JP2019212398A - Uv-curable resin composition for sealing organic el element, method for manufacturing organic el light-emitting device, and organic el light-emitting device - Google Patents

Abstract

To provide a UV-curable resin composition for sealing an organic EL element, which contains a moisture absorbent, which can be used to fabricate a sealing material for an organic EL light-emitting device, which can impart the adhesion with a member made of an inorganic material to such a sealing material, and which hardly causes the rise in viscosity.SOLUTION: The composition comprises: an acrylic compound (A); a photo-polymerization initiator (B); and a moisture absorbent (E) of 200 nm or less in average particle size. The acrylic compound (A) includes a compound (A1) represented by the formula (1) where Ris H or a methyl group, X is a single bond or a divalent hydrocarbon group, Rto Reach represent H, an alkyl group or -R-OH, Ris an alkylene group, at least one of Rto Ris an alkyl group or -R-OH, and Rto Rdo not make a chemical bond with each other.SELECTED DRAWING: None

Description

  The present invention relates to an ultraviolet curable resin composition for sealing an organic EL element, a method for producing an organic EL light-emitting device, and an organic EL light-emitting device, and more specifically, an organic material suitable for producing a sealing material in the organic EL light-emitting device. The present invention relates to an ultraviolet curable resin composition for sealing an EL element, a method for producing an organic EL light emitting device using the ultraviolet curable resin composition for sealing an organic EL element, and an organic EL light emitting device including the sealing material.

  Organic EL light-emitting devices are applied to lighting, displays, and the like, and are expected to become more widespread in the future.

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

  It has been proposed to produce a sealing material in an organic EL light emitting device by an inkjet method. For example, in Patent Document 1, 75 to 95 wt. % Polyethylene glycol dimethacrylate monomer and the like, 4 to 10 wt. % Pentaerythritol tetraacrylate, etc., having a viscosity in the range of about 14 to about 18 cps at 22 ° C. and a surface tension in the range of about 35 to about 39 dynes / cm at 22 ° C. It is disclosed that an encapsulant is produced by an ink jet method using an ink composition containing a% spread modifier.

  It has also been proposed to impart hygroscopicity to the sealing material by blending a hygroscopic agent in the composition for producing the sealing material. For example, Patent Document 2 discloses a sealing agent for organic electroluminescence display elements containing a radical polymerizable compound, a polymerization initiator and / or a curing agent, and a powdered molecular sieve.

Special table 2017-553049 gazette Japanese Patent Laid-Open No. 2006-012559

  In an organic EL light emitting device, a member made of an inorganic material is often applied as a transparent substrate, a passivation layer for protecting an organic EL element, or the like. If the adhesion between the sealing material and the inorganic material member is low, the moisture that has entered the organic EL light emitting device reaches the organic EL element through the gap formed between the sealing material and the member, and the organic There is a risk of deteriorating the EL element. For this reason, the sealing material may be required to have adhesiveness with a member made of an inorganic material.

  However, when an encapsulant is produced from an acrylic composition as described in Patent Document 1, the encapsulant and inorganic material are made while reducing the viscosity of the composition and allowing it to be molded by the inkjet method. It was difficult to ensure adhesion between the members. When a hygroscopic agent is included in the composition as in Patent Literature 2, it is more difficult to lower the viscosity of the composition. In particular, in order to reduce the diameter of the droplets ejected by the inkjet method in order to reduce the thickness of the sealing material, it is necessary to reduce the viscosity of the composition. It was very difficult to ensure adhesion between the material members.

  The subject of this invention contains a hygroscopic agent, can be used in order to produce the sealing material in an organic electroluminescent light-emitting device, can provide adhesiveness with the member made from an inorganic material, and viscosity. An ultraviolet curable resin composition for sealing an organic EL element that hardly causes an increase, a method for producing an organic EL light emitting device using the ultraviolet curable resin composition for sealing an organic EL element, and an ultraviolet curable for sealing the organic EL element It is providing an organic electroluminescent light emitting device provided with the sealing material which consists of hardened | cured material of a conductive resin composition.

