JP2020196858A - Uv-curable resin composition, method for producing uv-curable resin composition, method for producing light-emitting device, and light-emitting device - Google Patents

Abstract

To provide a UV-curable resin composition easily attaining a low moisture content rate because moisture in the composition is easily removed.SOLUTION: A UV-curable resin composition includes a photopolymerizable compound and a photopolymerization initiator. The Reynolds number when the UV-curable resin composition flows in a space between a circular pipe with a diameter of 0.015 m and a circular pipe with a diameter of 0.012 m included in the circular pipe at a flowing speed of 130 L/minute, is in the range of over 2,300 and 23,000 or less, and the Reynolds number when the composition flows in the circular pipe with an inner diameter of 0.001 m at a flow rate of 0.5 L/minute is 230 to 2,300.SELECTED DRAWING: Figure 1

Description

The present invention relates to an ultraviolet curable resin composition, a method for producing an ultraviolet curable resin composition, a method for producing a light emitting device, and a light emitting device. Specifically, the present invention relates to an ultraviolet curable compound containing a photopolymerizable compound and a photopolymerization initiator. A light emitting device including a resin composition, a method for producing the ultraviolet curable resin composition, a method for producing a light emitting device using the ultraviolet curable resin composition, and a sealing material comprising a cured product of the ultraviolet curable resin composition. Regarding.

Patent Document 1 contains a polymerizable compound and a polymerization initiator, has a viscosity at 25 ° C. of 5 to 50 mPa · s, a surface tension at 25 ° C. of 15 to 35 mN / m, and 25 ° C. A sealant for an organic EL display element having a water content of 1000 ppm or less at 25 ° C. after being allowed to stand in an environment of 50% RH for 24 hours is disclosed.

International Publication No. 2018/074507

In the disclosure of Patent Document 1, the sealing agent for an organic EL display element is made difficult to contain water, so that the organic EL display element sealed with the sealing agent is not deteriorated by water.

However, Patent Document 1 does not consider lowering the water content of the composition when the composition already contains water.

An object of the present invention is an ultraviolet curable resin composition that easily achieves a low water content because water is easily removed, a method for producing the ultraviolet resin composition, and a light emitting device using the ultraviolet curable resin composition. To provide a method and a light emitting device comprising a sealing material made from this UV curable resin composition.

The ultraviolet curable resin composition according to one aspect of the present invention contains a photopolymerizable compound and a photopolymerization initiator, and has a circular tube having an inner diameter of 0.015 m and an outer diameter of 0.012 m contained in the circular tube. The Reynolds number when flowing in the space between the circular pipes at a flow velocity of 130 L / min exceeds 2300 and is 23000 or less, and the Reynolds number when flowing in the circular pipe having an inner diameter of 0.001 m at a flow velocity of 0.5 L / min. It is 230 or more and 2300 or less.

In the method for producing a UV-curable resin composition according to one aspect of the present invention, an untreated composition containing a component of the UV-curable resin composition is obtained from a first surface and a second surface opposite to the first surface. It includes depressurizing the space in contact with the second surface while contacting the first surface and flowing along the first surface in the porous film having two surfaces. The porous membrane includes at least one of a zeolite membrane and a silica membrane.

In the method for producing a UV-curable resin composition according to another aspect of the present invention, an untreated composition containing a component of the UV-curable resin composition is passed through a filter while flowing through a flow path. including.

The method for manufacturing a light emitting device according to one aspect of the present invention is a method for manufacturing a light emitting device including a light emitting element and a sealing material covering the light emitting element. The production method includes forming a coating film by molding the ultraviolet curable resin composition by an inkjet method, and irradiating the coating film with ultraviolet rays to cure the coating material to produce a sealing material.

The light emitting device according to one aspect of the present invention includes 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 one aspect of the present invention, an ultraviolet curable resin composition that easily achieves a low water content by easily removing water, a method for producing the ultraviolet resin composition, and light emission using the ultraviolet curable resin composition. A light emitting device including a method for manufacturing the device and a sealing material made from the ultraviolet curable resin composition can be obtained.

It is a schematic cross-sectional view which shows the 1st example of the light emitting device in one Embodiment of this invention. It is a schematic cross-sectional view which shows the 2nd example of the light emitting device in one Embodiment of this invention. It is a schematic broken sectional view which shows the example of the structure of the dehydration apparatus in one Embodiment of this invention.

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

The ultraviolet curable resin composition (hereinafter, also referred to as composition (X)) according to the present embodiment contains a photopolymerizable compound and a photopolymerization initiator. Between a circular tube having an inner diameter of 0.015 m (hereinafter, also referred to as a first circular tube) and a circular tube having an outer diameter of 0.012 m (hereinafter, a second circular tube) contained in the circular tube. The Reynolds number (hereinafter, also referred to as the first Reynolds number) when flowing through the space at a flow velocity of 130 L / min exceeds 2300 and is 23000 or less. The Reynolds number (hereinafter, also referred to as the second Reynolds number) when the composition (X) flows in a circular pipe having an inner diameter of 0.001 m (hereinafter, also referred to as a third circular pipe) at a flow rate of 0.5 L / min is 230. It is 2300 or less.

In the present embodiment, when the number of first Reynolds exceeds 2300, the composition (X) or the composition (X) or not is used by utilizing the porous membrane while flowing the composition (X) or the untreated composition (Y) described later. When the treated composition (Y) is dehydrated, turbulence can easily occur in the composition (X) or the untreated composition (Y). The porous membrane includes at least one of a zeolite membrane and a silica membrane. Therefore, it is easy to increase the efficiency of dehydration using the porous membrane. The first Reynolds number is more preferably 3800 or more. Dehydration using a porous membrane will be described in detail later. Further, when the first Reynolds number is 23000 or less, turbulence can be less likely to occur when the composition (X) flows in the inkjet device. More preferably, the first Reynolds number is 11000 or less.

Further, when the second Reynolds number is 2300 or less, turbulence is less likely to occur in the composition (X) when the composition (X) is flowed inside a coating device such as an inkjet device. Therefore, when the composition (X) is applied by the coating device, misalignment or the like is unlikely to occur, and the composition (X) can be applied stably. More preferably, the first Reynolds number is 1200 or less. Further, when the second Reynolds number is 230 or more, the composition (X) is dehydrated by using a porous membrane such as a zeolite membrane while flowing the composition (X). It is possible to easily generate turbulence inside. The second Reynolds number is more preferably 400 or more.

The Reynolds number (hereinafter, also referred to as the third Reynolds number) when the composition (X) flows through the space in a circular pipe (hereinafter, also referred to as a fourth circular pipe) having an inner diameter of 0.00415 m at a flow velocity of 2.0 L / min. Is preferably 240 or more and 2400 or less. When the third Reynolds number is 2400 or less, the composition (X) is filtered by passing the composition (X) or the untreated composition (Y) through a filter while flowing. Alternatively, turbulence is unlikely to occur in the untreated composition (Y). Therefore, when the composition (X) or the untreated composition (Y) reaches the filter, the composition (X) or the untreated composition (Y) easily penetrates into the pores of the filter. This tends to increase the efficiency of filtration. It is more preferable that the third Reynolds number is 600 or less. Further, when the third Reynolds number is 240 or more, when the composition (X) is dehydrated by using the porous membrane while flowing, the composition (X) is turbulently flowed. Can be easily generated. It is more preferable that the third Reynolds number is 300 or more.

Such properties of composition (X) can be achieved by the composition of composition (X) described in detail below.

The water content of the composition (X) is preferably 200 mass ppm or less. In this case, when the light emitting element is sealed with the sealing material produced from the composition (X), the moisture contained in the sealing material is unlikely to deteriorate the light emitting element. The water content is more preferably 150 ppm or less, and even more preferably 100 ppm or less. The water content of the composition (X) can be easily achieved because the composition (X) is easily dehydrated as described above.

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

The composition (X) is preferably liquid at 25 ° C.

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

It is also preferable that the viscosity of the composition (X) at 40 ° C. is 1 mPa · s or more and 35 mPa · s or less. In this case, regardless of the viscosity of the composition (X) at room temperature, the viscosity can be reduced by slightly heating the composition (X). Therefore, when heated, the composition (X) can be easily molded by a method such as a casting method, and the composition (X) can also be molded by an inkjet method. Further, since the viscosity of the composition (X) can be reduced without significantly heating it, it is possible to prevent the composition (X) from changing due to volatilization of the components in the composition (X). It is more preferable if the viscosity is 30 mPa · s or less, further preferably 20 mPa · s or less, and particularly preferably 15 mPa · s or less. This viscosity is preferably 5 mPa · s or more, and more preferably 8 mPa · s or more. For example, it is preferable that this viscosity is 8 mPa · s or more and 35 mPa · s or less.

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

When the thickness dimension of the cured product of the composition (X) is 10 μm, the total light transmittance is preferably 90% or more. In this case, if the cured product is applied to the sealing material 5 in the light emitting device 1, the efficiency of taking out the light transmitted through the sealing material 5 and 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, when the composition (X) is applied by the inkjet method, the ejection stability is good, and it is possible to prevent the formation of defective droplets called satellites. It is more preferable that the surface tension is 30 mN / cm or more and 40 mN / cm or less, and more preferably 31 mN / cm or more and 38 mN / cm or less.

The sodium ion content of the composition (X) is preferably 1 mass ppm or less. In this case, problems due to elution of ions from the composition (X) are less likely to occur. Therefore, the reliability of the encapsulant produced from the composition (X) and the light emitting device including the encapsulant can be improved. It is more preferable that the sodium ion content is 0.8 mass ppm or less, and further preferably 0.5 mass ppm or less.

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

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 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 provided with 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 provided with the light emitting element 4 is, for example, a micro LED display. The EL is an electroluminescence, and the 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. This light emitting device 1 is a top emission type. The light emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 at intervals, a light emitting element 4 on the surface of the support substrate 2 facing the transparent substrate 3, and the support substrate 2 and the transparent substrate 3. A sealing material 5 is provided between the two. Further, in the first example, the light emitting device 1 includes a surface of the support substrate 2 facing the transparent substrate 3 and a passivation layer 6 covering the light emitting element 4. That is, the passivation layer 6 is interposed between the light emitting element 4 and the sealing material 5 that covers the light emitting element 4.

