JP2019210449A - Ultraviolet curable resin composition, method for manufacturing light-emitting device, and light-emitting device - Google Patents

Abstract

To provide an ultraviolet curable resin composition hardly generating satellite when discharged by an inkjet method, and also by which a heat-resistant cured product can be produced.SOLUTION: A maximum peak value of an apparent elongation viscosity-Henky strain curve at a temperature of 25°C of an ultraviolet curable resin composition is 350 mPa/s or less. A value of ratio of the maximum peak value to the viscosity of the ultraviolet curable resin composition at 25°C is 20 or less. The ultraviolet curable resin composition has such a property as to be formed into a cured product having a glass-transition temperature of 80°C or more by curing.SELECTED DRAWING: Figure 1

Description

  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 suitable for producing a sealing material in a light emitting device, and the ultraviolet curable resin composition. The present invention relates to a method for manufacturing a light emitting device using an object, and a light emitting device including the sealing material.

Patent Document 1 discloses that a composite material for protecting a device sensitive to permeation of H ₂ O from the external environment is composed of a polymerizable compound such as an acrylic resin and nano-zeolite whose surface is functionalized. Disclosed is a barrier composite material that includes a suitable dispersion.

Japanese Patent No. 5581332

  SUMMARY OF THE INVENTION An object of the present invention is to provide an ultraviolet curable resin composition capable of producing a cured product that hardly generates satellites and has heat resistance when ejected by an inkjet method, and a method for manufacturing a light emitting device using the ultraviolet curable resin composition And a light-emitting device provided with the sealing material produced from this ultraviolet curable resin composition is provided.

  The maximum peak value of the apparent elongational viscosity-Henkey strain curve at 25 ° C. of the ultraviolet curable resin composition according to one embodiment of the present invention is 350 mPa · s or less. The value of the ratio of the maximum peak value to the viscosity at 25 ° C. of the ultraviolet curable resin composition is 20 or less. The ultraviolet curable resin composition has a property of becoming a cured product having a glass transition temperature of 80 ° C. or higher when cured.

  The manufacturing method of the light-emitting device which concerns on 1 aspect of this invention is a method of manufacturing a light-emitting device provided with a light-emitting element and the sealing material which covers the said light-emitting element. The said manufacturing method includes producing the sealing material by shape | molding the said ultraviolet curable resin composition by the inkjet method, and then irradiating and hardening | curing the said ultraviolet curable resin composition by an ultraviolet-ray.

  The light-emitting device which concerns on 1 aspect of this invention is equipped with the light emitting element and the sealing material which covers the said light emitting element, and the said sealing material consists of hardened | cured material of the said ultraviolet curable resin composition.

  According to one embodiment of the present invention, an ultraviolet curable resin composition capable of producing a cured product that hardly generates satellites and has heat resistance when ejected by an inkjet method, and a light-emitting device using the ultraviolet curable resin composition And a light emitting device provided with a sealing material produced from the ultraviolet curable resin composition.

1 is a schematic cross-sectional view illustrating a first example of an organic EL light emitting device according to an embodiment of the present invention. It is a schematic sectional drawing which shows the 2nd example of the organic electroluminescent light-emitting device in one Embodiment of this invention. 2 is a graph showing an apparent elongational viscosity-Henkey strain curve of the composition of Example 1. FIG. 3 is a graph showing an apparent elongational viscosity-Henkey strain curve of the composition of Comparative Example 1. FIG.

  First, an outline of how the inventor has completed the present invention will be described.

  A light-emitting device including a light-emitting element, such as an organic EL light-emitting device, has been applied to lighting applications, display applications, and the like, and is expected to spread in the future.

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

  In particular, when the light-emitting element includes an organic EL element, the sealing material suppresses generation and growth of dark spots in the organic EL element by suppressing moisture from entering the organic EL element. The dark spot is a portion that does not emit light, which is generated when the organic EL element is deteriorated by moisture.

  The sealing material is made of a material containing, for example, an organic resin selected from an epoxy resin or an acrylic resin and nanozeolite whose surface is functionalized. In particular, when an acrylic resin is used, the sealing material can be manufactured by curing the material by ultraviolet irradiation or the like, so that the sealing material can be manufactured without applying a heat load to the light emitting element.

  High dimensional accuracy is required for a sealing material for a light emitting element. It can be expected that a sealing material with high dimensional accuracy can be produced if a composition for producing the sealing material is ejected by an inkjet method and molded.

  However, when droplets are ejected by the inkjet method, defective droplets called satellites may be generated. The satellite is a droplet that is separated from the original droplet and adheres to a position different from the original position where the droplet is applied on the application target. When the satellite is generated, the dimensional accuracy of the sealing material is deteriorated.

  When a sealing material is manufactured using an inkjet method, the amount of droplets ejected by the inkjet method may have to be reduced as the sealing material becomes thinner. In that case, satellites are particularly likely to occur. Satellites may be suppressed when the composition is heated to a low viscosity and then ejected by the ink jet method, but the composition of the composition changes because the components in the composition tend to volatilize when heated. Easy to do.

  In addition, the sealing material may be heated during the manufacturing process of the light emitting device and when the light emitting device is used, and thus heat resistance is required so that the sealing material is not easily deteriorated by heat.

  Therefore, the inventor has intensively studied to realize an ultraviolet curable resin composition that is difficult to produce satellites when ejected by an ink jet method and can produce a cured product having heat resistance. It came.

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

  The maximum peak value (hereinafter, simply referred to as the maximum peak value) of the apparent elongation viscosity-Henkey strain curve at 25 ° C. of the ultraviolet curable resin composition according to the present embodiment (hereinafter also referred to as the composition (X)). ) Is 350 mPa · s or less. The ratio of the maximum peak value to the viscosity at 25 ° C. of the composition (X) is 20 or less. Furthermore, the composition (X) has a property of becoming a cured product having a glass transition temperature of 80 ° C. or higher when cured.

The apparent elongation viscosity-Henkey strain curve (hereinafter also referred to as a characteristic curve) at 25 ° C. is a curve on a graph in which the horizontal axis is Henkey strain and the vertical axis is the apparent elongation viscosity. In order to obtain the characteristic curve, for example, first, the composition (X) is used by using a capillary breaking type elongation strain type rheometer.
To obtain a diameter-time curve at 25 ° C. A characteristic curve can be obtained by converting the diameter-time curve at 25 ° C. For example, model number CaBER 1 manufactured by Thermo Fisher Scientific Co., Ltd. can be used as the capillary breaking type elongation strain rheometer.

  In order to obtain a diameter-time curve at 25 ° C. using a capillary breaking type extension strain type rheometer, a liquid sample is arranged between an upper plate and a lower plate in the capillary breaking type extension strain type rheometer. In this state, the upper plate is pulled up with respect to the lower plate. The diameter of the sample, which changes as the upper plate is pulled up, is continuously measured with a laser micrometer. The test conditions were: upper plate and lower plate diameter 4 mm, initial gap 1 mm between upper plate and lower plate, upper plate lifting distance (displacement) 3 mm, upper plate lifting time 30 ms, diameter measurement rate 30000 Hz (30,000 times / second). The diameter-time curve at 25 ° C is obtained by plotting the measurement results of the obtained sample diameter on a graph with the horizontal axis representing the elapsed time from the beginning of the upper plate lifting and the vertical axis representing the sample diameter. It is done.

  In specifying the maximum peak value of the characteristic curve of the composition (X), a sample of the composition (X) is measured three times to obtain three characteristic curves. The maximum peak value of each of these three characteristic curves is obtained. The average value of the three obtained peak values is calculated. Let this average value be the maximum peak value of the characteristic curve of the composition (X).

On the other hand, the viscosity at 25 ° C. of the composition (X) is measured using a rheometer at a shear rate of 100 s ⁻¹ . As a rheometer, for example, Model No. DHR-2 manufactured by Anton Paar Japan Co., Ltd. can be used.

  Since the maximum peak value of the composition (X) is 350 mPa · s or less and the value of the ratio of the maximum peak value to the viscosity at 25 ° C. is 20 or less, the composition (X) is applied by the inkjet method. In some cases, defective droplets called satellites are not easily generated. The reason why satellites are less likely to occur is as follows.

  The maximum peak value of the characteristic curve reflects the behavior of the composition (X) in the strain hardening region (shrinkage reduction region) when the composition (X) is stretched, and the maximum peak value is high, It means that the degree of difficulty of deformation when the composition (X) is stretched is high. When ink is applied by an inkjet method, the ink droplet falls so as to draw a tail from the nozzle. That is, the droplet has a ball-shaped portion and a tail-shaped portion from the ball-shaped portion toward the nozzle. When the degree of increase in elasticity that occurs in the process of extending the tail-shaped part becomes large and it becomes difficult to deform, the tail-shaped part is difficult to separate from the nozzle, so that the liquid droplets are separated into a ball-shaped part and a tail-shaped part. Easy to separate. For this reason, the tail-shaped portion tends to be a satellite. When the maximum peak value of the characteristic curve is high, especially when the ratio of the maximum peak value to the viscosity is large, the degree of difficulty of deformation occurring in the tail-shaped part of the droplet is large, and therefore satellites are likely to occur. It is done.

  However, in the present embodiment, since the maximum peak value is 350 mPa · s or less and the ratio of the maximum peak value to the viscosity at 25 ° C. is 20 or less, the composition (X It is considered that the tail-shaped part of the liquid droplets of FIG. Therefore, the tail-shaped portion is easily separated from the nozzle quickly, and therefore the tail-shaped portion is easily absorbed by the ball-shaped portion. Therefore, the droplets are difficult to separate. As a result, it is considered that satellites are hardly generated.

  In addition, if the tail-shaped portion is easily absorbed by the ball-shaped portion, the droplet reaches the target even if the droplet speed is increased when the droplet of the composition (X) is ejected by the inkjet method. The tail-shaped part is easily absorbed by the ball-shaped part. For this reason, by increasing the speed of the liquid droplets, the trajectory of the liquid droplets is less affected by the disturbance, and thus the composition (X) can be precisely applied by the ink jet method.

  In addition, when the droplet of the composition (X) is ejected from the nozzle, the tail-shaped portion is easily deformed, so that the tail-shaped portion is easily separated from the nozzle quickly. That is, the droplets are likely to be quickly separated from the nozzle. For this reason, it is easy to apply the composition (X) by an inkjet method without heating the composition (X).

Furthermore, since the composition (X) has a property of becoming a cured product having a glass transition temperature of 80 ° C. or higher when cured, the cured product can have good heat resistance. Therefore, for example, when the cured product is subjected to a process accompanied by a temperature rise, the cured product is unlikely to deteriorate. Composition (X)
Is more preferable if it becomes a cured product having a glass transition temperature of 90 ° C. or higher by curing, and more preferably if it becomes a cured product having a glass transition temperature of 100 ° C. or higher.

  Therefore, in this embodiment, when applying the composition (X) by the inkjet method, it is difficult for defects to occur, and a cured product having good heat resistance can be produced from the composition (X).

  It is preferable to produce a sealing material that covers the organic EL element in the organic EL light-emitting device from the composition (X). That is, it is preferable that the sealing material which covers the organic EL element in an organic EL light-emitting device consists of the hardened | cured material of composition (X). In this case, in producing the encapsulant, since the satellite is hardly generated even when the composition (X) is applied by an ink jet method, the encapsulant can be produced with high accuracy. In addition, since the encapsulant can have good heat resistance, the encapsulant is less likely to deteriorate over time, and even if the encapsulant is subjected to a treatment with a temperature rise during the manufacture of the organic EL light emitting device. The sealing material is not easily deteriorated. Note that EL is an abbreviation for electroluminescence. The organic EL element is also called an organic light emitting diode.