  The ultraviolet curable resin composition for sealing an organic EL device according to one embodiment of the present invention contains an acrylic compound (A), a photopolymerization initiator (B), and a hygroscopic agent (E) having an average particle size of 200 nm or less, The acrylic compound (A) contains a compound (A1) represented by the following formula (1).

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

  The manufacturing method of the organic EL light-emitting device which concerns on 1 aspect of this invention is a method of manufacturing an organic EL light-emitting device provided with an organic EL element and the sealing material which covers the said organic EL element, For the said organic EL element sealing After forming an ultraviolet curable resin composition by an inkjet method, the ultraviolet curable resin composition for sealing an organic EL element is irradiated with ultraviolet rays and cured to prepare the sealing material.

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

  According to one embodiment of the present invention, it contains a hygroscopic agent and can be used to produce a sealing material in an organic EL light-emitting device, and can impart adhesion to a member made of an inorganic material to the sealing material. In addition, an ultraviolet curable resin composition for sealing an organic EL element that hardly causes an increase in viscosity, a method for producing an organic EL light emitting device using the ultraviolet curable resin composition for sealing an organic EL element, and the sealing of the organic EL element An organic EL light-emitting device including a sealing material made of a cured product of the ultraviolet curable resin composition for use can be provided.

FIG. 1 is a schematic cross-sectional view of a first example of an organic EL light emitting device. FIG. 2 is a schematic cross-sectional view of a second example of the organic EL light emitting device.

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

1. Outline of Embodiment The organic EL light emitting device 1 according to this embodiment includes an organic EL element 4 and a sealing material 5 that covers the organic EL element 4.

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

  The support substrate 2 is made of, for example, a resin material, but is not limited to this. The transparent substrate 3 is made from a material having translucency. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate. The organic EL element 4 is also called an organic light emitting diode. The organic EL element 4 includes, for example, a pair of electrodes and an organic light emitting layer located between the electrodes. The passivation layer 6 is preferably made from silicon nitride or silicon oxide.

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

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

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

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

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

  The sealing material 5 can be produced from the ultraviolet curable resin composition for sealing an organic EL element according to this embodiment. That is, the ultraviolet curable resin composition for sealing an organic EL element is used for producing a sealing material 5 for the organic EL element 4. In other words, the ultraviolet curable resin composition for sealing an organic EL element is preferably a composition for preparing a sealing material, a composition for sealing an organic EL element, or a composition for manufacturing an organic EL light emitting device. is there.

2. UV curable resin composition for sealing organic EL elements An ultraviolet curable resin composition for sealing organic EL elements (hereinafter also referred to as composition (X)) will be described.

  The composition (X) contains an acrylic compound (A), a photopolymerization initiator (B), and a hygroscopic agent (E) having an average particle size of 200 nm or less.

  The acrylic compound (A) contains a compound (A1) represented by the following formula (1). By the compound (A1), the sealing material 5 produced from the composition (X) can be provided with adhesion to a member made of an inorganic material such as the passivation layer 6.

  Further, simply dispersing the hygroscopic agent in the encapsulant 5 as disclosed in JP-A-2006-012559 causes a decrease in the transparency of the encapsulant 5, and the organic EL light emitting device. The light emission efficiency of 1 will fall. If the particle size of the encapsulant is reduced, the transparency of the encapsulant 5 can be expected to improve, but in this case, the viscosity of the composition for producing the encapsulant 5 increases, and the composition is molded. Becomes difficult. If the composition is simply made to contain a low-viscosity component to reduce the viscosity, the component is likely to volatilize from the composition, and the composition of the composition is likely to change during storage.

  However, in this embodiment, since the composition (X) contains the hygroscopic agent (E), the cured product has excellent hygroscopicity. Moreover, since the average particle diameter of a hygroscopic agent (E) is 200 nm or less, hardened | cured material can have high transparency.

  Further, the composition (X) contains the compound (A1), so that it can have a low viscosity despite containing the hygroscopic agent (E) having a small particle diameter of 200 nm or less. . For this reason, the applicability | paintability in the case of apply | coating composition (X) at the time of producing the sealing material 5 is favorable. For this reason, it is possible to apply the composition (X) by a casting method, an inkjet method or the like, and it is also possible to apply the composition (X) by an inkjet method at room temperature.