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

A second example of the structure of the light emitting device 1 will be described with reference to FIG. The elements common to the first example shown in FIG. 1 are designated by the same reference numerals as those in FIG. 2, and detailed description thereof will be omitted as appropriate. The light emitting device 1 shown in FIG. 2 is also a top emission type. The light emitting device 1 covers the support substrate 2, the transparent substrate 3 facing the support substrate 2 at intervals, the light emitting element 4 on the surface of the support substrate 2 facing the transparent substrate 3, and the light emitting element 4. The 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 case of the first example. The organic light emitting layer 42 includes, for example, a hole injection layer 421, a hole transport layer 422, an organic light emitting layer 423, and an electron transport layer 424, and these layers are laminated in the above order.

The light emitting device 1 includes a plurality of light emitting elements 4, and the plurality of light emitting elements 4 form an array 9 (hereinafter referred to as an element array 9) on the support substrate 2. The element array 9 also includes a partition wall 7. The partition wall 7 is located on the support substrate 2 and partitions between two adjacent light emitting elements 4. The partition wall 7 is manufactured, for example, by molding a photosensitive resin material by a photolithography method. The element array 9 also includes a connection wiring 8 that electrically connects the electrodes 43 of the adjacent light emitting elements 4 and the electron transport layers 424. 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 of silicon nitride or silicon oxide. The passivation layer 6 includes a first passivation layer 61 and a second passivation layer 62. The first passivation layer 61 covers the light emitting element 4 by covering the element array 9 in a state of being in direct contact with the element array 9. The second passivation layer 62 is arranged 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 that covers 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 composition (X). That is, the composition (X) is used to prepare the sealing material 5 for the light emitting element 4. In other words, the composition (X) is preferably a composition for producing a sealing material, a composition for encapsulating a light emitting element, or a composition for producing a light emitting device.

The composition (X) will be described.

The composition (X) contains a photopolymerizable compound and a photopolymerization initiator. The photopolymerizable compound contains, for example, a cationically polymerizable compound (F), and the photopolymerization initiator contains a cationic curing catalyst (photocationic polymerization initiator) (G). The photopolymerizable compound may contain a radically polymerizable compound, and the photopolymerization initiator may contain a photoradical polymerization initiator (B).

When the photopolymerizable compound contains a radically polymerizable compound and the photopolymerization initiator contains a photoradical polymerization initiator (B), the radically polymerizable compound preferably contains an acrylic compound (A). In this case, when the composition (X) is irradiated with ultraviolet rays, the photoradical polymerization initiator (B) initiates the photoradical polymerization reaction to cure the acrylic compound (A), 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 photoradical polymerization 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 make the composition (X1) particularly low in viscosity. The viscosity of the entire acrylic compound (A) is more preferably 30 mPa · s or less, and particularly preferably 20 mPa · s or less. The viscosity of the entire acrylic compound (A) is, for example, 3 mPa · s or more.

It is also preferable that the viscosity of the entire acrylic compound (A) at 40 ° C. is 50 mPa · s or less. In this case, the acrylic compound (A) can 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. The viscosity of the entire acrylic compound (A) is, for example, 3 mPa · s or more.

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

The acrylic compound (A) preferably contains a polyfunctional acrylic compound (A1) having two or more (meth) acryloyl groups in one molecule. In this case, the polyfunctional acrylic compound (A1) can increase the glass transition temperature of the cured product, and therefore the heat resistance of the cured product and the sealing material 5 can be increased. The amount of the polyfunctional acrylic compound (A1) is preferably 50% by mass or more and 100% by mass or less with respect to the entire 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, cyclohexanedimethanol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A polyethoxydiacrylate, bisphenol F polyethoxydiacrylate, pentatriester tetra Acrylate, propoxylation (2) neopentyl glycol diacrylate, trimethylolpropan triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated (3) trimethylol propantriacrylate, propoxylation (2) 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 Acrylate, 1,4-butanediol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, neopentyl hydroxypivalate Glycoldiacrylate, Trimethylolpropan triacrylate of hydroxypivalate, Triacrylate of ethoxylated phosphate, Tripropylene glycol diacrylate ethoxylated, Neopentyl glycol-modified trimethylol propandiacrylate, Stearate-modified pentaerythritol diacrylate, Tetramethylol propanthria Acrylate Rate, tetramethylolmethane triacrylate, caprolactone-modified trimethylolpropane triacrylate, propoxylate glyceryl triacrylate, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, di Pentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di ( It contains at least one compound selected from the group consisting of meth) acrylates, ethoxylated trimethylolpropane triacrylates, and propoxylated trimethylolpropane triacrylates.

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, shrinkage when the composition (X1) is cured can be particularly reduced. Further, 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 tricyclodecanedimethanol diacrylate, bisphenol A polyethoxydiacrylate, bisphenol F polyethoxydiacrylate, trimethylolpropane triacrylate and pentatriester tetraacrylate. It preferably contains at least one compound. These compounds can particularly reduce shrinkage as the composition (X1) cures. Furthermore, these compounds can also enhance the adhesion between the cured product and inorganic compounds such as silicon nitride and silicon oxide.

It is also preferable that the polyfunctional acrylic compound (A1) contains a compound (A11) having a structure represented by the following formula (40).

^{_{CH 2 = CR 1 -COO- (R}} 3 -O) n -CO-CR 2 = CH 2 ... (40)
In formula (40), each of R ¹ and R ² is a hydrogen or 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, it is in one molecule. The plurality of R ^3s may be the same as or different from each other.

Since the compound (A11) has the structure represented by the formula (40), and in particular, the carbon number of R ³ of the formula (40) is 3 or more, it is difficult to increase the affinity of the encapsulant 5 with water. Therefore, the light emitting element 4 is less likely to be deteriorated by water. The carbon number of R ³ is, for example, 3 or more and 15 or less. Further, the compound (A11) has a structure represented by the formula (40), 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 improved. Further, n in the equation (40) is, for example, an integer of 1 or more and 12 or less.

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 with respect to water is particularly difficult to increase. The percentage of the compound (A11) to the acrylic compound (A) is, for example, 100% by mass or less, or 95% by mass or less, preferably 80% by mass or less.

The compound (A11) preferably contains a compound (A12) having a boiling point of 270 ° C. or higher. That is, the acrylic compound (A) preferably contains the compound (A12) having the structure represented by the formula (40) and having a boiling point of 270 ° C. or higher. In this case, the acrylic compound (A) is less likely to volatilize from the composition (X) during storage of the composition (X) and when the composition (X) is heated. Therefore, the storage stability of the composition (X) is not easily impaired. Further, even if the compound (A12) remains unreacted in the cured product of the composition (X) and in the sealing material 5, outgas caused by 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 void in the light emitting device 1, moisture may enter the light emitting element 4 through the void, but if the void is less likely to occur, it is difficult for water to enter the light emitting element 4. The boiling point is the boiling point under normal pressure obtained by converting the boiling point under reduced pressure, and is obtained by, for example, the method shown in Science of Petroleum, Vol.II. P.1281 (1938). The boiling point of 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 enhanced, the outgas generation from the encapsulant 5 is effectively reduced, and the affinity of the encapsulant 5 for water is particularly difficult to be enhanced. .. The percentage of the compound (A12) to the acrylic compound (A) is, for example, 100% by mass or less, or 95% by mass or less, preferably 80% by mass or less.

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

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

The di (meth) acrylic acid ester of the alkylene glycol is a compound in which n is 1 in the formula (40). In this case, the carbon number of R ³ in the formula (40) is preferably 4 to 12. R ³ may be linear or may have a branch. In particular, the di (meth) acrylic acid ester of alkylene glycol is 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-. Nonandiol diacrylate, 1,10-decanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9 It preferably contains at least one compound selected from the group consisting of −nonandiol dimethacrylate, 1,10-decanediol dimethacrylate and 1,12-dodecanediol dimethacrylate. The di (meth) acrylic acid ester of alkylene glycol is a product number SR213 manufactured by Sartmer, a product number V195 manufactured by Osaka Organic Chemical Industry Co., Ltd., a product number SR212 manufactured by Sartmer, a product number SR247 manufactured by Sartmer, and a product number SR247 manufactured by Kyoei Chemical Industry Co., Ltd. Product name Light acrylate NP-A, product number SR238NS manufactured by Sartmer, product number V230 manufactured by Osaka Organic Chemical Industry Co., Ltd., product number HDDA manufactured by Daicel Co., Ltd., product number 1,6HX-A manufactured by Kyoei Chemical Industry Co., Ltd., Osaka Organic Chemical Industry Co., Ltd. Product number V260, product number 1,9-ND-A manufactured by Kyoei Chemical Industry Co., Ltd., product number A-NOD-A manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product number CD595 manufactured by Sartmer Co., Ltd., product number SR214NS manufactured by Sartmer Co., Ltd., Shin-Nakamura Product number BD manufactured by Kagaku Kogyo Co., Ltd., product number SR297 manufactured by Sartmer Co., Ltd., product number SR248 manufactured by Sartmer Co., Ltd., product name Light Ester NP manufactured by Kyoei Chemical Industry Co., Ltd., product number SR239NS manufactured by Sartmer Co., Ltd., product name Light Ester 1 manufactured by Kyoei Chemical Industry Co., Ltd. , 6HX, product number HD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name Light Ester 1,9ND manufactured by Kyoei Chemical Industry Co., Ltd., product number NOD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd. , 10DC, product number DOD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and product number SR262 manufactured by Sartmer Co., Ltd. preferably contain at least one compound selected from the group.

The di (meth) acrylic acid ester of the polyalkylene glycol is a compound in which n is 2 or more in the formula (40). n is, for example, 2 to 10, preferably 2 to 7, preferably 2 to 6, and preferably 2 to 3. The carbon number of R ³ is, for example, 2 to 5. The larger the number of carbon atoms, the higher the hydrophobicity of the cured product and the color resist 1, and the more difficult it is for the color resist 1 to permeate water. Di (meth) acrylic acid esters of polyalkylene glycol are particularly diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, dipropylene glycol diacrylate, and tripropylene glycol dimethacrylate. It preferably contains at least one compound selected from the group consisting of acrylates, tripropylene glycol dimethacrylates and tritetramethylene glycol diacrylates. Further, the di (meth) acrylic acid ester of polyalkylene glycol is particularly the product number SR230 manufactured by Sartmer, the product number SR508NS manufactured by Sartmer, the product number DPGDA manufactured by Daicel, the product number SR306NS manufactured by Sartmer, and the product number TPGDA manufactured by Daicel. , Product number V310HP manufactured by Osaka Organic Chemical Industry Co., Ltd., Product number APG200 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Product name Light Acrylate PTMGA-250 manufactured by Kyoei Chemical Industry Co., Ltd., Product number SR231NS manufactured by Sartmer Co., Ltd., Product name Light manufactured by Kyoei Chemical Industry Co., Ltd. Ester 2EG, product number SR205NS manufactured by Sartmer, product name Light Ester 3EG manufactured by Kyoei Chemical Industry Co., Ltd., product number SR210NS manufactured by Sartmer Co., Ltd., product name Light Ester 4EG manufactured by Kyoei Chemical Industry Co., Ltd., product name Acrylate HX manufactured by Mitsubishi Chemical Co., Ltd. It is preferable to contain at least one compound selected from the group consisting of product number 3PG manufactured by Nakamura Chemical Industry Co., Ltd.

