with a peak wavelength of 395 nm in an air atmosphere at normal temperature and pressure. is 150 ppm/° C. or more and 250 ppm/° C. or less;
The ultraviolet curable resin composition according to claim 6. The ratio of the linear expansion coefficient of the primary cured product to the linear expansion coefficient of the secondary cured product obtained by heating the primary cured product at 100 ° C. for 5 minutes is 1.2 or more.
The ultraviolet curable resin composition according to claim 6 or 7. The linear expansion coefficient of the secondary cured product obtained by heating the primary cured product at 100 ° C. for 5 minutes is 80 ppm / ° C. or more and 140 ppm / ° C. or less.
The ultraviolet curable resin composition according to any one of claims 6 to 8. Does not contain a solvent, or has a solvent content of 1% by mass or less,
The ultraviolet curable resin composition according to any one of claims 1 to 9. for making an optical component that transmits light emitted by a light source,
The ultraviolet curable resin composition according to any one of claims 1 to 10. A method for manufacturing a light-emitting device comprising a light source and an optical component for transmitting light emitted by the light source,
Forming a coating film by molding the ultraviolet curable resin composition according to any one of claims 1 to 11 by an inkjet method,
Producing the optical component by irradiating the coating film with light having a wavelength of 385 nm or more and 405 nm or less and then heating it at a temperature of 90 ° C. or more and 150 ° C. or less.
A method for manufacturing a light-emitting device. A light source and an optical component that transmits light emitted by the light source, wherein the optical component is made of a cured product of the ultraviolet curable resin composition according to any one of claims 1 to 11.
Luminescent device.

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