  Furthermore, the compound (A1) has a property of being less volatile in spite of having a low viscosity. Therefore, even if the composition (X) is stored, the composition (X) hardly changes in composition due to volatilization of the monofunctional cationically polymerizable compound (D). Moreover, since the compound (A1) does not easily react with the moisture absorbent (E), particularly zeolite particles, it is difficult to cause an increase in viscosity due to the reaction. For this reason, the composition (X) can be reduced in viscosity without impairing the storage stability of the composition (X).

  Thereby, in this embodiment, it can use in order to produce the sealing material 5 in the organic EL light-emitting device 1 containing a hygroscopic agent (E), and the sealing material 5 has adhesiveness with the member made of an inorganic material. A composition (X) that can be applied and hardly raises the viscosity is obtained.

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

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

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

In the formula (1), 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 among R ¹ to R ¹¹ is an alkyl group or —R ¹² —OH, and each of the remaining is H. Among R ¹ to R ¹¹ , it is particularly preferred that only R ⁶ is an alkyl group or —R ¹² —OH, and the remaining each is H. In this case, the compound represented by the formula (1) can have good reactivity, and is particularly easy to impart adhesion to the sealing material 5 with a member made of an inorganic material. This is because the cyclohexane ring in the compound represented by the formula (1) has a boat-type conformation, and the bulky alkyl group at the 4-position or -R ¹² -OH is easily located at the pseudo-equatorial position. it is conceivable that. It is considered that the reactivity of the (meth) acryloyl group in the compound represented by the formula (1) is enhanced by the compound represented by the formula (1) having such a structure. Moreover, when the compound shown by Formula (1) has such a structure, the compound shown by Formula (1) can enlarge the free volume in the sealing material 5. FIG. Therefore, it is considered that the interface free energy between the sealing material 5 and the member made of an inorganic material tends to be small, and the adhesion between the sealing material 5 and the member made of an inorganic material tends to be high. The higher the bulk alkyl group or -R ¹² -OH, alkyl or -R ¹² -OH is likely located in pseudo equatorial position. From this point of view, it is preferable that preferably larger the number of carbon atoms in the alkyl group or -R ¹² -OH, also an alkyl group or -R ¹² -OH and a branch. For example, the alkyl group or —R ¹² —OH is preferably a t-butyl group.

In the formula (1), it is also preferable that an alkyl group or —R ¹² —OH is connected to each of the 3-position and 5-position of the cyclohexane ring. That is, among R ¹ to R ¹¹ , at least one of R ⁴ and R ⁵ is an alkyl group or —R ¹² —OH, at least one of R ⁸ and R ⁹ is an alkyl group or —R ¹² —OH, It is preferred that each remaining is H. Of R ¹ to R ¹¹ , only one of R ⁴ and R ⁵ is an alkyl group or —R ¹² —OH, at least one of R ⁸ and R ⁹ is an alkyl group or —R ¹² —OH, and the rest More preferably, each is H. Among R ¹ to R ¹¹ , at least one of R ⁴ and R ⁵ is an alkyl group or —R ¹² —OH, only one of R ⁸ and R ⁹ is an alkyl group or —R ¹² —OH, and the rest It is also more preferable that each is H. Also in this case, the compound represented by the formula (1) can have good reactivity, and is particularly easy to impart adhesion to the sealing material 5 with a member made of an inorganic material. This is because the cyclohexane ring in the compound represented by the formula (1) has a boat-type conformation, and a bulky alkyl group or —R ¹² —OH in each of the 3-position and 5-position is located in the pseudo-equatorial position. This is probably because it is easy. For this reason, the reactivity of the (meth) acryloyl group in the compound represented by the formula (1) is increased as in the case where an alkyl group or —R ¹² —OH is connected only to the 4-position of the cyclohexane ring, and It is considered that the adhesion between the sealing material 5 and the inorganic material member tends to be high. The higher the bulk alkyl group or -R ¹² -OH, alkyl or -R ¹² -OH is likely located in pseudo equatorial position. From this point of view, it is preferable that preferably larger the number of carbon atoms in the alkyl group or -R ¹² -OH, also an alkyl group or -R ¹² -OH and a branch. For example, the alkyl group or —R ¹² —OH is preferably a t-butyl group.