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

The percentage of the component having a boiling point of 270 ° C. or higher in the acrylic compound (A) is preferably 80% by mass or more. When the acrylic compound (A) contains the compound (A12), the percentage of the components in the acrylic compound (A) including the compound (A12) having a boiling point of 270 ° C. or higher is 80% by mass or more. Is preferable. In this case, the storage stability of the composition (X) is not particularly impaired, and outgas is particularly unlikely to be generated from the cured product and the sealing material 5. It is more preferable that the percentage of the component in the acrylic compound (A) having a boiling point of 280 ° C. or higher is 80% by mass or more.

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

When the acrylic compound (A) contains the compound (A14), the percentage of the compound (A14) to the acrylic compound (A) is preferably more than 0% by mass and 25% by mass or less. The percentage of 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. Further, when the content of the compound (A14) is 25% by mass or less, the viscosity of the composition (X) due to the compound (A14) is unlikely to increase. When the percentage of the compound (A14) is 20% by mass or less, the viscosity increase of the composition (X) is particularly unlikely to occur.

When the acrylic compound (A) contains the compound (A11) having the structure represented by the formula (40), the compound (A11) preferably does not contain the compound having an n value of 5 or more in the formula (40). .. When (R ^3- O) _n is a polyethylene glycol skeleton, it is particularly preferable that the compound having a value of n greater than 5 in the formula (40) is not contained. Even when the compound (A11) contains a compound having an n value greater than 5 in the formula (40), the percentage of the compound having an n value greater than 5 in the formula (40) to the acrylic compound (A) is 20. It is preferably mass% or less. Further, even when the compound (A11) contains a compound having an n value greater than 5 in the formula (40), the compound (A11) preferably does not contain a compound having an n value greater than 9. It is more preferable that it does not contain a compound having a value greater than 7. In these cases, the increase in viscosity of the composition (X) is particularly unlikely to occur.

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

The amount of the monofunctional acrylic compound (A2) with respect to the total amount of the acrylic compound (A) is preferably more than 0% by mass and 50% by mass or less. When the amount of the monofunctional acrylic compound (A2) is more than 0% by mass, the shrinkage of the composition (X1) at the time of curing can be suppressed. Further, when the amount of the monofunctional acrylic compound (A2) is 50% by mass or less, the amount of the polyfunctional acrylic compound (A1) can be 50% by mass or more, so that the heat resistance of the cured product and the sealing material 5 is increased. Can be especially improved. It is more preferable that the amount of the monofunctional acrylic compound (A2) is 5% by mass or more, and further preferably 30% by mass or less.

The monofunctional acrylic compound (A2) is, for example, tetrahydrofurfuryl acrylate, isobolonyl 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, methoxydixyl ethyl acrylate, ethyldiglycol acrylate, cyclic trimethylolpropaneformal monoacrylate, Iimide acrylate, isoamyl acrylate, ethoxylated succinate acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, cyclohexyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, Isodecyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl acrylate, octyl / decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated (4) nylphenol acrylate, methoxypolyethylene glycol (350) monoacrylate, Methoxypolyethylene glycol (550) monoacrylate, phenoxyethyl acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl Acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, ethylene oxide adduct of 2-phenoxyethyl acrylate, propylene oxide adduct of 2-phenoxyethyl acrylate, acryloyl Morpholine, isobornyl acrylate, dicyclopentanyl acrylicate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1, It contains at least one compound selected from the group consisting of 4-cyclohexanedimethanol monoacrylate, 3-methacryloyloxymethylcyclohexene oxide and 3-acryloyloxymethylcyclohexene oxide.

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

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

The number of ring 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 at least one compound selected from the group consisting of, for example, 3-methacryloyloxymethylcyclohexene oxide and 3-acryloyloxymethylcyclohexene oxide.

The acrylic compound (A) is selected from the group consisting of a compound having silicon in the molecular skeleton (A41), a compound having phosphorus in the molecular skeleton (A42), and a compound having nitrogen in the molecular skeleton (A43). 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 the inorganic material is improved. Therefore, a gap is unlikely to occur between the sealing material 5 and the passivation layer 6, and moisture is unlikely to enter the light emitting element 4 through the gap.

In addition, compound (A41), compound (A42) and compound (A43) are defined by the type 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) includes, for example, 3- (trimethoxysilyl) propyl acrylate (for example, product number KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) and (meth) acrylic group-containing alkoxysilane oligomer (for example, product number KR-513 manufactured by Shin-Etsu Chemical Co., Ltd.). ) Contains at least one compound selected from the group consisting of. However, since the boiling point of 3- (trimethoxysilyl) propyl acrylate is 260 ° C., when the acrylic compound (A) contains 3- (trimethoxysilyl) propyl acrylate, the acrylic acid relative to the acrylic compound (A) The percentage of 3- (trimethoxysilyl) propyl should be 10% by mass or less.

Compound (A42) includes acid phosphoxy (meth) acrylates such as acid phosphooxypolyoxypropylene glycol monomethacrylate.

Compound (A43) includes, for example, at least one compound selected from the group consisting of acryloyl morpholine, diethyl acrylamide, dimethylaminopropyl acrylamide and pentamethylpiperidyl methacrylate.

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 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.

The acrylic compound (A) may contain a compound having an isobornyl skeleton. 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 reduce 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 viscosity of the composition (X1) can be made particularly low, and the composition (X1) can be particularly easily applied by the inkjet method. The ratio of the component (a) is more preferably 60% by mass or more, and further preferably 70% by mass or more. Further, the ratio of the component (a) is more preferably 95% by mass or less, and further preferably 90% by mass or less.

The component (a) preferably contains a compound having a glass transition temperature of 80 ° C. or higher. 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 lowering the viscosity of the composition (X1). It is more preferable that the component (a) contains a compound having a glass transition temperature of 90 ° C. or higher, and further preferably a compound having a glass transition temperature of 100 ° C. or higher is contained. The upper limit of the glass transition temperature of the compound contained in the component (a) is not limited, but is, for example, 150 ° C. or lower.

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

The acrylic compound (A) contains a component (b) consisting of a compound having at least one skeleton selected from the group consisting of a dicyclopentadiene skeleton, a dicyclopentanyl skeleton, a dicyclopentenyl skeleton, and a bisphenol skeleton. May be good. The 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 the component (b) may be a compound contained in the component (a).

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. When the ratio of the component (b) is 5% by mass or more, the adhesion of the cured product is further enhanced. Further, when the ratio of the component (b) is 50% by mass or less, the viscosity of the composition (X1) can be lowered to facilitate molding of the composition (X1) by an inkjet method. The ratio of the component (b) is more preferably 30% by mass or more, and further preferably 40% by mass or less. The acrylic compound (A) does not have to contain the component (b).

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

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

In formula (100), R ⁰ is H or a methyl group. X is a single bond or divalent hydrocarbon group. Each of R ¹ to R ¹¹ is an 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 of 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 preferable if X is a single bond or a methylene group. In this case, the compound (A1) has an advantage of having a small molecular weight and a low viscosity.

When at least one of R ¹ to R ¹¹ is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 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 linear and may have a branch. 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, the compound (A1) has an advantage of having a small molecular weight and a low viscosity.

In formula (100), it is preferable that an alkyl group or −R ¹² −OH is 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 of R ¹ to R ¹¹ is an alkyl group or −R ¹² −OH, and each of the rest is H. Of R ¹ to R ¹¹ , it is particularly preferred that only R ⁶ is an alkyl group or −R ¹² −OH and each of the rest is H. In this case, the compound represented by the formula (100) can have good reactivity, and it is particularly easy to impart adhesion to the sealing material 5 to the member made of the inorganic material. This is because the cyclohexane ring in the compound represented by the formula (100) has a boat conformation, and the bulky alkyl group or −R ¹² −OH at the 4-position is likely to be located at the pseudo-equatorial position. it is conceivable that. It is considered that when the compound represented by the formula (100) has such a structure, the reactivity of the (meth) acryloyl group in the compound represented by the formula (100) is enhanced. Further, when the compound represented by the formula (100) has such a structure, the compound represented by the formula (100) can increase the free volume in the encapsulant 5. Therefore, it is considered that the interfacial free energy between the sealing material 5 and the member made of the inorganic material tends to be small, and therefore the adhesion between the sealing material 5 and the member made of the 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 preferably has a t-butyl group.

In formula (100), it is also preferable that an alkyl group or −R ¹² −OH is connected only to each of the 3rd and 5th positions of the cyclohexane ring. That is, of R ¹ to R ¹¹ , at least one of R ⁴ and R ⁵ is an alkyl group or −R ¹² −OH, and at least one of R ⁸ and R ⁹ is an alkyl group or −R ¹² −OH. It is preferable that each of the remaining is H. Of R ¹ to R ¹¹ , only one of R ⁴ and R ⁵ is an alkyl group or −R ¹² −OH, and at least one of R ⁸ and R ⁹ is an alkyl group or −R ¹² −OH, and the rest. It is more preferable that each is H. Of R ¹ to R ¹¹ , at least one of R ⁴ and R ⁵ is an alkyl group or −R ¹² −OH, only one of R ⁸ and R ⁹ is an alkyl group or −R ¹² −OH, and the 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 it is particularly easy to impart adhesion to the sealing material 5 to the member made of the inorganic material. This is because the cyclohexane ring in the compound represented by the formula (100) has a boat conformation, and the bulky alkyl group or −R ¹² −OH at each of the 3 and 5 positions is located at the pseudo-equatorial position. It is thought that this is because it is easy. Therefore, the reactivity of the (meth) acryloyl group in the compound represented by the formula (100) is enhanced and the reactivity of the (meth) acryloyl group in the compound represented by the formula (100) is enhanced, as in the case where the alkyl group or −R ¹² −OH is connected only to the 4-position of the cyclohexane ring. It is considered that the adhesion between the sealing material 5 and the member made of the 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 carbon number of 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. It is particularly preferable that R ^{12 is a} methylene group. In this case, the compound (A1) has an advantage of having a small molecular weight and a low viscosity.