  The maximum peak value of the composition (X), the ratio of the maximum peak value to the viscosity at 25 ° C., and the glass transition temperature of the cured product are the compositions of the composition (X) described in detail below. Is achievable.

  The viscosity at 25 ° C. of the composition (X) is preferably 1 mPa · s or more and 30 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. In particular, when the viscosity is 30 mPa · s or less, when the composition (X) is applied by an inkjet method, the discharge rate of the composition (X) from the nozzle is difficult to decrease, and satellites are particularly unlikely to occur. The viscosity is more preferably 20 mPa · s or less, and further preferably 15 mPa · s or less. It is also preferable that this viscosity is 5 mPa · s or more.

  It is also preferable that the viscosity of the composition (X) at 40 ° C. is 1 mPa · s or more and 30 mPa · s or less. In this case, even if the viscosity of the composition (X) at normal temperature is any value, the viscosity 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 ink jet method. Further, since the viscosity of the composition (X) can be reduced without greatly heating, the composition (X) can be hardly changed due to volatilization of the components in the composition (X). The viscosity is more preferably 20 mPa · s or less, and further preferably 15 mPa · s or less. It is also preferable that this viscosity is 5 mPa · s or more.

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

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

  It is also preferable that the surface tension of the composition (X) is 20 mN / cm or more and 40 mN / cm or less. In this case, satellites are further less likely to occur when the composition (X) is applied by an inkjet method. This is because when the surface tension is 20 mN / cm or more, when the composition (X) droplet is separated from the nozzle, a tail-like portion is less likely to be formed in the droplet, and the surface tension is 40 mN / cm or less. This is considered to be because the droplet of the composition (X) is particularly easily separated from the nozzle. The surface tension is more preferably 30 mN / cm or more and 40 mN / cm or less, and further preferably 31 mN / cm or more and 38 mN / cm or less.

  Hereinafter, this embodiment will be described in more detail.

1. First, the structure of the light emitting device 1 will be described. The light emitting device 1 includes a light emitting element 4 and a sealing material 5 that covers the light emitting element 4. The sealing material 5 may cover the light emitting element 4 in a state of being in direct contact with the light emitting element 4, or may cover the light emitting element 4 with some layer 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).

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

  A first example of the structure of the light emitting device 1 will be described with reference to FIG. The light emitting device 1 is a top emission type. The light-emitting device 1 includes a support substrate 2, a transparent substrate 3 that faces the support substrate 2 with a gap, a light-emitting element 4 on a surface of the support substrate 2 that faces the transparent substrate 3, and the support substrate 2 and the transparent substrate 3. The sealing material 5 filled between is provided. In the first example, the light emitting device 1 includes a passivation layer 6 that covers the surface of the support substrate 2 facing the transparent substrate 3 and the light emitting element 4. That is, the passivation layer 6 is interposed between the light emitting element 4 and the sealing material 5 covering the light emitting element 4.

  The support substrate 2 is made of, for example, a resin material, but is not limited to this. The transparent substrate 3 is made from a material having translucency. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate. When the light emitting element 4 includes an organic EL element, the organic EL element includes, for example, a pair of electrodes and an organic light emitting layer located between the electrodes. The organic light emitting layer includes, for example, a hole injection layer, a hole transport layer, an organic light emitting layer, and an electron transport layer, and these layers are laminated in the order described above. Although only one light emitting element 4 is shown in FIG. 1, the light emitting device 1 includes a plurality of light emitting elements 4, and the plurality of light emitting elements 4 may constitute an array on the support substrate 2. Good. The passivation layer 6 is preferably made from silicon nitride or silicon oxide.

  A second example of the structure of the light emitting device 1 will be described with reference to FIG. In addition, about the element which is common in the 1st example shown in FIG. 1, the same code | symbol as FIG. 1 is attached | subjected to FIG. 2, and detailed description is abbreviate | omitted suitably. The light emitting device 1 shown in FIG. 2 is also a top emission type. The light-emitting device 1 includes a support substrate 2, a transparent substrate 3 that faces the support substrate 2 with a space therebetween, a light-emitting element 4 on a surface of the support substrate 2 that faces the transparent substrate 3, and a sealing that covers the light-emitting element 4. A 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 stacked 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 constitute an array 9 (hereinafter referred to as an element array 9) on the support substrate 2. The element array 9 also includes a partition wall 7. The partition wall 7 is on the support substrate 2 and partitions between the two adjacent light emitting elements 4. The partition wall 7 is produced, for example, by molding a photosensitive resin material by a photolithography method. The element array 9 also includes connection wirings 8 that electrically connect the electrodes 43 and the electron transport layers 424 of the adjacent light emitting elements 4. The connection wiring 8 is provided on the partition wall 7.

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

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

  The sealing material 5 in the light emitting device 1 having the structure exemplified above can be produced from the ultraviolet curable resin composition according to this embodiment. That is, the ultraviolet curable resin composition is used for producing the sealing material 5 for the light emitting element 4. In other words, the ultraviolet curable resin composition is preferably a composition for producing a sealing material, a composition for encapsulating a light emitting element, or a composition for producing a light emitting device.

2. Ultraviolet curable resin composition The ultraviolet curable resin composition (hereinafter also referred to as composition (X)) will be described.

  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 (G). The curable component may contain a radical polymerizable compound and a photo radical polymerization initiator (B).

  When the curable component contains a radical polymerizable compound and a photo radical polymerization initiator (B), the radical polymerizable compound preferably contains an acrylic compound (A). In this case, when the composition (X) is irradiated with ultraviolet rays, the photoradical polymerization initiator 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) (hereinafter also referred to as the composition (X1)) containing the acrylic compound (A) and the radical photopolymerization initiator (B) will be described in more detail.

  As described above, the composition (X1) contains the 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 entire acrylic compound (A) is more preferably 30 mPa · s or less, and particularly preferably 20 mPa · s or less. Moreover, the viscosity of the whole acrylic compound (A) is 3 mPa * s or more, for example.

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

  The 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 thus can increase the heat resistance of the cured product and the sealing material 5. It is preferable that the quantity of a polyfunctional acrylic compound (A1) is 50 to 100 mass% with respect to the whole acrylic compound (A). The acrylic compound (A) may contain only the polyfunctional acrylic compound (A1).

  The polyfunctional acrylic compound (A1) is, 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, cyclohexane dimethanol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, pentatriestol tetra Acrylate, propoxylated (2) neopentyl glycol diacrylate, trimethylolpropane triacryl , 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, 1,4-butanediol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2 N-butyl-2-ethyl-1,3-propanediol diacrylate, hydroxypivalate neopentyl glycol diacrylate, hydroxypivalate trimethylolpropane triacrylate, ethoxylated phosphate triacrylate, ethoxylated tripropylene glycol diacrylate , Neopentyl glycol modified trimethylolpropane diacrylate, stearic acid modified pentaerythritol diacrylate, tetramethylolpropane triacrylate Rate, tetramethylol methane triacrylate, caprolactone modified trimethylol propane triacrylate, propoxylate glyceryl triacrylate, tetramethylol methane 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 ( Meta Acrylate, containing at least one compound selected ethoxylated trimethylolpropane triacrylate, and from the group consisting of propoxylated trimethylol propane triacrylate.

  The acrylic equivalent of the polyfunctional acrylic compound (A1) is preferably 150 g / eq or less, and 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, and 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. The polar group is, for example, at least one of an OH group and an NHCO group. In this case, the shrinkage when the composition (X1) is cured can be particularly reduced. Furthermore, the adhesion between the cured product and an inorganic compound such as silicon nitride or silicon oxide can be enhanced. The polyfunctional acrylic compound (A1) is particularly selected from the group consisting of tricyclodecane dimethanol diacrylate, bisphenol A polyethoxydiacrylate, bisphenol F polyethoxydiacrylate, trimethylolpropane triacrylate and pentatriestol tetraacrylate. It is preferable to contain at least one compound. These compounds can particularly reduce shrinkage when the composition (X1) is cured. Furthermore, these compounds can also improve 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).

^{_{CH 2 = CR 1 -COO- (R}} 3 -O) n -CO-CR 2 = CH 2 ... (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, Several R < ³ > may mutually be same or different.

The compound (A11) has a structure represented by the formula (1), in particular, the number of carbon atoms of R ^{3 in} the formula (1) is 3 or more, so that it is difficult to increase the affinity of the sealing material 5 with water. For this reason, the light emitting element 4 is not easily 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 the formula (1), and in particular, by having two (meth) acryloyl groups in one molecule, 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 increased. Moreover, n of Formula (1) is an integer of 1-12, for example.

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

  The compound (A11) particularly preferably contains the 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 the formula (1) and having a boiling point of 270 ° C. or higher. In this case, the acrylic compound (A) is unlikely to volatilize from the composition (X) during storage of the composition (X) and when the composition (X) is heated. Therefore, the storage stability of the composition (X) is not easily impaired. Moreover, even if the compound (A12) remains unreacted in the cured product and the sealing material 5 of the composition (X), outgas resulting from the compound (A12) is generated from the cured product and the sealing material 5. Hateful. Therefore, voids due to outgas are unlikely 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. However, if the gap is not easily generated, moisture does not easily enter the light emitting element 4. The boiling point is a boiling point under normal pressure obtained by converting a boiling point under reduced pressure, and can be determined, for example, by the method shown in Science of Petroleum, Vol. II. P.1281 (1938). The boiling point of the compound (A12) is more preferably 280 ° C. or higher.

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

  The viscosity of the compound (A12) at 25 ° C. is preferably 25 mPa · s or less. In this case, the compound (A12) can reduce the viscosity of the composition (X). The viscosity at 25 ° C. of the compound (A12) is more preferably 25 mPa · s or less, further preferably 20 mPa · s or less, and particularly preferably 15 mPa · s or less. Further, the viscosity of the 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.

  Compound (A12) is, for example, a group consisting of di (meth) acrylic acid ester of alkylene glycol, di (meth) acrylic acid ester of polyalkylene glycol, and di (meth) acrylic acid ester of alkylene oxide-modified alkylene glycol. 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, it is preferable that the carbon number of R < ³ > in Formula (1) is 4-12. R ³ may be linear or branched. In particular, di (meth) acrylic acid esters of alkylene glycol 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 -It is preferable to contain at least one compound selected from the group consisting of nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, and 1,12-dodecanediol dimethacrylate. Further, di (meth) acrylic acid ester of alkylene glycol is Sartomer part number SR213, Osaka Organic Chemical Industry part number V195, Sartomer part number SR212, Sartomer part number SR247, Kyoei Chemical Co., Ltd. Product name Light acrylate NP-A, Sartomer product number SR238NS, Osaka Organic Chemical Industry product number V230, Daicel product number HDDA, Kyoei Chemical Industry product number 1,6HX-A, Osaka Organic Chemical Industry Co., Ltd. Product No. V260, Kyoei Chemical Industry Co., Ltd. product number 1,9-ND-A, Shin-Nakamura Chemical Industry Co., Ltd. product number A-NOD-A, Sartomer Co., Ltd. product number CD595, Sartomer Co., Ltd. product number SR214NS, Shin-Nakamura Product number BD manufactured by Kagaku Kogyo Co., product number SR297 manufactured by Sartomer, product number SR248 manufactured by Sartomer, Kyoei Chemical Product name Light Ester NP, Sartomer product number SR239NS, Kyoei Chemical Co., Ltd. product name light ester 1,6HX, Shin-Nakamura Chemical Co., Ltd. product number HD-N, Kyoei Chemical Industry Co., Ltd. product name Light Ester 1,9ND, product number NOD-N manufactured by Shin-Nakamura Chemical Co., Ltd., product name light ester 1,10DC manufactured by Kyoei Chemical Industry Co., Ltd., product number DOD-N manufactured by Shin-Nakamura Chemical Co., Ltd., and product number SR262 manufactured by Sartomer It is preferable to contain at least one compound selected from the group.