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

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

  The compound (A1) preferably contains at least one compound selected from the group consisting of a compound represented by the following formula (11), a compound represented by the following formula (12) and a compound represented by the following formula (13).

  It is particularly preferred that the compound (A1) contains at least one of the compound represented by the formula (11) and the compound represented by the formula (12). In this case, the composition (X) can be particularly easily reduced in viscosity, the glass transition temperature of the sealing material 5 can be particularly easily increased, and the adhesion between the sealing material 5 and the member made of an inorganic material can be particularly easily increased. Moreover, since the compound shown to Formula (11) and the compound shown to Formula (12) are hard to volatilize, it is easy to improve the storage stability of composition (X).

  The boiling point of the compound contained in the compound (A1) is preferably 200 ° C. or higher, and more preferably 250 ° C. or higher. In this case, the compound (A1) is particularly likely to improve the storage stability of the composition (X). Since the boiling point of the compound represented by the formula (11) is 265 ° C., the boiling point of the compound represented by the formula (12) is 234 ° C., and the boiling point of the compound represented by the formula (13) is 294 ° C. Is preferred.

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

  The acrylic compound (A) may further contain a compound (A2) other than the compound (A1).

  Compound (A2) contains, for example, a polyfunctional acrylic compound (A21) having two or more (meth) acryloyl groups in one molecule. In this case, polyfunctional acrylic compound (A21) can raise the glass transition temperature of the hardened | cured material of composition (X), and can improve the heat resistance of hardened | cured material and the sealing material 5 for this reason.

  When the acrylic compound (A) contains the polyfunctional acrylic compound (A21), the amount of the polyfunctional acrylic compound (A21) with respect to the total amount of the acrylic compound (A) is preferably 5% by mass or more and 85% by mass or less. When the amount of the polyfunctional acrylic compound (A21) is 5% by mass or more, the polyfunctional acrylic compound (A21) is particularly likely to increase the glass transition temperature of the cured product. Adhesiveness with the member made from an inorganic material of the sealing material 5 can be improved as the quantity of a polyfunctional acrylic compound (A21) is 85 mass% or less.

  The polyfunctional acrylic compound (A21) is, for example, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol oligoacrylate, diethylene glycol diacrylate, 1,6-hexanediol oligoacrylate, neopentyl glycol diacrylate, Triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclohexane dimethanol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, pentatriestol tetra Acrylate, propoxylated (2) neopentyl glycol diacrylate, trimethylolpropane triac Rate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated (3) trimethylolpropane triacrylate, propoxylated (3) glyceryl triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, Ethoxylated (4) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, hexadiol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol triacrylate, bis Pentaerythritol hexaacrylate, ethylene glycol diacryl 1,6-hexanediol diacrylate, ethoxylated 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, hydroxypivalate neopentyl glycol diacrylate, hydroxypivalate trimethylolpropane triacrylate, ethoxylated phosphate triacrylate, ethoxylated tripropylene glycol diacrylate Acrylate, neopentyl glycol modified trimethylolpropane diacrylate, stearic acid modified pentaerythritol diacrylate, tetramethylolpropane triacrylate Lilate, tetramethylol methane triacrylate, caprolactone modified trimethylol propane triacrylate, propoxylate glyceryl triacrylate, tetramethylol methane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, di Pentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di ( Me ) Acrylate contains at least one compound selected ethoxylated trimethylolpropane triacrylate, and from the group consisting of propoxylated trimethylol propane triacrylate.

  The acrylic equivalent of the polyfunctional acrylic compound (A21) 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 (A21) is, for example, from 100 to 1,000, and more preferably from 200 to 800.