In formula (100), it is particularly preferable that each of R ¹ to R ¹¹ is an 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 the formula (100) can have a particularly low viscosity, so that the composition (X) can have a particularly low viscosity. Therefore, the composition (X) can be particularly easily molded by the inkjet method.

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

It is particularly preferable 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 viscosity of the composition (X) is particularly easy to be lowered, the glass transition temperature of the sealing material 5 is particularly easy to be raised, and the adhesion between the sealing material 5 and the member made of the inorganic material is particularly easy to be raised. Further, since the compound represented by the formula (110) and the compound represented by the formula (120) are hard to volatilize, it is easy to improve the storage stability of the composition (X).

It is also preferred that compound (A1) contains at least one component selected from the group consisting of morpholine acrylate, diethylacrylamide, dimethylaminopropylacrylamide and pentamethylpiperidylmethacrylate. Since these compounds contain nitrogen, they have a good affinity with the inorganic material, and therefore, it is easy to improve the adhesion between the sealing material 5 and the member made of the inorganic material. In addition, the viscosities of these compounds are low, so that these compounds are unlikely to increase the viscosity of the composition (X). Further, since these compounds are hard to volatilize, it is easy to improve the storage stability of the composition (X).

The amount of the compound (A1) with respect 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 to 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 that the compound does not contain the compound. Therefore, it is preferable that the acrylic compound (A) does not contain any of the above-mentioned morpholine acrylate, diethyl acrylamide, dimethylaminopropyl acrylamide and pentamethylpiperidyl methacrylate. In this case, the viscosity of the composition (X1) is unlikely to increase during storage of the composition (X1). It is considered that this is because when the composition (X1) contains the compound having nitrogen and the hygroscopic agent (C), the compound having nitrogen and the hygroscopic agent (C) are likely to react with each other.

The composition (X1) may further contain a radically polymerizable compound (E) other than the acrylic compound (A). The radically polymerizable compound (E) is a polyfunctional radically polymerizable compound (E1) having two or more radically polymerizable functional groups in one molecule, and a monofunctional compound having only one radically polymerizable functional group in one molecule. Either one or both of the radically polymerizable compound (E2) can be contained. The amount of the radically polymerizable compound (E) with respect to the total amount of the acrylic compound (A) and the radically polymerizable compound (E) is, for example, 10% by mass or less. The polyfunctional radical polymerizable compound (E1) is, for example, a group consisting of aromatic urethane oligomers, aliphatic urethane oligomers, epoxy acrylate oligomers, polyester acrylate oligomers and other special oligomers having two or more ethylenic double bonds in one molecule. It may contain at least one compound selected from. The monofunctional radical polymerizable compound (E2) includes, for example, N-vinylformamide, vinylcaprolactam, vinylpyrrolidone, phenylglycidyl ether, p-tert-butylphenylglycidyl ether, butylglycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxidodecan, 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 oxides, N-vinylpyrrolidone and N-vinylcaprolactam.

The photoradical polymerization initiator (B) is not particularly limited as long as it is a compound that produces radical species when irradiated with ultraviolet rays. The photoradical polymerization initiator (B) includes, for example, aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole. It contains at least one compound selected from the group consisting of a compound, a ketooxime 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 photoradical polymerization initiator (B) preferably contains a component having photobleaching properties. The component having photobleaching property preferably contains an acylphosphine oxide-based photoinitiator, and it is also preferable to include a compound having photobleaching property among the oxime ester-based photoinitiators.

The photoradical polymerization 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-thioxanthene-9-one skeleton and an anthracene skeleton. That is, the photoradical polymerization initiator (B) preferably contains a component having at least one of a 9H-thioxanthene-9-one skeleton and an anthracene skeleton.

From the viewpoint of improving the curability and making it difficult for outgas to be generated from the cured product, the photoradical polymerization initiator (B) preferably contains an oxime ester-based photoinitiator regardless of the presence or absence of photobleaching property.

The oxime ester-based photoinitiator is aromatic in order to reduce the contamination of the composition (X) and the manufacturing apparatus due to the decomposition product from the composition (X), and to further reduce the generation of outgas from the cured product. It is preferable to include a compound having a ring, more preferably to contain a compound having a fused ring containing an aromatic ring, and further preferably to contain a compound having a fused ring containing a benzene ring and a heterocycle.

Oxime ester-based photoinitiators include, for example, 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], and etanone, 1- [9-ethyl-6- (2-). Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime), and JP-A-2000-80068, JP-A-2001-233842, JP-A-2010-527339, JP-A-2010- It can contain at least one compound selected from the group consisting of oxime ester-based photoinitiators described in 527338, JP2013-041153A, JP2015-93842A, and the like. The oxime ester-based photoinitiators are commercially available Irgacure OXE-02 (manufactured by BASF), ADEKA Arkuru's NCI-831, N-1919 (manufactured by ADEKA) and TR-PBG-304 (manufactured by Changshu Strong Electronics) having a carbazole skeleton. New Materials Co., Ltd.), Irgacure OXE-01 with diphenylsulfide skeleton, ADEKA Arkuru's NCI-930 (manufactured by ADEKA), TR-PBG-345 and TR-PBG-3057 (manufactured by Joshu Strong Electronics New Materials Co., Ltd.) , And at least one compound selected from the group consisting of TR-PBG-365 (manufactured by Changshu Strong Electronics New Materials Co., Ltd.) and SPI-04 (manufactured by Sanyo) having a fluorene skeleton may be contained. In particular, when the oxime ester-based photoinitiator contains a compound having a diphenylsulfide skeleton or a fluorene skeleton, it is preferable because the cured product is less likely to be colored by photobleaching. It is also preferable that the oxime ester-based photoinitiator contains a compound having a carbazole skeleton because the exposure sensitivity tends to increase.

It is also preferable that the oxime ester-based photoinitiator contains two or more compounds. In this case, for example, by containing two or more compounds having different exposure sensitivities in the oxime ester-based photoinitiator, it is possible to reduce the amount of the photoradical polymerization initiator (B) while maintaining good exposure sensitivity. Therefore, it is possible to further reduce the generation of outgas from the cured product.

The amount of the photoradical polymerization initiator (B) with respect to the radically polymerizable compound in the composition (X1) is preferably 0.5% by mass or more and less than 4% by mass. When the amount of the photoradical polymerization initiator (B) is 0.5% by mass or more, good photocurability can be imparted to the composition (X1). Further, when the amount of the photoradical polymerization initiator (B) is less than 4% by mass, the reactivity of the composition (X1) is unlikely to be excessively high.

The composition (X1) may contain a polymerization accelerator in addition to the photoradical polymerization 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 photoradical polymerization initiator (B) may contain a sensitizer as a part of the photoradical polymerization initiator (B). The sensitizer can accelerate the radical formation reaction of the photoradical polymerization initiator (B), improve the reactivity of radical polymerization, and improve the crosslink density. The sensitizers are, for example, 9,10-dibutoxyanthracene, 9-hydroxymethylanthracene, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, anthracinone, 1,2-. Dihydroxyanthracene, 2-ethylanthracene, 1,4-diethoxynaphthalene, p-dimethylaminoacetophenone, p-diethylaminoacetophenone, p-dimethylaminobenzophenone, p-diethylaminobenzophenone, 4,4'-bis (dimethylamino) benzophenone, It can contain at least one compound selected from the group consisting of 4,4'-bis (diethylamino) benzophenone, p-dimethylaminobenzaldehyde, and p-diethylaminobenzaldehyde.

The content of the sensitizer in the composition (X1) is, for example, 0.1 part by mass or more and 5 parts by mass or less, preferably 0.1 part by mass, with respect to 100 parts by mass of the solid content of the composition (X1). It is not less than 3 parts by mass. When the content of the sensitizer is within such a range, the composition (X1) can be cured in air, and it is necessary to cure the composition (X1) in an inert atmosphere such as a nitrogen atmosphere. It disappears.

The composition (X1) may contain a polymerization accelerator in addition to the photoradical polymerization 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 composition (X) (hereinafter, also referred to as the composition (X2)) when the photopolymerizable compound in the composition (X) contains the cationically polymerizable compound (F) and the cationic curing catalyst (G). The components 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 cationically polymerizable compound (F1) is one or both of a polyfunctional cationically polymerizable compound (F11) having no siloxane skeleton and a polyfunctional cationically polymerizable compound (F12) having a siloxane skeleton. Can 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 composed of, for example, a 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. It contains at least one compound among the selected compounds.

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

In formula (1), each of R ^{1 to} R ¹⁸ is independently a hydrogen atom, a halogen atom, or a hydrocarbon group. The number of carbon atoms of the hydrocarbon group is preferably in the range of 1 to 20. The hydrocarbon group is an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a propyl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group and an allyl group; or an alkenyl group having 2 to 20 carbon atoms such as an ethylidene group and a propylidene group. There are 20 alkylidene groups. The hydrocarbon group may contain an oxygen atom or a halogen atom. Each of R ^{1 to} R ¹⁸ is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms independently, 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 is independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The hydrocarbon group having 1 to 20 carbon atoms is, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group or a propyl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group or an allyl group; or an ethylidene group or propyridene. It is an alkylidene group having 2 to 20 carbon atoms such as a group. The hydrocarbon group having 1 to 20 carbon atoms may contain an oxygen atom or a halogen atom.

Each of R ^{1 to} R ¹² is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms independently, 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 a tetrahydroindene epoxide 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, for example, at least one compound selected from the group consisting of the compounds represented by the following formulas (4) to (7).

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

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

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

The polyfunctional alicyclic epoxy compound preferably contains either one or both of the compound represented by the formula (1) and the compound represented by the formula (20). In this case, the composition (X2) can have a higher cationic polymerization reactivity.

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

Further, since the compound represented by the formula (20) has a low viscosity, the composition (X2) can have good ultraviolet curability and particularly when the compound represented by the formula (20) is contained. It can have a low viscosity. Further, the compound represented by the formula (20) has a property of being hard to volatilize in spite of having a low viscosity. Therefore, even if the composition (X2) contains the compound represented by the formula (20), the composition (X2) is unlikely to change in composition due to volatilization of the compound represented by the formula (20). Therefore, the composition (X2) can be reduced in viscosity by containing the compound represented by the formula (20) without impairing the storage stability.

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

The compound represented by the formula (20) may contain four stereoisomers based on the configuration of the two epoxy rings. The compound represented by the formula (20) may contain 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. The ratio of the total amount of the exo-end form and the end-end form to the four stereoisomers in the compound represented by the formula (20) is 10% by mass or less with respect to the entire epoxy compound (A1). Is preferable, and more preferably 5% by mass or less. In this case, the heat resistance of the cured product can be improved. The ratio of a specific stereoisomer in the compound represented by the formula (20) can be determined based on the peak area ratio appearing in the chromatogram obtained by gas chromatography.