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

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

  The percentage of components having a boiling point of 270 ° C. or higher in the acrylic compound (A) is preferably 80% by 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 in the acrylic compound (A) including the compound (A12) is 80% by mass or higher. Is preferred. In this case, the storage stability of the composition (X) is not particularly impaired, and outgas is not particularly easily generated from the cured product and the sealing material 5. More preferably, the percentage of the components having a boiling point of 280 ° C. or higher in the acrylic compound (A) is 80% by mass or higher.

  The compound (A11) may contain a compound (A13) other than the 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, the compound (A14) can contain at least one selected from the group consisting of trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, for example. When the acrylic compound (A) contains the compound (A14), the compound (A14) can particularly increase the glass transition temperature of the cured product, and thus can particularly increase the heat resistance of the cured product and the color resist 1. it can.

  When the acrylic compound (A) includes 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. The percentage of the compound (A14) is more preferably 10% by mass or more. In this case, the glass transition temperature of the cured product can be particularly increased. Moreover, the viscosity increase of the composition (X) resulting from a compound (A14) does not arise easily that a compound (A14) is 25 mass% or less. When the percentage of the compound (A14) is 20% by mass or less, the viscosity increase of the composition (X) is particularly difficult to occur.

When the acrylic compound (A) contains the compound (A11) having a structure represented by the formula (1), the compound (A11) preferably does not contain a compound having a value of n of 5 or more in the formula (1). . In the case where (R ³ —O) _n is a polyethylene glycol skeleton, it is particularly preferable not to include a compound in which the value of n in formula (1) is greater than 5. Even when compound (A11) contains a compound having a value of n in formula (1) greater than 5, the percentage of the compound having a value of n in formula (1) greater than 5 relative to acrylic compound (A) is 20 It is preferable that it is below mass%. Further, even when the compound (A11) includes a compound having a value of n in the formula (1) larger than 5, it is preferable that the compound (A11) does not include a compound having a value of n larger than 9. More preferably, no compound with a value greater than 7 is included. In these cases, the viscosity increase of the composition (X) is particularly difficult to occur.

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

  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. If there is more quantity of a monofunctional acrylic compound (A2) than 0 mass%, the shrinkage | contraction at the time of hardening of a composition (X1) can be suppressed. Moreover, if the quantity of a monofunctional acrylic compound (A2) is 50 mass% or less, the quantity of a polyfunctional acrylic compound (A1) can be 50 mass% or more, and the heat resistance of hardened | cured material and the sealing material 5 is possible. Can be particularly improved. The amount of the monofunctional acrylic compound (A2) is more preferably 5% by mass or more, and further preferably 30% by mass or less.

  Monofunctional acrylic compound (A2) is, 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, phenoxy Ethyl acrylate, cyclohexyl (meta ) Acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylation Tribromophenyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl acrylate ethylene oxide adduct, 2-phenoxyethyl acrylate propylene oxide adduct, acryloylmorpholine, isobornyl acrylate, dicyclopentanyl acrylate, Phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1, - cyclohexanedimethanol monoacrylate, containing at least one compound selected from the group consisting of 3-methacryloyloxy methyl cyclohexene oxide, and 3-acryloyloxy methyl cyclohexene oxide.

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

Examples of the compound having an alicyclic structure include phenoxyethyl acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl acrylate, methylphenoxyethyl acrylate, and 4-t-butyl. Cyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl acrylate ethylene oxide adduct, 2-phenoxyethyl acrylate propylene oxide adduct, Acryloylmorpholine, isobornyl acrylate, dicyclopentanyl acrylate, phenoxydiethyl Glycol acrylate, containing at least one compound selected from the group consisting of 2-hydroxy-3-phenoxypropyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate.

  The number of members of the cyclic ether structure in the compound having a cyclic ether structure is preferably 3 or more, and 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, and 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 preferable to further contain at least one compound. In this case, the adhesion between the cured product and the sealing material 5 and the member made of an inorganic material is improved. For this reason, a gap is hardly formed between the sealing material 5 and the passivation layer 6, and moisture does not easily enter the light emitting element 4 through the gap.

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

  Compound (A41) is, for example, 3- (trimethoxysilyl) propyl acrylate (for example, product number KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) and (meth) acryl group-containing alkoxysilane oligomer (for example, product number KR-513 manufactured by Shin-Etsu Chemical Co., Ltd. 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 with respect to acrylic compound (A) The percentage of 3- (trimethoxysilyl) propyl needs to be 10% by mass or less.

  Compound (A42) contains acid phosphooxy (meth) acrylate, for example, acid phosphooxypolyoxypropylene glycol monomethacrylate.

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

  When the acrylic compound (A) contains at least one compound selected from the group consisting of the compound (A41), the compound (A42) and the compound (A43), the compound (A41) and the compound (A42) with respect to the acrylic compound (A) ) And the total amount of the compound (A43) are preferably 0.5% by mass or more and 20% by mass or less, and 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 droplets of the composition (X) discharged by the ink jet method are reduced in size, it is possible to make it difficult to generate satellites. That is, it is easy to reduce the size of the droplets without generating satellites. For this reason, it becomes easy to form small droplets of the composition (X) by the ink jet method at high density, and therefore, the sealing material 5 can be easily thinned. When the acrylic compound (A) contains a compound having an isobornyl skeleton, the percentage of the compound having an isobornyl skeleton with respect to the entire acrylic compound (A) is preferably more than 0% by mass and 80% by mass or less. When the percentage is greater than 0% by mass, it is particularly easy to reduce the size of the droplet. Moreover, outgas is easy to reduce because this percentage is 80 mass% or less. In particular, in order to reduce outgas, the percentage of the compound having an isobornyl skeleton relative to the entire acrylic compound (A) is preferably 40% by mass or less, and 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 a component (a) composed of at least one compound having a viscosity at 25 ° C. of 20 mPa · s or less. In this case, the component (a) can lower the viscosity of the composition (X1). The compound contained in the 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 the component (a) to the total amount of the acrylic compound (A) is preferably 50% by mass or more and 100% by mass or less. In this case, the composition (X1) can have a particularly low viscosity, and the composition (X1) can be particularly easily applied by an ink jet method. The proportion of component (a) is more preferably 60% by mass or more, and further preferably 70% by mass or more. Moreover, it is more preferable that the ratio of a component (a) is 95 mass% or less, and it is still more preferable that it is 90 mass% or less.

  It is preferable that a component (a) contains the compound which has a glass transition temperature of 80 degreeC or more. That is, the component (a) preferably contains a compound having a viscosity at 25 ° C. of 20 mPa · s or less 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). The component (a) is more preferable if it contains a compound having a glass transition temperature of 90 ° C. or higher, and more preferably if it contains a compound having a glass transition temperature of 100 ° C. or higher. Although there is no restriction | limiting in the upper limit of the glass transition temperature of the compound contained in a component (a), For example, it is 150 degrees C or less.

  Component (a) is, for example, a group consisting of isobornyl acrylate, dicyclopentanyl acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol 200 dimethacrylate, and polyethylene glycol 200 diacrylate. It 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 It is preferable to do. These compounds can particularly reduce the maximum peak value of the composition (X1). Therefore, the maximum peak value of the composition (X1) is 350 mPa · s or less, and the value of 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), can increase the glass transition temperature of the cured product, and can 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 the acrylic compound (A) is 50% by mass or more. It is preferable that it is 95 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 when the composition (X1) is cured can be reduced. The total amount of these compounds is more preferably 60% by mass or more, and further preferably 70% by mass or less.

  The acrylic compound (A) contains a component (b) composed 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. Also good. Component (b) can enhance the adhesion between the cured product and an inorganic compound such as silicon nitride or silicon oxide. The compound contained in the 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 a compound contained in component (a).

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

  The ratio of the component (b) to the total amount of the acrylic compound (A) is preferably 5% by mass or more and 50% by mass or less. The adhesiveness of hardened | cured material increases more that the ratio of a component (b) is 5 mass% or more. 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) is further lowered to reduce the composition (X1). Can be easily formed by an inkjet method. The proportion of component (b) is more preferably 30% by mass or more, and further preferably 40% by mass or less. The acrylic compound (A) may not contain the component (b), and in this case, the maximum peak value of the composition (X1) can be particularly lowered.

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

  The acrylic compound (A) is a component (c) that is at least one component selected from the group consisting of a compound represented by the following formula (100), morpholine acrylate, diethyl acrylamide, dimethylaminopropyl acrylamide, and pentamethylpiperidyl methacrylate. ) Is also preferable. By the component (c), the sealing material 5 made from the composition (X) can be given adhesion to a member made of an inorganic material such as the passivation layer 6. The compound contained in component (c) may be a compound contained in component (a).

In the 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, the number of carbon atoms in X is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less. The divalent hydrocarbon group is, for example, a methylene group, an ethylene group or a propylene group. 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 carbon number of the alkyl group is 1
It is preferably 8 or less. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. The alkyl group may be straight 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. When the alkyl group is an octyl group, the octyl group may be, for example, a t-octyl group. It is particularly preferable that the alkyl group is a methyl group or a t-butyl group. 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, it is preferable that at least one of R ⁶ and R ⁷ among R ¹ to R ¹¹ is an alkyl group or —R ¹² —OH, and each of the remaining is H. Among R ¹ to R ¹¹ , it is particularly preferred that only R ⁶ is an alkyl group or —R ¹² —OH, and the remaining each is H. In this case, the compound represented by the formula (100) can have good reactivity, and is particularly easy to impart adhesion to the sealing material 5 with a member made of an inorganic material. This is because the cyclohexane ring in the compound represented by the formula (100) has a boat-type conformation, and the bulky alkyl group or —R ¹² —OH at the 4-position is easily located at the pseudo-equatorial position. it is conceivable that. It is considered that the reactivity of the (meth) acryloyl group in the compound represented by the formula (100) is increased when the compound represented by the formula (100) has such a structure. Further, when the compound represented by the formula (100) has such a structure, the compound represented by the formula (1) can increase the free volume in the sealing material 5. Therefore, it is considered that the interface free energy between the sealing material 5 and the member made of an inorganic material tends to be small, and the adhesion between the sealing material 5 and the member made of an inorganic material tends to be high. The higher the bulk alkyl group or -R ¹² -OH, alkyl or -R ¹² -OH is likely located in pseudo equatorial position. From this point of view, it is preferable that preferably larger the number of carbon atoms in the alkyl group or -R ¹² -OH, also an alkyl group or -R ¹² -OH and a branch. For example, the alkyl group or —R ¹² —OH is preferably a t-butyl group.