  The polyfunctional acrylic compound (A21) preferably has at least one of a benzene ring, an alicyclic ring and a polar group. The polar group is, for example, at least one of an OH group and an NHCO group. In this case, the shrinkage when the composition (X1) is cured can be particularly reduced. Furthermore, the adhesion between the cured product and an inorganic compound such as silicon nitride or silicon oxide can be enhanced. The polyfunctional acrylic compound (A21) is particularly selected from the group consisting of tricyclodecane dimethanol diacrylate, bisphenol A polyethoxydiacrylate, bisphenol F polyethoxydiacrylate, trimethylolpropane triacrylate and pentatriestol tetraacrylate. It is preferable to contain at least one compound. These compounds can particularly reduce shrinkage when the composition (X) is cured. Furthermore, these compounds can further enhance the adhesion between the cured product and a member made of an inorganic material such as silicon nitride or silicon oxide.

  It is also preferable that the compound (A2) contains a monofunctional acrylic compound (A22) having only one (meth) acryloyl group in one molecule other than the compound (A1). The monofunctional acrylic compound (A22) can suppress shrinkage during curing of the composition (X).

  The amount of the monofunctional acrylic compound (A22) with respect to the total amount of the acrylic compound (A) is preferably more than 0% by mass and 70% by mass or less. When the amount of the monofunctional acrylic compound (A22) is greater than 0% by mass, the monofunctional acrylic compound (A22) can suppress shrinkage during curing of the composition (X).

  The monofunctional acrylic compound (A22) is, for example, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, 2-methoxyethyl acrylate , Methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydixylethyl acrylate, ethyl diglycol acrylate, cyclic trimethylolpropane formal monoacrylate, Imido acrylate, isoamyl acrylate, ethoxylated 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, phenoxy Ethyl acrylate, cyclohexyl (medium Acrylate), dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl acrylate, methylphenoxyethyl 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, isobornyl acrylate, morpholine acrylate, diethyl acrylamide, dimethylaminopropyl acrylamide, pentamethylpiperidyl methacrylate, Dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate And at least one compound selected from the group consisting of 2-hydroxy-3-phenoxypropyl acrylate, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide and dicyclopentenyloxyethyl acrylate .

  The monofunctional acrylic compound (A22) preferably contains 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, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, isobornyl acrylate, dicyclopentanyl acrylate. It contains at least one compound selected from the group consisting of a rate and dicyclopentenyloxyethyl acrylate.

  In particular, the acrylic compound (A) preferably contains at least one of isobornyl acrylate and dicyclopentenyloxyethyl acrylate. Isobornyl acrylate and dicyclopentenyloxyethyl acrylate have a high glass transition temperature, and can particularly increase the glass transition temperature of the sealing material 5.

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

  The compound (A2) may contain an acrylic component (A23) composed of at least one of polyethylene glycol dimethacrylate and polyethylene glycol diacrylate. The acrylic component (A23) preferably has a number average molecular weight of 230 or more and 430 or less.

  When the acrylic component (A23) contains polyethylene glycol dimethacrylate, the polyethylene glycol dimethacrylate includes, for example, polyethylene glycol 200 dimethacrylate represented by the following formula (21). N in the formula (21) is 4 on average. When the acrylic component (A23) contains polyethylene glycol diacrylate, the polyethylene glycol diacrylate includes, for example, polyethylene glycol 200 diacrylate represented by the following formula (22). N in the formula (22) is 4 on average.

_{CH 2 = C (CH 3)} -CO- (OCH 2 CH 2) n -OCO-C (CH 3) = CH 2 ... (21)
_{CH 2 = CH-CO- (OCH} 2 CH 2) n -OCO-CH = CH 2 ... (22)
When the compound (A2) contains an acrylic component (A23), the compound (A2) preferably further contains an acrylic component (A24) composed of at least one of pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate.

  When the compound (A2) contains the acrylic component (A23), the composition (X) may further contain a spreading agent (C). The spreading agent (C) has a viscosity of 14 mPa · s to 18 mPa · s at 22 ° C., and a surface tension of 35 mN / m to 39 mN / m at 22 ° C. The spreading agent (C) can adjust the spreading characteristics of the composition (X). The spreading agent (C) is preferably a liquid having a lower surface tension than the acrylic component (A23) at the molding temperature. The molding temperature is the temperature of the composition (X) when the composition (X) is molded by a method such as an ink jet method.

  The spreading agent (C) preferably contains at least one component selected from the group consisting of alkoxylated aliphatic diacrylates and alkoxylated aliphatic dimethacrylates.