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

When the composition (X2) contains the polyfunctional cationically polymerizable compound (F11), the ratio of the polyfunctional cationically polymerizable compound (F11) to the total amount of the resin component is preferably in the range of 5 to 95% by mass. .. The resin component refers to a compound having cationically polymerizable properties in the composition (X2), and includes a polyfunctional cationically polymerizable compound (F1) and a monofunctional cationically polymerizable compound (F2). When the proportion of the polyfunctional cationically polymerizable compound (F11) is 5% by mass or more, the composition (X2) can have particularly excellent reactivity during the photocationic polymerization reaction, whereby the cured product has high strength. Can have (hardness). Further, when the ratio of the polyfunctional cationically polymerizable compound (F11) is 95% by mass or less, when the composition (X2) contains the hygroscopic agent (C), the hygroscopic agent (C) is contained in the composition (X2). ) Can be easily dispersed particularly uniformly. The proportion of the polyfunctional cationically 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 preferable. The proportion of the polyfunctional cationically polymerizable compound (F11) is more preferably 85% by mass or less, and further preferably 60% by mass or less. For example, the proportion of the polyfunctional cationically polymerizable compound (F11) is preferably in the range of 20 to 60% by mass.

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

The polyfunctional cationically polymerizable compound (F12) has a siloxane skeleton and two or more cationically polymerizable functional groups per molecule. The number of cationically polymerizable functional groups per molecule of the polyfunctional cationically polymerizable compound (F12) is preferably 2 to 6, and more preferably 2 to 4. The polyfunctional cationically polymerizable compound (F12) can contribute to the improvement of the cationic polymerization reactivity of the composition (X2) and the heat-resistant discoloration of the cured product and the encapsulant 5. When the heat-resistant discoloration property of the sealing material 5 is high, it is possible to suppress the deterioration of the light emitting intensity of the light emitting device 1 provided with the sealing material 5 with time and the change of the light emitting color with time. Further, the polyfunctional cationically polymerizable compound (F12) can also contribute to lowering the elastic modulus of the cured product and the sealing material 5, and therefore, imparts flexibility to the light emitting device 1 provided with the sealing material 5. It is also possible. When the composition (X2) contains the hygroscopic agent (C), the polyfunctional cationically polymerizable compound (F12) improves the dispersibility of the hygroscopic agent (C) in the composition (X2) and the cured product. Can contribute. Therefore, even if the hygroscopic agent (C) is not subjected to a surface treatment for improving dispersibility, the hygroscopic agent (C) can be satisfactorily dispersed in the composition (X2) and the cured product. ..

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

The cationically polymerizable functional group contained in 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 cationically 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 to 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, further preferably in the range of 2 to 7, and particularly preferably in the range of 3 to 6.

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

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

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

R in the formula (10a) is a single bond or a divalent organic group, and is preferably an alkylene group having 1 to 4 carbon atoms. N in the equation (10a) is an integer of 0 or more. n is preferably in the range of 0 to 12, more preferably in the range of 0 to 8, further 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 the compound represented by the following formula (30). That is, the polyfunctional cationically polymerizable compound (F12) preferably contains the compound represented by the following formula (30).

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

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

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

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

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

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

More specifically, the polyfunctional 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. Containing at least one component selected from the group consisting of -22-169AS, X-22-169B, X-22-2046, X-22-343, X-22-163, and X-22-163B. Is preferable.

The polyfunctional cationically polymerizable compound (F12) preferably has an alicyclic epoxy structure, and it is particularly preferable that the polyfunctional cationically polymerizable compound (F12) contains the compound represented by the formula (10a). The compound represented by the formula (10a) can particularly contribute to the improvement of the cationic polymerization reactivity and the reduction of the viscosity of the composition (X2), and also the improvement of the heat-resistant discoloration property and the low elastic modulus of the cured product and the sealing material 5. Can especially contribute to. When the composition (X2) contains the 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 cationically polymerizable compound (F12), the ratio of the polyfunctional cationically polymerizable compound (F12) to the total amount of the resin component is preferably in the range of 5 to 95% by mass. .. When the proportion of the polyfunctional cationically polymerizable compound (F12) is 5% by mass or more, especially when the composition (X2) contains the hygroscopic agent (C), it is contained in the composition (X2) and in the cured product. By particularly improving the dispersibility of the hygroscopic agent (C), the transparency of the cured product is particularly improved. Further, when the proportion of the polyfunctional cationically polymerizable compound (F12) is 95% by mass or less, the composition (X2) can have a particularly high photocationic polymerization reactivity, and therefore the cured product has a particularly high strength ( Hardness). The proportion of the polyfunctional cationically polymerizable compound (F12) is more preferably 6% by mass or more, more preferably 13% by mass or more, and particularly preferably 20% by mass or more. Further, the proportion of the polyfunctional cationically 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 proportion of the polyfunctional cationically polymerizable compound (F12) is more preferably 45% by mass or less. For example, the proportion of the polyfunctional cationically polymerizable compound (F12) is preferably in the range of 20 to 70% by mass.

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

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

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

The ratio of the monofunctional cationically polymerizable compound (F2) to the total amount of the resin component is preferably in the range of 5 to 50% by mass. When the proportion of the monofunctional cationically polymerizable compound (F2) is 5% by mass or more, the viscosity of the composition (X2) can be particularly reduced. Further, when the proportion of the monofunctional cationically polymerizable compound (F2) is 50% by mass or less, the composition (X2) can have particularly excellent reactivity at the time of the photocationic polymerization reaction, and thereby the cured product. Can have high strength (hardness). The proportion of the monofunctional cationically polymerizable compound (F2) is more preferably 10% by mass or more, and further preferably 15% by mass or more. The proportion of the monofunctional cationically 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. When the proportion of the monofunctional cationically polymerizable compound (F2) is particularly 35% by mass or less, the amount of volatilization of the components in the composition (X2) during storage of the composition (X2) can be effectively reduced. Therefore, even if the composition (X2) is stored for a long period of time, the characteristics of the composition (X2) are not easily impaired. Further, it is possible to particularly suppress the occurrence of tack on the cured product. For example, the proportion of the monofunctional cationically polymerizable compound (F2) is preferably in the range of 10 to 35% by mass.

Further, particularly when the composition (X2) contains the polyfunctional cationically polymerizable compound (F11) and the polyfunctional cationically polymerizable compound (F12), the polyfunctional cationically polymerizable compound (F11) is used with respect to the total amount of the resin component. The ratio of the polyfunctional cationically polymerizable compound (F12) is in the range of 15 to 30% by mass, and the ratio of the monofunctional cationically polymerizable compound (F2) is in the range of 15 to 40% by mass. It is preferably in the range of%. In this case, good storage stability of the composition (X2), low viscosity and good cationic polymerization reactivity can be achieved in a well-balanced manner, and further, excellent transparency, excellent hygroscopicity and high refractive index of the cured product are balanced. Can be achieved well.

The cationically polymerizable compound (F) preferably contains a compound having an oxetane group. In this case, it is easy to moderately slow the progress of the curing reaction when producing a photocurable product from the composition (X2).

The amount of the compound having an oxetane group is preferably 25% by mass or more and 80% by mass or less with respect to the total amount of the resin components. When the amount of the compound having an oxetane group is 25% by mass or more, the storage stability of the composition (X) tends to be particularly improved. Further, when the amount of the compound having an oxetane group is 80% by mass or less, the reaction can be sufficiently promoted when the composition (X) is cured by irradiating it with ultraviolet rays and then heating it. As a result, for example, the glass transition temperature of the cured product can be easily increased, and the linear expansion coefficient of the cured product can be easily lowered. It is more preferable that the amount of the compound having an oxetane group is 30% by mass or more and 70% by mass or less, and further preferably 30% by mass or more and 65% by mass or less.

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

If the cationically polymerizable compound (F) contains the compound represented by the formula (3) and the compound represented by the formula (16), a photocured product is prepared from the composition (X2) by adjusting the ratio of both. It is possible to reduce the viscosity of the composition (X2) and improve the storage stability while appropriately adjusting the ease of progress of the curing reaction.

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

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

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

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

More specific examples of compounds that can be contained in the cation curing catalyst (G) are DPI series (105, 106, 109, 201, etc.), BI-105, MPI series (103, 105, 106, 109, etc.) manufactured by Midori Chemical Co., Ltd. ), 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, etc.) , 165, etc.), DAM series (101, 102, 103, 105, 201, etc.), SI series (105, 106, etc.), PI-106, NDI series (105, 106, 109, 1001, 1004, etc.), PAI series (01, 101, 106, 1001, 1002, 1003, 1004, etc.), MBZ-101, PYR-100, NB series (101, 201, etc.), NAI series (100, 1002, 1003, 1004, 101, 105, 106, etc.) , 109, etc.), TAZ series (100, 101, 102, 103, 104, 107, 108, 109, 110, 113, 114, 118, 122, 123, 203, 204, etc.), NBC-101, ANC-101, TPS-Actate, DTS-Actate, Di-Boc Bisphinol A, tert-Butyl lithocholate, tert-Butyl deoxycholate, tert-Butyl chocolate, BX, BC-2, MPI-103, BDS-105, TPS-103 , BMS-105, and TMS-105;
Union Carbide, USA Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, and Cyracure UVI-950;
BASF's Irgacure 250, Irgacure 261 and Irgacure 264;
CG-24-61 manufactured by Ciba Geigy Co., Ltd .;
ADEKA Corporation ADEKA OPTMER SP-150, ADEKA OPTMER SP-151, ADEKA OPTMER SP-170 and ADEKA OPTMER SP-171;
DAICAT II manufactured by Daicel Corporation;
UVAC1590 and UVAC1591 manufactured by Daicel Cytec Co., Ltd .;
CI-2064, CI-2369, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758, and CIT-1682; manufactured by Nippon Soda Corporation;
PI-2074, a tetrakis (pentafluorophenyl) borate toluyl cumyl iodonium salt manufactured by Rhodia;
3M FFC509;
CD-1010, CD-1011 and CD-1012 manufactured by Sartomer, USA;
Includes CPI-100P, CPI-101A, CPI-110P, CPI-110A and CPI-210S from Sun Appro Co., Ltd .; and UVI-6992 and UVI-6976 from Dow Chemical. The cationic curing catalyst (G) can contain at least one compound selected from the group consisting of these compounds.