In the formula (100), it is also preferable that an alkyl group or —R ¹² —OH is connected to each of the 3-position and 5-position 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 remaining is H. 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; More preferably, it is H. Among 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 rest It is also more preferable that each is H. Also in this case, the compound represented by the formula (100) can have good reactivity, and is particularly easy to impart adhesion to the sealing material 5 with a member made of an inorganic material. This is because the cyclohexane ring in the compound represented by the formula (100) has a boat-type conformation, and a bulky alkyl group or —R ¹² —OH in each of the 3-position and 5-position is located in the pseudo-equatorial position. This is probably because it is easy. For this reason, the reactivity of the (meth) acryloyl group in the compound represented by the formula (100) is increased as in the case where an alkyl group or —R ¹² —OH is connected only to the 4-position of the cyclohexane ring, and It is considered that the adhesion between the sealing material 5 and the member made of an inorganic material tends to be high. The higher the bulk alkyl group or -R ¹² -OH, alkyl or -R ¹² -OH is likely located in pseudo equatorial position. From this point of view, it is preferable that preferably larger the number of carbon atoms in the alkyl group or -R ¹² -OH, also an alkyl group or -R ¹² -OH and a branch. For example, the 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, the number of carbon atoms in R ¹² is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less. R ¹² is, for example, a methylene group, an ethylene group or a propylene group. R ¹² is particularly preferably 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 that 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 represented by formula (100) can have a particularly low viscosity, so that the composition (X) can have a particularly low viscosity. Therefore, the composition (X) is particularly easy to mold by the ink jet method.

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

  It is particularly preferred that the compound (A1) contains at least one of the compound represented by the formula (110) and the compound represented by the formula (120). In this case, the composition (X) can be particularly easily reduced in viscosity, the glass transition temperature of the sealing material 5 can be particularly easily increased, and the adhesion between the sealing material 5 and the member made of an inorganic material can be particularly easily increased. Moreover, since the compound shown to Formula (110) and the compound shown to Formula (120) are hard to volatilize, it is easy to improve the storage stability of composition (X).

  It is also preferred that the compound (A1) contains at least one component selected from the group consisting of morpholine acrylate, diethyl acrylamide, dimethylaminopropyl acrylamide and pentamethylpiperidyl methacrylate. These compounds contain nitrogen and have a good affinity with the inorganic material, and therefore, it is particularly easy to improve the adhesion between the sealing material 5 and the member made of the inorganic material. Moreover, the viscosity of these compounds is low, and therefore these compounds are difficult to increase the viscosity of the composition (X). Furthermore, since these compounds are less likely to volatilize, the storage stability of the composition (X) is likely to be improved.

  The amount of the compound (A1) relative to the entire acrylic compound (A) is preferably 5% by mass or more and 80% by mass or less. In this case, the sealing material 5 can achieve both a high glass transition temperature and adhesion with a member made of an inorganic material. The amount of the 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) is contained and the hygroscopic agent (C) contains zeolite particles, the acrylic compound (A) contains nitrogen. It is preferable not to contain the compound which has. For this reason, it is preferable that an acrylic compound (A) does not contain any of said morpholine acrylate, diethyl acrylamide, dimethylaminopropyl acrylamide, and pentamethyl piperidyl methacrylate. In this case, the viscosity of the composition (X1) is hardly increased during the storage of the composition (X1). This is considered to be because when the composition (X1) contains a nitrogen-containing compound and a hygroscopic agent (C), the nitrogen-containing compound and the hygroscopic agent (C) easily react.

  The composition (X1) may further contain a radical polymerizable compound (E) other than the acrylic compound (A). The radical polymerizable compound (E) is composed of a polyfunctional radical polymerizable compound (E1) having two or more radical polymerizable functional groups in one molecule and a monofunctional having only one radical polymerizable functional group in one molecule. Either one or both of the radical polymerizable compound (E2) can be contained. The amount of the radical polymerizable compound (E) relative to the total amount of the acrylic compound (A) and the radical polymerizable compound (E) is, for example, 10% by mass or less. The polyfunctional radically polymerizable compound (E1) is, for example, a group consisting of an aromatic urethane oligomer, an aliphatic urethane oligomer, an epoxy acrylate oligomer, a polyester acrylate oligomer, and other special oligomers having two or more ethylenic double bonds in one molecule. You may contain the at least 1 sort (s) of compound selected from these. Monofunctional radically polymerizable compound (E2) is, 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 monooxide, 1,2-epoxydodecane, 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. Examples of the radical photopolymerization initiator (B) include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazoles. It contains at least one compound selected from the group consisting of a compound, a ketoxime ester compound, a borate compound, an azinium compound, a metallocene compound, an active ester compound, a compound having a carbon halogen bond, and an alkylamine compound. The amount of the photo radical polymerization initiator (B) with respect to 100 parts by mass of the composition (X1) is, for example, 1 part by weight or more and 10 parts by weight or less.

  The radical photopolymerization initiator (B) preferably contains a component having photobleaching properties. The component having photobleaching property preferably contains an acyl phosphine oxide photoinitiator, and 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 includes a component having at least one of a 9H-thioxanthen-9-one skeleton and an anthracene skeleton.

  The radical photopolymerization initiator (B) preferably contains an oxime ester-based photoinitiator regardless of the presence or absence of photobleaching properties from the viewpoint of improving curability and making it difficult to generate outgas from the cured product.

  The oxime ester-based photoinitiator is used in order to prevent contamination of the composition (X) and the production apparatus due to decomposition products from the composition (X), and to further prevent outgassing from the cured product. It is preferable to include a compound having a ring, more preferable to include a compound having a condensed ring including an aromatic ring, and further preferable to include a compound having a condensed ring including a benzene ring and a hetero ring.

  Examples of the oxime ester photoinitiator include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], and ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), JP-A No. 2000-80068, JP-A No. 2001-233842, JP-T 2010-527339, JP-T 2010- It can contain at least one compound selected from the group consisting of oxime ester-based photoinitiators described in Japanese Patent No. 527338, Japanese Patent Application Laid-Open No. 2013-041153, Japanese Patent Application Laid-Open No. 2015-93842, and the like. Oxime ester photoinitiators are commercially available Irgacure OXE-02 (manufactured by BASF) having a carbazole skeleton, Adeka Arcles NCI-831, N-1919 (manufactured by ADEKA) and TR-PBG-304 (Changzhou Power Electronics) New Material Company), Irgacure OXE-01 having a diphenyl sulfide skeleton, Adeka Arcles NCI-930 (manufactured by ADEKA), TR-PBG-345 and TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Material Company) , And TR-PBG-365 having a fluorene skeleton (manufactured by Changzhou Power Electronics New Materials Co., Ltd.) and SPI-04 (manufactured by Sanyo) may be contained. 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 hardly colored by photobleaching. It is also preferable that the oxime ester photoinitiator contains a compound having a carbazole skeleton because exposure sensitivity is likely to increase.

  It is also preferred that the oxime ester photoinitiator contains two or more compounds. In this case, for example, when the oxime ester photoinitiator contains two or more compounds having different exposure sensitivities, the amount of the photoradical polymerization initiator (B) can be reduced while maintaining good exposure sensitivity. Therefore, outgas can be further hardly generated from the cured product.

  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 accelerates the radical generation reaction of the photoradical polymerization initiator (B), can improve the reactivity of radical polymerization, and can improve the crosslinking density. Examples of the sensitizer include 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, At least selected from the group consisting of 4,4′-bis (diethylamino) benzophenone, p-dimethylaminobenzaldehyde, and p-diethylaminobenzaldehyde It may contain one compound.

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 with respect to 100 parts by mass of the solid content of the composition (X1). Part to 3 parts by mass. When the content of the sensitizer is in such a range, the composition (X1) can be cured in the air, and the composition (X1) needs to be cured in an inert atmosphere such as a nitrogen atmosphere. Disappear.

  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.

  Component of composition (X) (hereinafter also referred to as composition (X2)) when curable component in composition (X) contains cationically polymerizable compound (F) and cationic curing catalyst (G) Will be described.

  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 cation polymerizable compound (F1) is either or both of a polyfunctional cation polymerizable compound (F11) having no siloxane skeleton and a polyfunctional cation polymerizable compound (F12) having a siloxane skeleton. Can be contained.

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

  The polyfunctional cationic polymerizable compound (F11) is, for example, from the group consisting of a polyfunctional alicyclic epoxy compound, a polyfunctional heterocyclic epoxy compound, a polyfunctional oxetane compound, an alkylene glycol diglycidyl ether, and an alkylene glycol monovinyl monoglycidyl ether. Among the selected compounds, contains at least one 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 hydrocarbon group preferably has 1 to 20 carbon atoms. 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 2 to 2 carbon atoms such as 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 preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

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

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

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

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

  The polyfunctional heterocyclic epoxy compound contains, for example, a trifunctional epoxy compound as shown in the following formula (2).

  The polyfunctional oxetane compound contains, for example, a bifunctional oxetane compound as shown in the following formula (3).

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

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

  More specifically, the polyfunctional cationically polymerizable compound (F11) includes, for example, Celcel 2021P and Celoxide 8010 manufactured by Daicel, TEPIC-VL manufactured by Nissan Chemical, OXT-221 manufactured by Toagosei, and 1, manufactured by Yokkaichi Chemical. 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 can be contained.

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

  It is preferable that especially a polyfunctional alicyclic epoxy compound contains either one or both among the compound shown to Formula (1), and the compound shown to Formula (20). In this case, the composition (X2) can have higher cationic polymerization reactivity.

  When a polyfunctional alicyclic epoxy compound contains the compound shown in Formula (1), it is preferable that the compound shown in Formula (1) contains the compound shown in Formula (1a). In this case, the composition (X2) can have a particularly low viscosity as well as higher cationic polymerization reactivity.

  In particular, since the compound represented by the formula (20) has a low viscosity, when the compound represented by the formula (20) is contained, the composition (X2) can have good ultraviolet curability, Can have a low viscosity. Furthermore, the compound represented by the formula (20) has a property of being less volatile in spite of having a low viscosity. Therefore, even if the composition (X2) contains a 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). For this reason, composition (X2) can be made low-viscosity by impairing storage stability by containing the compound shown in Formula (20).

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

  The compound represented by formula (20) may contain four stereoisomers based on the configuration of two epoxy rings. The compound represented by the formula (20) may include any of the four stereoisomers. That is, the compound represented by the 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 based on the entire epoxy compound (A1). Is preferable, and if it is 5 mass% or less, it is still more preferable. In this case, the heat resistance of the cured product can be improved. In addition, the ratio of the specific stereoisomer in the compound shown in Formula (20) can be calculated | required based on the peak area ratio which appears in the chromatogram obtained by a gas chromatography.

  In order to reduce the amount of exo-endo and endo-endo in the compound represented by formula (20), a method of precision distillation of the compound represented by formula (20), column chromatography using silica gel or the like as a packing material. An appropriate method such as a method of applying a graphic can be applied.