  The alkoxylated aliphatic diacrylate is represented, for example, by the following formula (3). In the formula (3), n is a number from 3 to 12. The alkoxylated aliphatic dimethacrylate is represented, for example, by the following formula (4). In the formula (4), n is a number from 3 to 12.

_{CH 2 = CH-COO- (CH} 2) n -OCO-CH = CH 2 ... (3)
_{CH 2 = C (CH 3)} -COO- (CH 2) n -OCO-C (CH 3) = CH 2 ... (4)
Specific examples of components that can be contained in the alkoxylated aliphatic diacrylate are Sartomer part number SR-238B (1,6 hexanediol diacrylate, surface tension of about 35 mN / m at 25 ° C.) and Sartomer part number SR. -9209A (surface tension at 22 ° C. about 35 mN / m, viscosity at 22 ° C. about 25 mN / m).

  When the acrylic compound (A) contains the acrylic component (A23), the amount of the acrylic component (A23) with respect to the total amount of the acrylic compound (A) is preferably 5% by mass or more and 60% by mass or less. When the acrylic compound (A) contains the acrylic component (A24), the amount of the acrylic component (A24) with respect to the total amount of the acrylic compound (A) is preferably 1% by mass or more and 20% by mass or less.

  The acrylic compound (A) preferably does not contain a compound having a nitrogen atom. For this reason, it is preferable that the acrylic compound (A) does not contain any of morpholine acrylate, diethyl acrylamide, dimethylaminopropyl acrylamide, and pentamethylpiperidyl methacrylate. In this case, the viscosity increase of the composition (X) hardly occurs during the storage of the composition (X). This is considered to be because when the composition (X) contains a compound having nitrogen and a hygroscopic agent (E), the compound having nitrogen and the hygroscopic agent (E) easily react. Moreover, when an acrylic compound (A) does not contain the compound which has a nitrogen atom, there also exists an advantage that the sealing material 5 becomes difficult to discolor.

  The composition (X) may further contain a radical polymerizable compound (D) other than the acrylic compound (A). The radical polymerizable compound (D) is composed of a polyfunctional radical polymerizable compound (E1) having two or more radical polymerizable functional groups in one molecule and a monofunctional having only one radical polymerizable functional group in one molecule. Either one or both of the radical polymerizable compound (E2) can be contained.

  The amount of the radical polymerizable compound (D) with respect to the total amount of the acrylic compound (A) and the radical polymerizable compound (D) is, for example, 10% by mass or less.

  The polyfunctional radically polymerizable compound (E1) is, for example, a group consisting of an aromatic urethane oligomer, an aliphatic urethane oligomer, an epoxy acrylate oligomer, a polyester acrylate oligomer, and other special oligomers having two or more ethylenic double bonds in one molecule. You may contain the at least 1 sort (s) of compound selected from these. More specifically, the polyfunctional radical polymerizable compound (A) is, for example, UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV-3200B, UV-3300B manufactured by Nippon Synthetic Chemical Industry Co., Ltd. UV-3700B, UV-6640B, UV-8630B, UV-7000B, UV-7610B, UV-1700B, UV-7630B, UV-6300B, UV-6640B, UV-7550B, UV-7600B, UV-7605B, UV- 7610B, UV-7630B, UV-7640B, UV-7650B, UT-5449, UT-5454; CN902, CN902J75, CN929, CN940, CN944, CN944B85, CN959, CN961E75, CN961 manufactured by Sartomer 62, CN963, CN963A80, CN963B80, CN963E75, CN963E80, CN963J85, CN964, CN965, CN965A80, CN966, CN966A80, CN966B85, CN966H90, CN966J75, CN968, CN969, CN970, CN970A60, CN970E60, CN971, CN971A80, CN971J75, CN972, CN973, CN973A80, CN973H85, CN973J75, CN975, CN977, CN977C70, CN978, CN980, CN981, CN981A75, CN981B88, CN982, CN982A75, CN982B88, CN982C98C, CN982C98C CN986, CN989, CN991, CN992, CN994, CN996, CN997, CN999, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009, CN9010, C9011, CN9013, C9011, CN9013, C9090 CN9029, CN9030, CN9060, CN9165, CN9167, CN9178, CN9290, CN9782, CN9783, CN9788, CN9873; and EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270B, EBECRYL270B L8210, EBECRYL8301, EBECRYL8804, EBECRYL8807, EBECRYL9260, KRM7735, KRM8296, KRM8452, EBECRYL4858, EBECRYL8402, EBECRYL9270, EBECRYL8311, EBECRYL8311