The ratio of the cationic curing catalyst (G) to the total amount of the resin component is preferably 1% by mass or more and 4% by mass or less. When this ratio is 1% by mass or more, the composition (X2) can have a particularly good cationic polymerization reactivity. Further, when this 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 excess cation curing catalyst (G). Is. It is also preferable that the ratio of the cationic curing catalyst (G) to the total amount of the resin component is 0.5% by mass or more and 3% by mass or less. In this case, the reactivity of the composition (X2) can be moderately moderated.

The composition (X2) may contain a sensitizer (H). 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 preferably in the range of 1% by mass or less. In this case, the sensitizer (H) does not easily inhibit the transparency of the cured product, so that the cured product can have good transparency. It is more preferable that the amount of the sensitizer (H) is more than 0% by mass and 0.8% by mass or less with respect to the total amount of the resin component. In this case, the reactivity of the composition (X2) can be moderately moderated.

The composition (X) may further contain a hygroscopic agent (C). When the composition (X) contains the hygroscopic agent (C), the cured product of the composition (X) and the sealing material 5 can have hygroscopicity. Therefore, the sealing material 5 can further prevent moisture from entering the light emitting element 4 in the light emitting device 1. The average particle size of the hygroscopic agent (C) is preferably 200 nm or less. In this case, the cured product can have high transparency.

The hygroscopic agent (C) is preferably inorganic particles having hygroscopicity, and contains at least one component selected from the group consisting of, for example, zeolite particles, silica gel particles, calcium chloride particles, and titanium oxide nanotube particles. Is preferable. It is particularly preferable 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 a 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. Examples of such methods for producing zeolite particles are disclosed in JP-A-2016-69266, JP-A-2013-049602, and the like.

Zeolite particles preferably contain sodium ions. Therefore, the zeolite particles are preferably produced from at least one selected from the group consisting of A-type zeolite, X-type zeolite and Y-type zeolite. It is particularly preferable that the zeolite particles are produced from 4A-type zeolite among A-type zeolites. In these cases, the zeolite particles have a crystal structure suitable for adsorbing water.

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 less likely to be destroyed, so that the encapsulant prepared from the composition (X) containing the zeolite particles can have particularly high hygroscopicity. Further, when the pH of the zeolite particles is 10 or less, the zeolite particles are less likely to inhibit the curing when the composition (X) is cured. The pH of the zeolite particles is determined by heating a dispersion obtained by adding 0.05 g of zeolite particles to 99.95 g of ion-exchanged water at 90 ° C. for 24 hours, and then measuring the pH of the supernatant of the dispersion with a pH meter. It is a value obtained by measuring with. As the pH measuring device, for example, a compact pH meter <LAQUAtwin> B-711 manufactured by HORIBA, Ltd. can be used.

The average particle size of the hygroscopic agent (C) is preferably 10 nm or more and 200 nm or less. When the average particle size is 200 nm or less, the cured product can have particularly high transparency. Further, when the average particle size is 10 nm or more, good hygroscopicity of the hygroscopic agent (C) can be maintained. The average particle size is the median diameter calculated from the measurement result by the dynamic light scattering method, that is, the cumulative 50% diameter (D50). As the measuring device, the Nanotrack Nanotrac Wave series manufactured by Microtrack Bell Co., Ltd. can be used.

The average particle size 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. Further, the average particle size of the hygroscopic agent (C) is preferably 20 nm or more, and more preferably 50 nm or more. In this case, the cured product can have particularly good transparency and hygroscopicity.

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

When the composition (X) contains the hygroscopic agent (C), 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. When 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 hygroscopic agent (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 inkjet 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. 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 efficiency of taking out the light transmitted through the sealing material 5 and emitted to the outside. The average particle size of the high refractive index particles is preferably in the range of 5 to 30 nm, and more preferably in the range of 10 to 20 nm.

The proportion of 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) so that the refractive index of the cured product is in the range of 1.45 or more and less than 1.55. In this case, the light extraction efficiency of the light emitting device 1 is particularly improved.

When the composition (X) contains a hygroscopic agent (C), the composition (X) preferably further contains a dispersant (D). In this case, the dispersant (D) can improve the dispersibility of the hygroscopic agent (C) in the composition (X). Therefore, the composition (X) is unlikely to have an increase in viscosity and a decrease in storage stability due to the hygroscopic agent (C).

The dispersant (D) is a surfactant that can be adsorbed on the particles. The dispersant (D) has an adsorbing group that can be adsorbed on the particles (generally also referred to as an anchor) and a molecular skeleton (generally also referred to as a tail) that adheres to the particles when the adsorbing group is adsorbed on the particles. The dispersant (D) is, for example, an acrylic dispersant having an acrylic molecular chain at the tail, a urethane dispersant having a urethane molecular chain at the tail, and a polyester-based dispersion having a polyester molecular chain at the tail. It contains at least one ingredient selected from the group if it is an agent. The adsorbent group contains, for example, at least one of a basic polar functional group and an acidic polar functional group. The basic polar functional group includes, for example, at least one group selected from the group consisting of an amino group, an imino group, an amide group, an imide group, and a nitrogen-containing heterocyclic group. The acidic polar functional group includes, for example, at least one group selected from the group consisting of a carboxyl group and a phosphoric acid group. The dispersant (D) is at least one compound selected from the group consisting of, for example, a sparse sparse series manufactured by Nippon Louvre Resol Co., Ltd., a DISPERBYK series manufactured by Big Chemie Japan Co., Ltd., and an azisper series manufactured by Ajinomoto Fine-Techno Co., Ltd. Can be contained.

When the composition (X) contains the hygroscopic agent (C), the amount of the dispersant (D) with respect to the hygroscopic agent (C) is preferably 5 parts by mass or more and 60 parts by mass or less. When the amount of the dispersant (D) is 5 parts by mass or more, the function of the dispersant (D) can be effectively exhibited, and when it is 60 parts by mass or less, the dispersant (D) in the encapsulant 5 is used. It is possible to prevent the free molecules of the material from inhibiting the adhesion between the sealing material 5 and the member made of the inorganic material. The amount of the dispersant (D) is more preferably 15 parts by mass or more, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. preferable.

The composition (X) preferably does not contain a solvent, or the content of the solvent is 1% by mass or less. In this case, it is not necessary to dry the composition (X) to volatilize the solvent when producing a cured product from the composition (X). In addition, the storage stability of the composition (X) is further increased. 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 unavoidably mixed.

The content of particles having a particle size of 0.5 μm or more in the composition (X) is preferably 100,000 or less per 1 mL of the composition (X). In this case, ejection defects are less likely to occur when the composition (X) is molded by the inkjet method, and defects due to large particles are less likely to occur in the optical component manufactured from the composition (X). The particles having a particle size of 0.5 μm or more include, for example, the particles in the hygroscopic agent (C) having a particle size of 0.5 μm or more and the particles contained in the inorganic filler having a particle size of 0. It may include at least one of those having a diameter of 5 μm or more. Further, the particles having a particle size of 0.5 μm or more are the untreated composition (Y) or the composition when the untreated composition (Y) or the composition (X) is dehydrated using a hygroscopic agent, as will be described later. It may contain particles of a hygroscopic agent having a particle size of 0.5 μm or more mixed in the object (X). Further, the particles having a particle size of 0.5 μm or more may contain particles other than the above, which are mixed in the untreated composition (Y) or the composition (X). The content of particles having a particle size of 0.5 μm or more is more preferably 50,000 or less, and even more preferably 30,000 or less. The number of particles having a particle size of 0.5 μm or more can be confirmed by measuring by the side scattering method based on JIS Z8825. As a measuring device for measuring the number of particles, for example, a particle counter (model number KS-42C) manufactured by Rion Co., Ltd. can be used.

The method for producing the composition (X) will be described.

First, the untreated composition (Y) is prepared by mixing the components of the composition (X) described above. The untreated composition (Y) has the same composition as the composition (X) except that it has not been dehydrated by the dehydration treatment described later.

The composition (X) is obtained by subjecting the untreated composition (Y) to a dehydration treatment using the porous membrane 21. Thereby, a low water content of the composition (X) can be realized, and the water content of the composition (X) can be realized to be 200 mass ppm or less. The porous membrane 21 preferably contains at least one of a zeolite membrane and a silica membrane. In the dehydration treatment, a porous film 21 having a first surface 211 and a second surface 212 on the opposite side of the first surface 211 is used, and the untreated composition (Y) is applied to the first surface 211 of the porous film 21. The space in contact with the second surface 212 is depressurized while being brought into contact with the surface and flowing along the first surface 211. In this case, among the components in the untreated composition (Y), water easily permeates the porous membrane 21 from the first surface 211 to the second surface 212. As a result, the untreated composition (Y) is dehydrated.

In particular, the zeolite membrane can also permeate cations that can be placed in the pores of the zeolite skeleton. Therefore, when the untreated composition (Y) contains cations such as sodium ions as impurities, the porous membrane 21 containing the zeolite membrane is directed from the first surface 211 to the second surface 212 during the dehydration treatment. Permeation facilitates the removal of cations from the untreated composition (Y). Therefore, in the present embodiment, the concentration of cations such as sodium, which is an impurity in the untreated composition (Y), can be reduced at the same time as the dehydration treatment.

The zeolite constituting the zeolite membrane has, for example, sodium ions in the pores. The zeolite constituting the zeolite membrane is at least one selected from the group consisting of, for example, A-type zeolite, X-type zeolite, and Y-type zeolite. It is preferable that the zeolite membrane is made of 4A type zeolite among A type zeolites. In this case, the zeolite has a crystal structure suitable for allowing water to permeate.

Further, the pore size of the silica film can be controlled by the firing conditions at the time of film formation, and by controlling the pore size to about 0.8 nm or less, moisture can be selectively permeated with high efficiency. ..

More specifically, at the time of dehydration treatment, for example, as shown in FIG. 3, a dehydrator 20 including an outer cylinder 22 and a cylinder 210 (hereinafter, referred to as an inner cylinder 210) made of a porous membrane 21 is used. In this case, the outer peripheral surface of the inner cylinder 210 is the first surface 211 of the porous membrane 21, and the inner peripheral surface of the inner cylinder 210 is the second surface 212 of the porous membrane 21. The outer diameter of the inner cylinder 210 is, for example, 0.005 m or more and 0.015 mm or less. The outer cylinder 22 has an inner diameter larger than the outer diameter of the inner cylinder 210. The inner cylinder 210 is arranged in the outer cylinder 22 so that the longitudinal direction of the inner cylinder 210 is along the longitudinal direction of the outer cylinder. The inner diameter of the outer cylinder 22 is, for example, 0.01 m or more and 0.02 mm or less. The length of the outer cylinder 22 and the inner cylinder 210 is, for example, 0.5 m or more and 2 m or less. The material of the outer cylinder 22 is not particularly limited as long as the composition (X) can be held in the outer cylinder 22 and the composition (X) can flow in the outer cylinder 22. As a result, inside the outer cylinder 22, a space 24 (hereinafter referred to as a flow space 24) between the inner peripheral surface of the outer cylinder 22 and the outer peripheral surface (first surface 211) of the inner cylinder 210 and the inner cylinder There is a space 23 inside the 210 (hereinafter referred to as a decompression space 23). Therefore, the decompression space 23 is in contact with the second surface 212 of the porous membrane 21 and is surrounded by the second surface 212.