  When the composition (X2) contains the polyfunctional cation polymerizable compound (F11), the ratio of the polyfunctional cation 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 compound having cationic polymerizability in the composition (X2), and includes a polyfunctional cationic polymerizable compound (F1) and a monofunctional cationic polymerizable compound (F2). If the ratio of the polyfunctional cationically polymerizable compound (F11) is 5% by mass or more, the composition (X2) can have particularly excellent reactivity during the photocationic polymerization reaction, whereby the cured product has high strength. (Hardness). Moreover, if the ratio of the polyfunctional cation polymerizable compound (F11) is 95% by mass or less, when the composition (X2) contains the hygroscopic agent (C), the hygroscopic agent (C ) Can be easily dispersed particularly uniformly. The ratio of the polyfunctional cation polymerizable compound (F11) is more preferably 12% by mass or more, further preferably 15% by mass or more, further preferably 20% by mass or more, and 25% by mass or more. Is particularly preferred. Further, the ratio of the polyfunctional cation polymerizable compound (F11) is more preferably 85% by mass or less, and further preferably 60% by mass or less. For example, the ratio of the polyfunctional cation polymerizable compound (F11) is preferably in the range of 20 to 60% by mass.

  When the polyfunctional cation polymerizable compound (F11) contains a polyfunctional alicyclic epoxy compound, the polyfunctional alicyclic epoxy compound may be a part of the polyfunctional cation polymerizable compound (F11), and all It may be. The ratio of the polyfunctional alicyclic epoxy compound to the polyfunctional cationic polymerizable compound (F11) is preferably in 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 the improvement of the ultraviolet curable property 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 cation polymerizable functional groups per molecule of the polyfunctional cation polymerizable compound (F12) is preferably 2 to 6, more preferably 2 to 4. The polyfunctional cation polymerizable compound (F12) can contribute to the improvement of the cationic polymerization reactivity of the composition (X2), and can contribute to the improvement of the heat discoloration of the cured product and the sealing material 5. When the heat-resistant discoloration of the sealing material 5 is high, it is possible to suppress the deterioration with time of the light emission intensity and the change with time of the emission color of the light emitting device 1 including the sealing material 5. In addition, the polyfunctional cation polymerizable compound (F12) can 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. It is also possible. Moreover, when the composition (X2) contains a hygroscopic agent, the polyfunctional cation polymerizable compound (F12) can contribute to the improvement of the dispersibility of the hygroscopic agent in the composition (X2) and in the cured product. For this reason, even if it is a case where surface treatment for a dispersibility improvement etc. is not given to a hygroscopic agent, a hygroscopic agent can be disperse | distributed favorably in a composition (X2) and hardened | cured material.

  The polyfunctional cation polymerizable compound (F12) is preferably liquid at 25 ° C. In particular, the viscosity at 25 ° C. of the polyfunctional cation 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 of the polyfunctional cationically polymerizable compound (F12) is at least one group selected from the group consisting of, for example, an epoxy group, an oxetane group, and a vinyl ether group.

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

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

  R in each of the formula (10) and the formula (11) is a single bond or a divalent organic group, and is preferably an alkylene group. Y is a siloxane skeleton, which may be linear, branched or cyclic, and the number of Si atoms is preferably in the range of 2 to 14, preferably in the range of 2 to 10. Is more preferable, and is more preferably in the range of 2 to 7, and particularly preferably in the range of 3 to 6. n is an integer greater than or equal to 2, and it is preferable to exist in the range of 2-4.

  More specifically, for example, the polyfunctional cation 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, and is preferably an alkylene group having 1 to 4 carbon atoms. N in the formula (10a) is an integer of 0 or more. n is preferably in the range of 0 to 12, more preferably in the range of 0 to 8, more preferably in the range of 0 to 5, and particularly preferably in the range of 1 to 4. preferable.

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

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

  Examples of the compound represented by the formula (30) include a compound represented by the following formula (10a-1).

  The polyfunctional cationic polymerizable compound (F12) is replaced with the compound represented by the formula (10a) or together with the compound represented by the formula (10a), and the following formulas (10b) to (10d) and (11a) to (11b): You may contain at least 1 type of compound among the compounds shown to.

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

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

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

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

  The polyfunctional cation polymerizable compound (F12) preferably has an alicyclic epoxy structure, and it is particularly preferable if the polyfunctional cation polymerizable compound (F12) contains a compound represented by the formula (10a). The compound represented by the formula (10a) can contribute particularly to the improvement of the cationic polymerization reactivity of the composition (X2) and the reduction of the viscosity, as well as the improvement of the heat discoloration and the low elastic modulus of the cured product and the sealing material 5. Can particularly contribute. In the case where the composition (X2) contains a hygroscopic agent (C), it can particularly contribute to the improvement of the dispersibility of the hygroscopic agent (C) in the composition (X2).

  When the composition (X2) contains the polyfunctional cation polymerizable compound (F12), the ratio of the polyfunctional cation polymerizable compound (F12) to the total amount of the resin components is preferably in the range of 5 to 95% by mass. . If the ratio of the polyfunctional cation polymerizable compound (F12) is 5% by mass or more, particularly in the case where the composition (X2) contains a hygroscopic agent (C), in the composition (X2) and in the cured product. When the dispersibility of the moisture absorbent (C) is particularly improved, the transparency of the cured product is particularly improved. Moreover, if the ratio of the polyfunctional cation polymerizable compound (F12) is 95% by mass or less, the composition (X2) can have particularly high photocationic polymerization reactivity, and therefore the cured product has particularly high strength ( Hardness). The ratio of the polyfunctional cation 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 ratio of the polyfunctional cation polymerizable compound (F12) is more preferably 70% by mass or less, and in this case, the cured product can have a high refractive index. The ratio of the polyfunctional cation polymerizable compound (F12) is more preferably 45% by mass or less. For example, the ratio of the polyfunctional cation polymerizable compound (F12) is preferably in the range of 20 to 70% by mass.

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

  The viscosity at 25 ° C. of the monofunctional cation polymerizable compound (F2) 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 cation polymerizable compound (F2) is preferably in the range of 0.1 to 8 mPa · s.

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

  The monofunctional cation polymerizable compound (F2) preferably contains a compound represented by the above formula (16). In this case, the viscosity of the composition (X2) can be reduced. Furthermore, since the compound represented by the formula (16) has a high boiling point and low volatility among the components that the monofunctional cationic polymerizable compound (F2) can contain, the viscosity of the composition (X2) with time Effective rise can be effectively suppressed. Therefore, even when the composition (X2) is stored for a long period of time, the composition (X2) can have good coatability and can maintain good ink jet coatability.

  The ratio of the monofunctional cation polymerizable compound (F2) to the total amount of the resin component is preferably in the range of 5 to 50% by mass. If the ratio of the monofunctional cation polymerizable compound (F2) is 5% by mass or more, the viscosity of the composition (X2) can be particularly reduced. If the proportion of the monofunctional cation polymerizable compound (F2) is 50% by mass or less, the composition (X2) can have particularly excellent reactivity during the photocationic polymerization reaction, and thereby a cured product can be obtained. Can have high strength (hardness). The proportion of the monofunctional cation polymerizable compound (F2) is more preferably 10% by mass or more, and further preferably 15% by mass or more. The proportion of the monofunctional cation polymerizable compound (F2) is more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less. If the proportion of the monofunctional cation 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 not easily impaired. Furthermore, it can suppress especially that a hardened | cured material produces a tack. For example, the ratio of the monofunctional cation polymerizable compound (F2) is preferably in the range of 10 to 35% by mass.

  In particular, when the composition (X2) contains the polyfunctional cation polymerizable compound (F11) and the polyfunctional cation polymerizable compound (F12), the polyfunctional cation polymerizable compound (F11) with respect to the total amount of the resin components. Is within the range of 30 to 60% by mass, the ratio of the polyfunctional cation polymerizable compound (F12) is within the range of 15 to 30% by mass, and the ratio of the monofunctional cation polymerizable compound (F2) is 15 to 40% by mass. % Is preferable. 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, and the excellent transparency, excellent hygroscopicity and high refractive index of the cured product are balanced. Can be achieved well.

  The composition (X2) preferably contains a sensitizer (H). In this case, the composition (X2) can have particularly high cationic polymerization reactivity. The 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 more than 0% by mass and in the range of 1% by mass or less. In this case, the sensitizer (H) hardly inhibits the transparency of the cured product, and thus the cured product can have good transparency.

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

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

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

More specific examples of compounds that the cationic curing catalyst (G) can contain include DPI series (105, 106, 109, 201, etc.), BI-105, MPI series (103, 105, 106, 109, etc.) manufactured by Midori Chemical. ), BBI series (101, 102, 103, 105, 106, 109, 110, 200, 210, 300, 301 etc.), TSP series (102, 103, 105, 106, 109, 200, 300, 1000 etc.), HDS-109, MDS series (103, 105, 109, 203, 205, 209, etc.), BDS-109, MNPS-109, DTS series (102, 103, 105, 200, etc.), NDS series (103, 105, 155) , 165, etc.), DAM series (101, 102, 103, 10) 201, 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 Bispinol A, tert -Butyl l thocholate, tert-Butyl deoxycholate, tert-Butyl cholate, BX, BC-2, MPI-103, BDS-105, TPS-103, NAT-103, BMS-105, and TMS-105;
Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, and Cyracure UVI-950 from Union Carbide, USA;
Irgacure 250, Irgacure 261 and Irgacure 264 made by BASF;
CG-24-61 manufactured by Ciba Geigy;
Adekaoptomer SP-150, Adekaoptomer SP-151, Adekaoptomer SP-170 and Adekaoptomer SP-171 manufactured by ADEKA Corporation;
DAICAT II manufactured by Daicel Corporation;
UVAC1590 and UVAC1591 manufactured by Daicel-Cytec Corporation;
CI-2064, CI-2638, CI-2624, CI-2434, CI-2734, CI-2855, CI-2823, CI-2758, and CIT-1682 manufactured by Nippon Soda Co., Ltd .;
PI-2074, a tetrakis (pentafluorophenyl) borate toluylcumyl iodonium salt manufactured by Rhodia;
FFC509 manufactured by 3M;
CD-1010, CD-1011 and CD-1012 from Sartomer, USA;
CPI-100P, CPI-101A, CPI-110P, CPI-110A and CPI-210S manufactured by San Apro Co., Ltd., and UVI-6922 and UVI-6976 manufactured by Dow Chemical Co., Ltd. are included. The cationic curing catalyst (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 in the range of 1 to 4% by mass. When the proportion is 1% by mass or more, the composition (X2) can have particularly good cationic polymerization reactivity. In addition, when the ratio is 4% by mass or less, the composition (X2) can have good storage stability, and the production cost can be reduced by not containing an excessive cationic curing catalyst (G). It is.

  Even if the composition (X) contains any curable component, the composition (X) may further contain a hygroscopic agent (C). That is, the composition (X1) may further contain a hygroscopic agent (C), and the composition (X2) may further contain a hygroscopic agent (C). When composition (X) contains a hygroscopic agent (C), the cured product can have excellent hygroscopicity. It is preferable that the average particle diameter of the hygroscopic agent (C) is 200 nm or less. In this case, the cured product can have high transparency despite containing the hygroscopic agent (C). In particular, when the composition (X) is applied by an ink jet method, when the average particle size of the hygroscopic agent (C) is 200 nm or less, there is an advantage that the composition (X) hardly clogs the nozzle. Furthermore, when the average particle diameter of the hygroscopic agent (C) is 200 nm or less, the hygroscopic agent (C) hardly impairs 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 cured product can have high hygroscopicity by the hygroscopic agent (C). The moisture absorption rate of the cured product is preferably 0.5% by mass or more, more preferably 1% by mass or more, and most preferably 2% by mass or more. In addition, a moisture absorption rate is calculated | required with the following method. A film having a thickness of 10 μm is produced by applying the composition (X) in an argon atmosphere and then irradiating with ultraviolet rays. The ultraviolet irradiation conditions are, for example, an ultraviolet peak wavelength of 365 nm, an ultraviolet intensity of 3000 mW / cm ² , and an ultraviolet irradiation time of 10 seconds. This film is vacuum-dried using, for example, a vacuum dryer under the conditions of a heating temperature of 120 ° C. and a heating time of 3 hours. The mass of the film after drying is measured. This measurement result is defined as an initial mass (M ₀ ). Subsequently, the film is sufficiently absorbed. For this purpose, for example, the film is exposed under conditions of 85 ° C. and 85% RH for 24 hours. The mass of the film after moisture absorption is measured. This measurement result is referred to as mass after moisture absorption (M). From these initial mass (M ₀ ) and mass after moisture absorption (M), the moisture absorption rate can be calculated by the formula (M−M ₀ ) / M ₀ × 100 (% by mass).

  The hygroscopic agent (C) is preferably inorganic particles having hygroscopicity, and contains at least one component selected from the group consisting of zeolite particles, silica gel particles, calcium chloride particles, and titanium oxide nanotube particles, for example. Is preferred. It is particularly preferred that the hygroscopic agent (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. Such a method for producing zeolite particles is known from Japanese Patent Application Laid-Open Nos. 2006-69266 and 2013-049602.

  The zeolite particles are preferably produced from zeolite containing sodium ions as a raw material, and at least one selected from the group consisting of A-type zeolite, X-type zeolite and Y-type zeolite among the zeolites containing sodium ions is used as the raw material More preferably. It is particularly preferable that the zeolite particles are produced using 4A-type zeolite as a raw material among the A-type zeolite. 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, a raw material zeolite powder is prepared, and the zeolite powder is physically pulverized. For example, the zeolite powder can be physically pulverized by mixing the zeolite powder with water to prepare a slurry and applying this slurry to a bead mill pulverizer.

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

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

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

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

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

Crystallization of the zeolite powder can also be performed in the presence of silicate and alkali metal oxide. The specific example of the manufacturing method of the zeolite particle of the average particle diameter of 200 nm or less in that case is shown. First, zeolite powder is prepared. The zeolite powder preferably has a composition of aM1 ₂ O · bSiO ₂ · Al ₂ O ₃ · cMe. M1 is an alkali metal, proton, or ammonium ion (NH ₄ ⁺ ), Me is an alkaline earth metal, a is a number in the range of 0.01 to 1, and b is in the range of 20 to 80. C is a number within the range of 0-1. The zeolite powder preferably contains a zeolite containing sodium ions, and contains at least one material selected from the group consisting of A-type zeolite, X-type zeolite and Y-type zeolite among the zeolites containing sodium ions. More preferred. It is particularly preferable that the zeolite powder contains 4A-type zeolite among A-type zeolites. The zeolite powder is physically pulverized. For example, zeolite powder can be physically pulverized by applying it to a bead mill pulverizer.

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

  By heating this slurry in an autoclave, the zeolite powder can be crystallized. The conditions are, for example, in the range of heating temperature 100 to 230 ° C. and in the range of heating time 1 to 24 hours. Subsequently, the zeolite powder is washed and dried. Thereby, zeolite particles having an average particle size of 200 nm or less can be obtained.

  The pH of the zeolite particles is preferably 7 or more and 10 or less. When the pH of the zeolite particles is 7 or more, the crystals of the zeolite particles are not easily broken, and therefore the sealing material produced from the composition (X) containing the zeolite particles can have a particularly high hygroscopic property. Further, when the pH of the zeolite particles is 10 or less, the zeolite particles hardly inhibit the curing when the composition (X) is cured.

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

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

  The average particle diameter of the hygroscopic agent (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, if this average particle diameter is 10 nm or more, the good hygroscopicity of the hygroscopic agent (C) can be maintained. The average particle diameter is a median diameter calculated from a measurement result by a dynamic light scattering method, that is, a cumulative 50% diameter (D50). In addition, as a measuring apparatus, the nano track Nanotrac Wave series of Microtrack Bell Inc. can be used.

  The average particle diameter of the hygroscopic agent (C) is more preferably 150 nm or less, further preferably 100 nm or less, and particularly preferably 70 nm or less. Moreover, it is preferable that the average particle diameter of a hygroscopic agent (C) is 20 nm or more, and it is more preferable if it is 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 hygroscopic agent (C) is 100 nm or less. In this case, the cured product can have particularly high transparency.

  The ratio of the hygroscopic agent (C) to the total amount of the composition (X) is preferably 1% by mass or more and 20% by mass or less. If the ratio of the hygroscopic agent (C) is 1% by mass or more, the cured product can have particularly high hygroscopicity. Further, when the proportion of the moisture absorbent (C) is 20% by mass or less, the viscosity of the composition (X) can be particularly reduced, and the composition (X) has a sufficiently low viscosity that can be applied by an ink jet method. You can also. The proportion of the hygroscopic agent (C) is more preferably 3% by mass or more, and particularly preferably 5% by mass or more. Further, the proportion of the hygroscopic agent (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 hygroscopic agent (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, it is possible to improve the extraction efficiency of light transmitted through the sealing material 5 and emitted to the outside. The average particle diameter of the high refractive index particles is preferably in the range of 5 to 30 nm, and more preferably in the range of 10 to 20 nm.

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

  When the composition (X) contains a hygroscopic agent (C), the composition (X) may further contain a dispersant (D). The dispersant (D) is a surfactant that can be adsorbed on the moisture absorbent (C). The dispersing agent (D) includes, for example, an adsorbing group (also referred to as an anchor) that can be adsorbed on the particles of the hygroscopic agent (C), and a chain attached to the particles by adsorbing the adsorbing group to the particles of the hygroscopic agent (C) Or a tail which is a comb-shaped molecular skeleton. The dispersing agent (D) includes, for example, an acrylic dispersing agent whose tail is an acrylic molecular chain, a urethane dispersing agent whose tail is a urethane molecular chain, and a polyester dispersing whose tail is a polyester molecular chain. It contains at least one component selected from the group.

  When the composition (X) contains the dispersant (D), the hygroscopic agent (C) can be favorably dispersed in the composition (X) and the cured product. For this reason, although the cured product and the sealing material 5 contain the hygroscopic agent (C), the transparency of the cured product and the sealing material 5 is not easily lowered by the hygroscopic agent (C). Moreover, the dispersing agent (D) can effectively suppress aggregation of the moisture absorbent (C) during storage of the composition (X). Therefore, the storage stability of the composition (X) is not easily lowered by the hygroscopic agent (C).

  Furthermore, the adhesion between the cured product and silicon nitride and silicon oxide is not easily lowered by the dispersant (D). This is because the dispersant (D) is easily adsorbed to the moisture absorbent (C) as described above, and the dispersant (D) hardly affects the interface between the cured product, silicon nitride and silicon oxide. It is believed that there is. For this reason, the sealing material 5 can have high adhesiveness with a glass-made base material. Silicon nitride and silicon oxide may be used as a material for the passivation layer 6 in the light emitting device 1. For this reason, 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 less likely to volatilize from the composition (X), the storage stability of the composition (X) is further improved.

  It is preferable that a dispersing agent (D) has any one or both among a basic polar functional group and an acidic polar functional group as an adsorption group. In this case, the hygroscopic agent (C) can be dispersed particularly well in the composition (X) and in the cured product. This is because the dispersant (D) has either one or both of a basic polar functional group and an acidic polar functional group, so that it is easily adsorbed to the hygroscopic agent (C), and therefore the hygroscopic agent (C). This is thought to be due to the remarkable manifestation of the effect of dispersing the water.

  The dispersant (D) may include a polymer. The weight average molecular weight of the polymer is, for example, 1000 or more. Examples of the polymer include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, and a high molecular weight unsaturated acid ester. , Modified polyurethane, modified polyacrylate, polyether ester type anionic activator, salt of naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl phenyl ether, polyester polyamine, and stearylamine acetate Contains at least one component selected from the group. When the dispersing agent (D) contains a polymer, the steric hindrance effect produced when the polymer is adsorbed on the particles of the hygroscopic agent (C) is improved, so that the dispersibility of the hygroscopic agent (C) can be improved.

  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 When the dispersant (F1) has a basic polar functional group, the dispersant (F1) is likely to be adsorbed on the moisture absorbent (C), so that 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 the composition (X). An amino group is preferably included because the viscosity can be particularly reduced.

  Examples of the dispersant (F1) having a basic polar functional group include 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 Japan Louvre Resol Co., Ltd .; trade name: DISPERBYK-108, DISPERBYK-2013, DISPERBYK -180, DISPERBYK-106, DISPERBYK-162 (amine value: 13 mgKOH / g), trade name: DISPERBYK-163 (amine value: 10 mgKOH / g), trade name: DISPERBYK-168 (amine value: 1 mgKOH / g), trade name: DISPERBYK-2050 (amine value: 30.7 mgKOH / g), trade name: DISPERBYK-2150 (amine value: 56.7 mgKOH / g), etc. Product name: BYKJET-9151 (amine value: 17.2 mgKOH / g), product name: BYKJET-9152 (amine value: 27.3 mgKOH / g), etc. BYKJET Japan made BYKJET series; and product name: Ajinomoto Fine Techno Co., Ltd., such as Ajisper PB821 (amine value: 11.2 mgKOH / g), trade name: Azisper PB822 (amine value: 18.2 mgKOH / g), trade name: Azisper PB881 (amine value: 17.4 mgKOH / g) Company made Including di-spar series.

  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 further preferably 15 mgKOH / g or more and 30 mgKOH / g or less. Moreover, it is preferable that a dispersing agent (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 not more than the amine value. In this case, the dispersant (F1) can disperse the hygroscopic agent (C) particularly well, can particularly improve the storage stability of the composition (X), and particularly enhance the transparency of the cured product. In addition, the adhesion between the cured product and silicon nitride and silicon oxide can be particularly enhanced. Of the components that can be contained in the dispersant (F1), examples of the dispersant having an amino group and not having a phosphate group include DISPERBYK-108 manufactured by BYK Chemie. Examples of the dispersant 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.

  The acidic polar functional group in the dispersant (F2) having an acidic polar functional group is, for example, a carboxyl group. Dispersant (F2) contains DISPERBYK-P105 made by, for example, Big Chemie.

  The amount of the dispersant (D) relative to 100 parts by mass of the hygroscopic agent (C) is preferably 5 parts by mass or more and 60 parts by mass or less. When the amount of the dispersing agent (D) is 5 parts by mass or more, the advantage of the dispersing agent (D) can be exhibited particularly. If the quantity of a dispersing agent (D) is 60 mass parts or less, the adhesiveness between hardened | cured material, silicon nitride, and a silicon oxide can be improved more. The amount of the dispersant (D) is more preferably 15 parts by mass or more. The amount of the dispersant (D) is more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less.

  It is preferable that the composition (X) does not contain a solvent. In this case, it is not necessary to dry the composition (X) and volatilize the solvent when producing a cured product from the composition (X). Further, the storage stability of the composition (X) is further increased. When the composition (X) contains a solvent, the content of the solvent (percentage of the solvent relative to the entire composition (X)) is preferably 1% by mass or less. The content of the solvent is more preferably 0.5% by mass or less, further preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. It is particularly preferable that the composition (X) does not contain a solvent or contains only a solvent that is inevitably mixed.