Assuming that one direction along the longitudinal direction of the outer cylinder 22 is defined as the first direction and the other direction is defined as the second direction, the end of the flow space 24 on the first direction side and the end on the second direction side are defined. Both parts are closed. On the outer peripheral surface of the outer cylinder 22, the supply port 25 is located at the position closer to the first direction, and the outlet port 26 is located at the position closer to the second direction. The supply port 25 is passed through the outside of the dehydrator 20 and the flow space 24, and the outlet 26 is also passed through the outside of the dehydrator 20 and the flow space 24. The second facing end of the decompression space 23 is closed. An exhaust port 27 is provided at the first facing end of the decompression space 23, and the decompression space 23 leads to the outside of the dehydrator 20 via the exhaust port 27.

During the dehydration treatment, the decompression space 23 is depressurized. Therefore, for example, the gas in the decompression space 23 is exhausted from the exhaust port 27 using a decompression device such as a vacuum pump. The decompression space 23 is decompressed so that the pressure in the decompression space is, for example, 0.1 KPa or more and 1 KPa or less. While depressurizing the depressurized space 23, the untreated composition (Y) is flowed in the flow space 24 in the longitudinal direction of the outer cylinder 22 and the inner cylinder 210. For that purpose, for example, the untreated composition (Y) is supplied to the flow space 24 through the supply port 25, and is derived from the flow space 24 through the outlet 26. As a result, the untreated composition (Y) flows along the first surface 211 of the porous membrane 21 in the flow space 24. The flow velocity of the untreated composition (Y) in the flow space 24 is, for example, 10 L / min or more and 150 L / min or less.

When the untreated composition (Y) is flowed in the flow space 24 as described above, the decompression space 23 is depressurized. Therefore, when the untreated composition (Y) contains water, the water content is the porous membrane 21. Is transmitted from the first surface 211 to the second surface 212, and is discharged into the decompression space 23. As a result, the untreated composition (Y) is dehydrated. When the untreated composition (Y) contains a cation such as sodium ion, the cation also moves to the porous membrane 21 and is discharged into the reduced pressure space 23. As a result, the concentration of the impurity cation in the untreated composition (Y) is reduced.

During this dehydration treatment, the first Reynolds number of the composition (X) exceeds 2300 and is 23000 or less. Therefore, dehydration conditions such as the dimensions and shapes of the outer cylinder 22 and the inner cylinder 210, and the untreated composition (Y). ), By adjusting the conditions such as the flow velocity, turbulence is likely to occur in the untreated composition (Y) in the flow space 24. Specifically, for example, the inner diameter of the outer cylinder 22 is within the range of 0.013 m or more and 0.018 m or less, the outer diameter of the inner cylinder 210 is within the range of 0.008 m or more and 0.012 m or less, and the untreated composition (Y) By appropriately adjusting the flow velocity of the above in the range of 20 L / min or more and 40 L / min or less, turbulence is likely to occur in the untreated composition (Y) in the flow space 24. Therefore, the untreated composition (Y) is easily agitated in the flow space 24, so that the water content in the untreated composition (Y) easily reaches the second surface 212 of the porous membrane 21. As a result, the untreated composition (Y) is easily dehydrated, and the concentration of cations in the untreated composition (Y) is likely to be reduced.

The composition (X) is obtained by dehydrating the untreated composition (Y) as described above. In the above description, for convenience, the composition that has not been dehydrated is defined as the untreated composition (Y), and the composition obtained by dehydrating the untreated composition (Y) is the composition (X). ), But the composition containing the components of the composition (X) may be regarded as the composition (X) regardless of whether or not it has been dehydrated.

The untreated composition (Y) may not be dehydrated in the production step of the composition (X), but the produced composition (X) may be dehydrated as described above. In this case, even if the produced composition (X) absorbs water, the water content of the composition (X) can be lowered. Therefore, the composition (X) can be molded by an inkjet method in a state where the water content is low to produce an optical component. At least one of the untreated composition (Y) and the composition (X) may be dehydrated, or both the untreated composition (Y) and the composition (X) may be dehydrated. Good.

When the composition (X) is dehydrated, the composition (X) is dehydrated, the composition (X) is placed in a container (storage container), and the composition is sent from the storage container to the inkjet device through piping. (X) may be supplied.

The storage container and the inkjet device may be connected by a supply pipe (supply pipe), and a dehydrator 20 may be provided in the middle of the supply pipe. In this case, the composition (X) can be dehydrated by the dehydrating device 20 while supplying the composition (X) from the storage container to the inkjet device through the supply pipe.

Further, the storage container and the inkjet device may be connected by a supply pipe and also connected by a recovery pipe (recovery pipe), and the dehydrator 20 may be provided in the middle of the recovery pipe. In this case, when the composition (X) once supplied from the storage container to the inkjet device through the supply pipe is returned to the storage container through the recovery pipe without being used, the composition (X) is dehydrated by the dehydrator 20. Can be processed. Therefore, even if the composition (X) absorbs water between the time it is supplied from the storage container to the ink jet device and the time it is recovered, the water content of the composition (X) is lowered by the dehydration treatment, so that the composition (X) contains water. The composition (X) can be used in a state where the rate is lowered.

It is preferable that the composition (X) is easily dehydrated when the porous membrane 21 is dehydrated, and the composition (X) is dehydrated. (X) may not be dehydrated. That is, the composition (X) has an advantage that it can be efficiently dehydrated if it is dehydrated.

Further, the composition (X) may be dehydrated without using the porous membrane 21. For example, by using a dehydrator containing a column and a granular dehydrating agent filled in the column, the untreated composition (Y) or the composition (X) is passed through the column to pass the untreated composition (Y). ) Or the composition (X) may be dehydrated. Further, the composition (X) or the untreated composition (Y) is dehydrated by stirring the composition (X) or the untreated composition (Y) and the dehydrating agent in a container. May be given. The dehydrating agent in these cases is, for example, molecular sieves, aluminum oxide, calcium chloride, calcium oxide, magnesium oxide, magnesium perchlorate, anhydrous magnesium sulfate, phosphorus oxide (V), anhydrous potassium carbonate, silica gel, sodium hydroxide, anhydrous. Examples include sodium sulfate and zinc chloride. Of these, molecular sieves is preferable because it has excellent drying ability.

The untreated composition (Y) or the composition (X) may be filtered using a filter. In this case, the content of particles having a certain size or more according to the performance of the filter in the composition (X) can be reduced. In the filtration process, for example, a filtration device including a flow path and a filter provided in the middle of the flow path is used. The pore diameter of the filter is preferably 0.5 μm or less. In this case, the filtration treatment can effectively reduce the particles having a particle size of 0.5 μm or more in the composition (X). In particular, when the untreated composition (Y) or the composition (X) is dehydrated using a dehydrating agent as described above and then filtered, the dehydrating agent particles are removed from the untreated composition ( Even if it is mixed with Y) or the composition (X), the content of particles above a certain level can be reduced by the filtration treatment. Therefore, when the composition (X) is applied by the inkjet method, the coatability tends to be good.

The filter is, for example, a membrane filter, but is not limited thereto. The material of the filter is, for example, polyethylene terephthalate, polyethylene, nylon and the like. Specific examples of the filter include the MCF series manufactured by Advantech Co., Ltd., the DFA series manufactured by Nippon Pole Co., Ltd., and the Polyfix PE series manufactured by KITZ Microfilter Co., Ltd.

In the present embodiment, particularly when the third Reynolds number of the composition (X) is 240 or more and 2400 or less, the untreated composition (Y) or the composition (X) is allowed to flow through the filter as described above. Therefore, when filtering, the efficiency of filtration tends to increase. In particular, for example, in the filtration treatment, the inner diameter of the flow path is within the range of 3.5 mm or more and 5.0 mm or less, and the flow velocity of the untreated composition (Y) or the composition (X) in the flow path is 1 L / min or more and 5 L / min. Filtration efficiency is likely to increase by making appropriate adjustments within the following range. When the third Reynolds number is 2400 or less, the untreated composition (Y) or the composition (X) is dehydrated by a dehydrating apparatus including the above-mentioned column and filler. Since the substance (Y) or the composition (X) easily flows through the gaps between the fillers, the efficiency of the dehydration treatment tends to increase.

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

In the present embodiment, the composition (X) is molded by an inkjet method to prepare a coating film, and then the coating film is irradiated with ultraviolet rays to the composition (X) and subsequently heated to form a sealing material 5. It is preferable to prepare. In the present embodiment, the composition (X) can be applied and molded by an inkjet method.

When the composition (X) is applied 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 50 mPa · s or less, the composition (X) ) Can be molded by applying by the inkjet method without heating.

When the composition (X) has a property of lowering the viscosity by heating, the composition (X) may be heated and then the composition (X) may be applied and molded by an inkjet method. When the viscosity of the composition (X) at 40 ° C. is 50 mPa · s or less, the viscosity of the composition (X) can be reduced by slightly heating the composition (X). It can be ejected by the inkjet method. The heating temperature of the composition (X) is, for example, 20 ° C. or higher and 50 ° C. or lower.

When the coating film obtained by molding the composition (X) is irradiated with light to be cured, the light irradiated to the coating film is, for example, ultraviolet rays. Ultraviolet rays mean light rays having a wavelength of 200 nm or more and 410 nm or less. The wavelength of the light irradiating the coating film is preferably 350 nm or more and 410 nm or less, and more preferably 385 nm or more and 405 nm or less. One of the typical examples of the light irradiating the coating film is light having a wavelength of 395 nm. The wavelength of the light irradiating 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 irradiating 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.

The shape of the portion irradiated with light when the coating film is irradiated with light may be an area type having a certain area or 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 moving the light source with respect to the coating film. In this case, it is easy to adjust the time for irradiating the coating film with light, and it is easy to adjust the integrated light amount by adjusting this time.

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

More specifically, for example, first, the support substrate 2 is prepared. A partition wall is formed on one surface of the support substrate 2 by a photolithography method using, for example, a photosensitive resin material. Subsequently, a plurality of light emitting elements 4 are provided on one surface of the support substrate 2. The light emitting element 4 can be manufactured by an appropriate method such as a vapor deposition method or a coating method. In particular, it is preferable that the light emitting element 4 is manufactured by a coating method such as an inkjet method. As a result, the element array 9 is manufactured on the support substrate 2.

Next, the 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, the composition (X) is molded on the first passivation layer 61 by, for example, an inkjet method to prepare a coating film. If the inkjet method is applied to both the formation of the light emitting element 4 and the coating of the composition (X), the production efficiency of the light emitting device 1 can be particularly improved. Subsequently, the coating film is cured by irradiating it with ultraviolet rays to prepare a sealing material 5. 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, since it is easy to form small droplets of the composition (X) at high density by the inkjet method, it is easy to realize a thin sealing material 5 having a thickness of 4 μm or more and 15 μm or less. When the sealing material 5 is made thinner in this way, tensile stress and compressive stress are less likely to occur in the sealing material 5 in the light emitting device 1. Therefore, it becomes easy to realize the flexible light emitting device 1.

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

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

As described above, the sealing material 5 made of the cured product of the composition (X) can have good heat resistance. Therefore, when the passivation layer 6 (second passivation layer 62) is manufactured by a vapor deposition method such as a plasma CVD method on top of the sealing material 5, the sealing material 5 deteriorates even if the temperature of the sealing material 5 rises. It's hard to do. Further, even if the temperature of the light emitting device 1 rises when the light emitting device 1 is used, the sealing material 5 is unlikely to deteriorate.

The application of the composition (X) according to the present embodiment is not limited to the production of the sealing material 5 for the light emitting element 4. The composition (X) can be used to produce various products molded by an inkjet method. For example, the composition (X) may contain a phosphor to prepare a color resist in a color filter from the composition (X). In this case, it is easy to fabricate the color resist in the color filter with high density and 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. 1. Preparation of Composition The compositions of Examples and Comparative Examples were prepared by mixing the components shown in the “Composition” column of the table below.

The details of the components shown in the table are as follows. The viscosities of the following components are values measured using a rheometer (manufactured by Anton Paar Japan K.K., model number DHR-2) under the conditions of a temperature of 25 ° C. and a shear rate of 1000 s ^-1 .

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

(1) Radical polymerizable compound-Polyethylene glycol 200 dimethacrylate: manufactured by Shin Nakamura Chemical Industry Co., Ltd., viscosity 14 mPa · s (25 ° C.), glass transition temperature 41 ° C.
-Pentatriestol tetraacrylate: manufactured by Shin Nakamura Chemical Industry Co., Ltd., viscosity 200 mPa · s (40 ° C.), glass transition temperature 103 ° C.
Trimethylolpropane triacrylate: viscosity 106 mPa · s, glass transition temperature 62 ° C., refractive index 1.472, boiling point 300 ° C. or higher, manufactured by Sartmer, product number SR351S.

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

(3) Monofunctional cationically polymerizable compound ・ AL-EOX: manufactured by Yokkaichi Chemical Company Limited, product name AL-EOX, compound represented by formula (16) (3-allyloxymethyl-3-ethyloxetane), viscosity 2 mPa · s.

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

(5) Photocation Initiator-CPI-210S: Photocation initiator (sulfonium salt) manufactured by Sun Appro Co., Ltd., product number CPI-210S.

2. 2. Dehydration 2-1. Method 1: Dehydration using a porous membrane In Examples 1 to 9 and Comparative Examples 1 and 2, a dehydrator having the configuration shown in FIG. 3 and having a zeolite membrane as the porous membrane was prepared. The outer diameter of the inner cylinder in the dehydrator is 0.012 m, and the inner diameter of the outer cylinder is 0.015 m. The composition was flowed in the flow space at a flow rate of 130 L / min while depressurizing the depressurized space in this dehydrator to a pressure of 0.3 KPa. This dehydrated the composition.

2-2. Method 2: Dehydration using a column and a dehydrating agent In Example 10, the composition was dehydrated by flowing the composition on a column packed with a dehydrating agent (molecular sieves) at a flow rate of 2.5 L / h.

2-3. Method 3: Dehydration by stirring using a dehydrating agent In Example 11, 10 to 40% by mass of the dehydrating agent (molecular sieves) of the composition was added to the composition, and the mixture was stirred and then left to stand for about 12 hours.

3. 3. Filtration treatment Using a filtration device provided with a membrane filter (manufactured by Advantech) with a pore diameter of 0.2 μm in a flow path with an inner diameter of 0.004 m, a membrane was applied to the composition while flowing the composition through the flow path at a flow rate of 2 L / min. It was filtered by passing it through a filter.

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

(1) Transmittance A coating film having a thickness of 10 μm is prepared by applying the composition after dehydration treatment and filtration treatment, and an LED-UV irradiator (peak wavelength 395 nm) manufactured by Panasonic Electric Works Co., Ltd. is used for this coating film. Then, in the atmosphere, ultraviolet rays were irradiated at an irradiation intensity of 3 W / cm ² for 5.3 seconds, and then heated at 100 ° C. for 5 minutes to prepare a film. The total light transmittance of this film according to JIS K7361-1 was measured.

(2) Viscosity The viscosity of the composition after dehydration treatment and filtration treatment was measured using a rheometer (manufactured by Anton Paar Japan K.K., model number DHR-2) under the conditions of a temperature of 25 ° C. and a shear rate of 1000 s ^-1 . ..

(3) Reynolds number The first Reynolds number, the second Reynolds number, and the third Reynolds number of the composition were calculated by the formula of Re = ρUL / μ. Re is the Reynolds number. ρ is the density of the composition (unit: kg / m ³ ), which is a value measured according to JIS Z8804: 2012 using a specific gravity bottle. U is the cross-sectional average flow velocity of the composition, which is 34.1 m / s for the first Reynolds number, 10.6 m / s for the second Reynolds number, and 2.7 m / s for the third Reynolds number. is there. L is 0.003 m, which is the difference between the inner diameter of the first circular pipe of 0.015 m and the outer diameter of the second circular pipe of 0.012 m in the case of the first Reynolds number, and is the third in the case of the second Reynolds number. The inner diameter of the circular pipe is 0.001 m, and in the case of the third Reynolds number, it is 0.00415 m, which is the inner diameter of the fourth circular pipe. μ is the viscosity coefficient (unit: Pa · s) of the composition, which is the measurement result of the above “(2) viscosity”.

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

(5) Moisture content The water content of the composition after the dehydration treatment and the filtration treatment was measured by the Karl Fischer method. A Karl Fischer titer MKC-710M (Kyoto Denshi Kogyo) was used as the measuring device.

(6) Sodium ion content The sodium ion content of the composition after the dehydration treatment and the filtration treatment was measured by an ICP emission spectrometer (Optima 4300DV manufactured by Perkin Elmer).

(7) Number of particles having a particle size of 0.5 μm or more The number of particles having a particle size of 0.5 μm or more per 1 mL of the composition in the composition after dehydration treatment and filtration treatment is measured by a side scattering method based on JIS Z8825. did. A particle counter (model number KS-42C) manufactured by Rion Co., Ltd. was used as the measuring device.

Claims (16)

Contains a photopolymerizable compound and a photopolymerization initiator,
The Reynolds number when flowing in the space between a circular pipe with an inner diameter of 0.015 m and a circular pipe with an outer diameter of 0.012 m contained in the circular pipe at a flow velocity of 130 L / min is more than 2300 and 23000 or less, and the inner diameter is 23000 or less. The Reynolds number is 230 or more and 2300 or less when flowing in a circular pipe of 0.001 m at a flow velocity of 0.5 L / min.
UV curable resin composition. Sodium ion content is 1 ppm by mass or less,
The ultraviolet curable resin composition according to claim 1. Moisture content is 200 mass ppm or less,
The ultraviolet curable resin composition according to claim 1 or 2. The viscosity at 25 ° C. is 5 mPa · s or more and 50 mPa · s or less.
The ultraviolet curable resin composition according to any one of claims 1 to 3. The viscosity at 40 ° C. is 5 mPa · s or more and 50 mPa · s or less.
The ultraviolet curable resin composition according to any one of claims 1 to 4. The photopolymerizable compound contains a radically polymerizable compound and contains
The photopolymerization initiator contains a photoradical polymerization initiator.
The ultraviolet curable resin composition according to any one of claims 1 to 5. The photopolymerizable compound contains a cationically polymerizable compound and contains
The photopolymerization initiator contains a cationic curing catalyst.
The ultraviolet curable resin composition according to any one of claims 1 to 6. It does not contain a solvent, or the content of the solvent is 1% by mass or less.
The ultraviolet curable resin composition according to any one of claims 1 to 7. For making encapsulants for light emitting elements,
The ultraviolet curable resin composition according to any one of claims 1 to 8. Molded by the inkjet method,
The ultraviolet curable resin composition according to any one of claims 1 to 9. The content of particles having a particle size of 0.5 μm or more is 100,000 or less per 1 mL of the ultraviolet curable resin composition.
The ultraviolet curable resin composition according to any one of claims 1 to 10. The method for producing an ultraviolet curable resin composition according to any one of claims 1 to 11.
The untreated composition containing the components of the ultraviolet curable resin composition is brought into contact with the first surface of the porous film having the first surface and the second surface opposite to the first surface, and said. The porous membrane comprises at least one of a zeolite membrane and a silica membrane, comprising depressurizing the space in contact with the second plane while flowing along the first plane.
A method for producing an ultraviolet curable resin composition. The method for producing an ultraviolet curable resin composition according to any one of claims 1 to 11.
The untreated composition containing the components of the ultraviolet curable resin composition is passed through a filter while flowing through a flow path.
A method for producing an ultraviolet curable resin composition. The untreated composition containing the components of the ultraviolet curable resin composition is passed through a filter while flowing through a flow path.
The method for producing an ultraviolet curable resin composition according to claim 12. A method of manufacturing a light emitting device including a light emitting element and a sealing material covering the light emitting element.
The ultraviolet curable resin composition according to any one of claims 1 to 11 is molded by an inkjet method to prepare a coating film, and the coating film is irradiated with ultraviolet rays to prepare the sealing material. Including that
Manufacturing method of light emitting device. A light emitting element and a sealing material covering the light emitting element are provided, and the sealing material comprises a cured product of the ultraviolet curable resin composition according to any one of claims 1 to 11.
Light emitting device.