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

3. Method for Manufacturing Sealant and Method for Manufacturing Light-Emitting Device A method for manufacturing the sealant 5 using the composition (X) and a method for manufacturing the light-emitting device 1 will be described.

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

  In applying the composition (X) by the 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 formed by applying the composition (X) by an inkjet method without heating.

  In the case where the composition (X) has a property of lowering viscosity by being heated, the composition (X) may be heated and then applied by an inkjet method to be molded. When the viscosity at 40 ° C. of the composition (X) is 30 mPa · s or less, particularly 15 mPa · s or less, the composition (X) can be reduced in viscosity only by slightly heating. The composition (X) can be discharged by an inkjet method. The heating temperature of the composition (X) is, for example, 20 ° C. or more and 50 ° C. or less.

  When the coating film obtained by molding the composition (X) is irradiated with light and cured, the light irradiated to the coating film is, for example, ultraviolet rays. Ultraviolet light means light rays having a wavelength in the range of 200 nm to 410 nm. The wavelength of light applied to the coating film is preferably in the range of 350 nm to 410 nm. As a typical example of light irradiated to the coating film, light having a wavelength of 365 nm can be given. In addition, the wavelength of the light irradiated to the coating film is not limited to the above description as long as the coating film can be cured.

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

  When the coating film is irradiated with light, the shape of the portion irradiated with light may be an area type having a certain area or a line type. In the case of the line type, the entire coating film can be irradiated with light by moving the coating film with respect to the light source or by moving the light source with respect to the coating film. In this case, it is easy to adjust the time during which the coating film is irradiated with light, and the integrated light quantity can be easily adjusted by adjusting this time.

  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, for example, a photolithography method using 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 manufactured by an appropriate method such as a vapor deposition method or a coating method. In particular, the light-emitting element 4 is preferably manufactured by a coating method such as an inkjet method. Thereby, the element array 9 is produced on the support substrate 2.

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

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

  The thickness of the sealing material 5 is preferably 4 μm or more and 50 μm or less, and more preferably 4 μm or more and 15 μm or less. As described above, in the present embodiment, small droplets of the composition (X) are easily formed with high density by the ink jet method, and thus it is easy to realize the thin sealing material 5 of 4 μm or more and 15 μm or less. When the thickness of the sealing material 5 is reduced as described above, tensile stress and compressive stress are hardly generated in the sealing material 5 in the light emitting device 1. Therefore, it becomes easy to realize the flexible light-emitting device 1.

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

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

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

  In the present embodiment, as described above, even if the composition (X) is applied by an ink jet method, satellites are not easily generated, and therefore the encapsulant 5 can be accurately produced from the composition (X). The amount of the droplet of the composition (X) ejected by the inkjet method is, for example, 7 pl or more and 10 pl or less, but may be smaller than this. In the present embodiment, even if the droplets are reduced in size, it is difficult to generate satellites. For this reason, the amount of droplets can be reduced to less than 7 pl. In particular, when the droplets of the composition (X) ejected by the inkjet method are small, for example, even when the droplets are 2 pl or more and less than 7 pl, or 2 pl or more and 5 pl or less, satellites hardly occur. As described above, when the acrylic compound (X) contains a compound having an isobornyl skeleton, the droplets are particularly easily miniaturized. Therefore, for example, even if the droplet of the composition (X) discharged by the inkjet method is made small in order to produce a thin sealing material 5 having a thickness of 2 μm or more and 8 μm or less, the sealing material 5 from the composition (X) is reduced. Can be manufactured with high accuracy. That is, by forming small droplets with high density, the sealing material 5 can be easily thinned. In the present embodiment, the amount of droplets and the thickness of the sealing material 5 are not limited to the above ranges. That is, the amount of droplets may be greater than 5 pl, and the thickness of the sealing material 5 may be greater than 8 μm.

  Furthermore, the sealing material 5 which consists of a hardened | cured material of composition (X) as mentioned above can have favorable heat resistance. For this reason, when the passivation layer 6 (second passivation layer 62) is formed on the sealing material 5 by a vapor deposition method such as a plasma CVD method, the sealing material 5 deteriorates even if the temperature of the sealing material 5 rises. Hard to do. Further, even when the temperature of the light emitting device 1 rises when the light emitting device 1 is used, the sealing material 5 is hardly deteriorated.

  The use of the composition (X) according to this embodiment is not limited to the production of the sealing material 5 for the light emitting element 4. The composition (X) can be used for producing various products molded by an ink jet method. For example, a phosphor may be contained in the composition (X), and a color resist in a color filter may be produced from the composition (X). In this case, it is easy to produce a color resist in the color filter with high density and high accuracy. This color filter can be provided in a display device such as an organic EL display or a micro LED display.

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

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

Details of the components shown in the table are as follows. Moreover, the viscosity of the following component is a value measured using a rheometer (manufactured by Anton Paar Japan, model number DHR-2) under conditions of a temperature of 25 ° C. and a shear rate of 1000 s ⁻¹ .

Moreover, the glass transition temperature of the following acrylic compound was measured with the following method. The acrylic compound and a photopolymerization initiator (Irgacure 184) having a percentage by weight of 5% by mass with respect to the acrylic compound were mixed to obtain a mixture. An acrylic compound is polymerized by irradiating a molded body obtained by molding this mixture into a film shape by irradiating ultraviolet rays from a high pressure mercury lamp under the conditions of a maximum illuminance of 200 mW / cm ² and an integrated light amount of 1500 mJ / cm ^2. A 10 μm film was prepared. When the differential scanning calorimetry of this film was performed using a viscoelastic spectrometer “DMS100” manufactured by Seiko Instruments Inc. under the condition of a temperature rising rate of 5 ° C./min, The glass transition temperature of the compound was used.

(1) Acrylic compound / tricyclodecane dimethanol diacrylate: manufactured by Nippon Kayaku Co., Ltd., product number R684, viscosity 110 mPa · s (25 ° C.), glass transition temperature 187 ° C.
Bisphenol A polyethoxydiacrylate: Nippon Kayaku Co., Ltd., product number R551, viscosity 800 mPa · s (25 ° C.), glass transition temperature 60 ° C.
Bisphenol F polyethoxydiacrylate: Nippon Kayaku Co., Ltd., product number R712, viscosity 330 mPa · s (25 ° C.), glass transition temperature 45 ° C.
Trimethylolpropane triacrylate: manufactured by Sartomer, part number SR351S, viscosity 106 mPa · s (25 ° C.), glass transition temperature 62 ° C.
Pentatriestol tetraacrylate: manufactured by Shin-Nakamura Chemical Co., Ltd., viscosity 200 mPa · s (40 ° C.), glass transition temperature 103 ° C.
Isobornyl acrylate: manufactured by Osaka Organic Chemical Industry, product number IBXA, viscosity 8 mPa · s (25 ° C.), glass transition temperature 97 ° C.
Dicyclopentanyl acrylate: manufactured by Hitachi Chemical Co., Ltd., product number FA-513AS, viscosity 13 mPa · s (25 ° C.), glass transition temperature 120 ° C.
4-tertiary butylcyclohexyl acrylate: compound represented by formula (110), viscosity 7 mPa · s (25 ° C.), glass transition temperature 77 ° C.
3,3,5-trimethylcyclohexyl = acrylate: compound represented by the formula (120), manufactured by Osaka Organic Chemical Industry, product name Biscoat # 196, viscosity 3 mPa · s (25 ° C.), glass transition temperature 52 ° C.
Neopentyl glycol diacrylate: manufactured by Sartomer, product number SR247, viscosity 6 mPa · s (25 ° C.), glass transition temperature 117 ° C.
1,6-hexanediol diacrylate, manufactured by Sartomer, product number SR238B, viscosity 7 mPa · s (25 ° C.), glass transition temperature 105 ° C.
Polyethylene glycol 200 dimethacrylate: manufactured by Shin-Nakamura Chemical Co., Ltd., viscosity 14 mPa · s (25 ° C.), glass transition temperature 41 ° C.
Polyethylene glycol 200 diacrylate, manufactured by Osaka Organic Chemical Co., Ltd., viscosity 17 mPa · s (25 ° C.), glass transition temperature 41 ° C.

(2) 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.
X-40-2732: manufactured by Shin-Etsu Chemical Co., Ltd., product number X-40-2732, compound represented by formula (10a) (mixture of n = 1 to 4, R = C ₂ H ₄ ), specific gravity 0.996, viscosity 20 mPa · s, refractive index 1.4512.
OXT-221: manufactured by Toagosei Co., Ltd., product number OXT-221, compound represented by formula (3), specific gravity 0.998, viscosity 10 mPa · s, refractive index 1.4538.
3-allyloxymethyl-3-ethyloxetane: compound represented by formula (16), boiling point 200 ° C., specific gravity 0.933, viscosity 2 mPa · s, refractive index 1.4445.

(3) Photoradical polymerization initiator Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF, product number Irgacure 184.
Irgacure TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, product number Irgacure TPO.

(4) Cationic curing catalyst DTS-200: Product number DTS-200 manufactured by Midori Chemical.

(5-1) Zeolite particles 1
Zeolite particles 1 are produced by the following method, having a D50 of 20 nm, a D90 of 50 nm, and a pH of 11.

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

  After adding 400 g of zirconia beads having a particle diameter of 100 μm to this slurry, the zeolite powder in the slurry was pulverized for 3 hours with a bead mill pulverizer, so that the average particle diameter of the zeolite powder was 120 nm. The slurry flow rate at this time is 10 kg / h, and the slurry viscosity is 10 mPa · s.

  Subsequently, zirconia beads having a particle diameter of 100 μm were removed from the slurry, and instead of adding 400 g of zirconia beads having a particle diameter of 50 μm, the zeolite powder in the slurry was pulverized for 1 hour with a bead mill pulverizer. The particle size was 70 nm. The slurry flow rate at this time is 10 kg / h, and the slurry viscosity is 6 mPa · s.

  Subsequently, zirconia beads having a particle size of 50 μm are removed from the slurry, and 450 g of zirconia beads having a particle size of 30 μm are put in place of the slurry, and then the zeolite powder in the slurry is ground for 1 hour by a bead mill grinder. The particle size was 20 nm. The slurry flow rate at this time is 10 kg / h, and the slurry viscosity is 4 mPa · s.

  Subsequently, the slurry was allowed to stand at a temperature of 180 ° C. for 2 to 3 hours to obtain finely pulverized zeolite powder. This zeolite powder was crushed in a mortar and then passed through a mesh to adjust the particle size, whereby zeolite particles 1 were obtained.

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

(5-2) Zeolite particles 2
Zeolite particles 2 are produced by the following method, having a D50 of 60 nm, a D90 of 110 nm, and a pH of 11.

  4A-type zeolite sodium ions having an average particle diameter of 5 μm were prepared as the starting material zeolite powder, and 100 g of this zeolite powder and 100 g of ion-exchanged water were mixed to prepare a slurry. The zeolite powder in this slurry was pulverized by the method according to the case of the zeolite particles 1 so that the average particle diameter became 60 nm.

  Subsequently, the slurry was allowed to stand at a temperature of 180 ° C. for 2 to 3 hours to obtain finely pulverized zeolite powder. This zeolite powder was pulverized in a mortar and then passed through a mesh to adjust the particle size, whereby zeolite particles 2 were obtained.

(5-3) Zeolite particles 3
The zeolite particles 3 are produced by the following method, and have a D50 of 150 nm, a D90 of 250 nm, and a pH of 11.

  4A-type zeolite sodium ions having an average particle diameter of 5 μm were prepared as the starting material zeolite powder, and 100 g of this zeolite powder and 100 g of ion-exchanged water were mixed to prepare a slurry. The zeolite powder in the slurry was pulverized by a method according to the case of the zeolite particles 1 so that the average particle diameter became 150 nm.

  Subsequently, the slurry was allowed to stand at a temperature of 180 ° C. for 2 to 3 hours to obtain finely pulverized zeolite powder. This zeolite powder was crushed with a mortar and then passed through a mesh to adjust the particle size, thereby obtaining zeolite particles 3.

(5-4) Zeolite particles 4
The zeolite particles 4 are produced by the following method, and have a D50 of 60 nm, a D90 of 110 nm, and a pH of 11.

  4A-type zeolite sodium ions having an average particle diameter of 5 μm were prepared as the starting material zeolite powder, and 100 g of this zeolite powder and 100 g of ion-exchanged water were mixed to prepare a slurry. The zeolite powder in this slurry was pulverized by the method according to the case of the zeolite particles 1 so that the average particle diameter became 60 nm.

  Hydrothermal synthesis treatment was performed on the zeolite powder in the treated slurry by the following method. 50 g of the slurry was placed in a fluororesin container, and this fluororesin container was placed in a stainless steel (SUS316) container of an autoclave. The stainless steel container has a capacity of 100 cc, a heat-resistant temperature of 200 ° C., a pressure-resistant pressure of 50 MPa, and has a sealed structure sealed with a lid provided with a safety valve. This stainless steel container was placed in a dryer, sealed, and heated at 180 ° C. for 24 hours. Next, the stainless steel container was taken out of the dryer and rapidly cooled by placing it in water at room temperature.

  The fluororesin container was taken out of the stainless steel container, placed in a vat, and allowed to stand at a temperature of 180 ° C. for 2 to 3 hours to dry the slurry in the fluororesin container. Thereby, finely pulverized zeolite powder was obtained. This zeolite powder was taken out from the fluororesin container, crushed in a mortar, and then passed through a mesh to adjust the particle size, whereby zeolite particles 4 were obtained.

(5-5) Zeolite particles 5
The zeolite particles 5 are Tosoh product number Zeorum 4A, 100 mesh pass product, which is a powder product that has not been surface-treated. Its D50 is 13 μm, its D90 is 30 μm, and its pH is 10.

(6) Dispersant Solsperse 32000: Comb-type resin dispersant of fatty acid amine having polyethyleneimine as a main skeleton, amine value 31 mgKOH / g, acid value 15 mgKOH / g, boiling point 200 ° C. or higher, manufactured by Lubrizol Corporation, product name Solsperse 32000 .

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

(1) Transmittance A coating film was prepared by applying the composition, and this coating film was subjected to a condition of about 30 mW / cm ² using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works Co., Ltd. A film having a thickness of 10 μm was prepared by irradiating with ultraviolet rays for 20 seconds to be photocured. 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 number DHR-2) under conditions of a temperature of 25 ° C. and a shear rate of 1000 s ⁻¹ .

(3) Maximum peak value of characteristic curve Using capillary break type elongation strain rheometer, temperature 25 ° C, upper plate and lower plate diameter 4 mm, initial gap 1 mm between upper plate and lower plate, pulling up upper plate The composition was measured under the conditions of a distance (displacement) of 3 mm, an upper plate lifting time of 30 milliseconds, and a diameter measurement rate of 30000 Hz (30,000 times / second), and a diameter-time curve at 25 ° C. was obtained. . A characteristic curve was obtained by converting the diameter-time curve at 25 ° C. The same composition was measured three times to obtain three characteristic curves. The average value of the maximum peak values of these characteristic curves was calculated and used as the maximum peak value of the characteristic curve of the composition. A characteristic curve in the case of Example 1 is shown in FIG. 3, and a characteristic curve in the case of Comparative Example 1 is shown in FIG. In Comparative Example 4, since the zeolite particles were precipitated, the variation in the characteristic curve was large, so that an effective value as the maximum peak value could not be obtained.

(4) Value of ratio of maximum peak value to viscosity By dividing the maximum peak value of the characteristic curve of the composition obtained in (3) above by the viscosity value obtained in (2) above, the viscosity The value of the ratio of the maximum peak value with respect to was calculated.

(5) Glass transition temperature of cured product The composition is put in a cartridge of an inkjet printer (“NanoPrinter300” manufactured by MicroJet Co., Ltd.), and the composition is discharged from the nozzle of the inkjet printer while maintaining the composition at 25 ° C. Thus, a coating film was prepared. This coating film was allowed to stand for 24 hours in a 20 ° C argon atmosphere (dew point temperature -70 ° C). Subsequently, the coating film was photocured by UV irradiation for 20 seconds under the condition of about 30 mW / cm ² using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works Co., Ltd. A film was prepared.

  The glass transition temperature of the film obtained above was measured using a viscoelastic spectrometer “DMS100” manufactured by Seiko Instruments Inc. At this time, dynamic viscoelasticity measurement (DMA) is performed with a tensile module at a frequency of 10 Hz, and the temperature at which tan δ is maximized when the temperature is raised from room temperature to 230 ° C. at a temperature rising rate of 5 ° C./min is a glass transition. It was temperature.

(6) Inkjet property (6-1) Evaluation 1
Using Ricoh Model No. MH2420 as an inkjet printer, the composition was placed in an inkjet printer cartridge, and the composition was maintained at 25 ° C. and the composition was heated to 40 ° C. A droplet of the composition was ejected from the nozzle. In this case, the minimum amount of droplets was 7.0 pl. The state in which the droplets were ejected from the nozzles was photographed with a high-speed camera, and it was confirmed whether the droplets were separated and satellites were generated. As a result, a case where no satellite was generated was evaluated as “good”, and a case where a satellite was generated was evaluated as “bad”. In addition, from the result of photographing with a high-speed camera, the droplet velocity at the maximum voltage discharged without satellite generation was measured.

(6-2) Evaluation 2
Inkjet performance was evaluated by the same method as “(6-1) Evaluation 1” except that Ricoh Model No. MH5420 was used as the inkjet printer. In this case, the minimum amount of droplets was 2.5 pl.

(7) Shrinkage The volume and mass of the composition were measured, and the specific gravity of the composition was calculated from the results. In addition, a coating film is prepared by applying this composition, and this coating film is applied for 20 seconds under the condition of about 30 mW / cm ² using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works Co., Ltd. A film having a thickness of 200 μm was produced by photocuring by ultraviolet irradiation. The specific gravity of the sample cut out from this film was measured using a specific gravity bottle. From these results, the shrinkage rate was calculated by the following formula.
Shrinkage rate (%) = {1- (specific gravity of composition)} / (specific gravity of sample) × 100
As a result, when the shrinkage rate is 2% or more and less than 5%, the evaluation is “A”, when the shrinkage rate is 5% or more and less than 10%, “B”, and when the shrinkage rate is 10% or more, “C” is evaluated. did.

(8) Adhesiveness A silicon nitride film (refractive index of 1.81) having a thickness of 100 nm was formed on the surface of a quartz glass piece (size: 50 mm × 25 mm × 1 mm) by plasma CVD. The composition was applied on the silicon nitride film to prepare a coating film having a thickness of 50 μm. This produced the 1st test piece.

  A silicon nitride film (refractive index of 1.81) having a thickness of 100 nm was formed on the surface of another piece of quartz glass (size: 76 mm × 52 mm × 1 mm) by plasma CVD. This produced the 2nd test piece.

On the coating film in the first test piece, the silicon nitride film in the second test piece was overlaid so that the size of the region where both contacted was 25 mm × 25 mm. Subsequently, the coating film was cured by UV irradiation for 30 seconds under the condition of about 100 mW / cm ² using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works Co., Ltd.

  Next, the adhesion strength between the two quartz glass pieces was evaluated by performing a tensile shear test (tensile speed of 5 mm / min) according to JIS-K-6850.

Claims (21)

The maximum peak value of the apparent elongational viscosity-Henkey strain curve at 25 ° C. is 350 mPa · s or less,
The value of the ratio of the maximum peak value to the viscosity at 25 ° C. is 20 or less,
It has the property of becoming a cured product having a glass transition temperature of 80 ° C. or higher by curing.
UV curable resin composition. Containing an acrylic compound (A) and a radical photopolymerization initiator (B),
The ultraviolet curable resin composition according to claim 1. The acrylic compound (A) contains a polyfunctional acrylic compound (A1) having two or more (meth) acryloyl groups in one molecule.
The ultraviolet curable resin composition according to claim 2. The acrylic compound (A) contains a component (a) composed of at least one compound having a viscosity at 25 ° C. of 20 mPa · s or less.
The ultraviolet curable resin composition according to claim 2. The component (a) contains a compound having a glass transition temperature of 80 ° C. or higher.
The ultraviolet curable resin composition according to claim 4. The component (a) comprises 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. contains,
The ultraviolet curable resin composition according to claim 4 or 5. The ratio of the component (a) to the total amount of the acrylic compound (A) is 50% by mass or more and 100% by mass or less.
The ultraviolet curable resin composition according to any one of claims 4 to 6. The acrylic compound (A) contains a component (b) composed 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. ,
The ratio of the component (b) to the total amount of the acrylic compound (A) is 5% by mass or more and 50% by mass or less.
The ultraviolet curable resin composition according to any one of claims 2 to 7. Further containing a moisture absorbent (C),
The ultraviolet curable resin composition according to any one of claims 1 to 8. The hygroscopic agent (C) contains zeolite particles,
The ultraviolet curable resin composition according to claim 9. Containing a dispersant (D),
The ultraviolet curable resin composition of Claim 9 or 10. The boiling point of the dispersant (D) is 200 ° C. or higher.
The ultraviolet curable resin composition according to claim 11. The amount of the dispersant (D) with respect to 100 parts by mass of the moisture absorbent (C) is 5 parts by mass or more and 50 parts by mass or less.
The ultraviolet curable resin composition according to claim 11 or 12. It contains no solvent, or the solvent content is 1% by mass or less,
The ultraviolet curable resin composition according to any one of claims 1 to 13. The light transmittance of the cured product is 90% or more,
The ultraviolet curable resin composition according to any one of claims 1 to 14. The viscosity at 25 ° C. is 1 mPa · s or more and 15 mPa · s or less,
The ultraviolet curable resin composition according to any one of claims 1 to 15. The viscosity at 40 ° C. is 1 mPa · s or more and 15 mPa · s or less,
The ultraviolet curable resin composition according to any one of claims 1 to 15. For producing a sealing material for a light emitting element,
The ultraviolet curable resin composition according to any one of claims 1 to 17. Molded by inkjet method,
The ultraviolet curable resin composition according to any one of claims 1 to 18. A method of manufacturing a light emitting device comprising a light emitting element and a sealing material covering the light emitting element,
An ultraviolet ray curable resin composition according to any one of claims 1 to 19 is molded by an ink jet method, and then the ultraviolet ray curable resin composition is irradiated with ultraviolet rays and cured to produce a sealing material. Including
Manufacturing method of light-emitting device. It comprises a light emitting element and a sealing material that covers the light emitting element, and the sealing material is made of a cured product of the ultraviolet curable resin composition according to any one of claims 1 to 19.
Light emitting device.