  Monofunctional radically polymerizable compound (E2) is, for example, N-vinylformamide, vinylcaprolactam, vinylpyrrolidone, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene It contains at least one compound selected from the group consisting of oxide, N-vinylpyrrolidone and N-vinylcaprolactam.

  The photopolymerization initiator (B) is not particularly limited as long as it is a compound that generates radical species when irradiated with ultraviolet rays. The photopolymerization 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 compounds And at least one compound selected from the group consisting of a ketoxime ester compound, a borate compound, an azinium compound, a metallocene compound, an active ester compound, a compound having a carbon halogen bond, and an alkylamine compound.

  The photopolymerization initiator (B) preferably contains an acylphosphine oxide photopolymerization initiator. Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphinate. Examples of product names of acylphosphine oxide photopolymerization initiators include Irgacure TPO, Irgacure TPO-L and Irgacure 819 manufactured by BASF.

  The amount of the photopolymerization initiator (B) with respect to 100 parts by mass of the composition (X) is, for example, 1 part by weight or more and 10 parts by weight or less.

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

  The content of the sensitizer in the composition (X) is, for example, 0.1 parts by mass or more and 5 parts by mass or less, preferably 0.1 parts by mass with respect to 100 parts by mass of the solid content of the composition (X). Part to 3 parts by mass. When the content of the sensitizer is in such a range, the composition (X) can be cured in the air, and the composition (X) needs to be cured in an inert atmosphere such as a nitrogen atmosphere. Disappear.

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

  As described above, the composition (X) contains a hygroscopic agent (E) having an average particle size of 200 nm or less. The hygroscopic agent (E) is preferably inorganic particles having hygroscopicity, and contains at least one component selected from the group consisting of zeolite particles, silica gel particles, calcium chloride particles, and titanium oxide nanotube particles, for example. Is preferred. It is particularly preferred that the hygroscopic agent (E) contains zeolite particles.

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

  The zeolite particles preferably contain sodium ions. For this purpose, the zeolite particles are preferably produced from zeolite containing sodium ions, and are produced from at least one material selected from the group consisting of A-type zeolite, X-type zeolite and Y-type zeolite among sodium ions. More preferably. It is particularly preferred that the zeolite particles are produced from 4A type zeolites among the A type zeolites. In these cases, the zeolite particles have a crystal structure suitable for moisture adsorption.

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

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

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

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

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

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

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

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

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

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

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

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

  The average particle diameter of the hygroscopic agent (E) is preferably 10 nm or more and 200 nm or less. If this average particle diameter is 200 nm or less, the cured product can have particularly high transparency. Moreover, if this average particle diameter is 10 nm or more, the good hygroscopicity of the hygroscopic agent (E) can be maintained. The average particle diameter is a median diameter calculated from a measurement result by a dynamic light scattering method, that is, a cumulative 50% diameter (D50). In addition, as a measuring apparatus, the nano track Nanotrac Wave series of Microtrack Bell Inc. can be used.

  The average particle diameter of the hygroscopic agent (E) is more preferably 150 nm or less, still more preferably 100 nm or less, and particularly preferably 70 nm or less. Moreover, it is preferable that the average particle diameter of a hygroscopic agent (E) is 20 nm or more, and it is more preferable if it is 50 nm or more. In this case, the cured product can have particularly good transparency and hygroscopicity.

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

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

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

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

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

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

  When the composition (X) contains the dispersant (F), the hygroscopic agent (E) can be favorably dispersed in the composition (X) and the cured product. For this reason, although hardened | cured material and the sealing material 5 contain a hygroscopic agent (E), transparency of hardened | cured material and the sealing material 5 is hard to be reduced with a hygroscopic agent (E). Further, the dispersant (F) can effectively suppress the aggregation of the hygroscopic agent (E) during storage of the composition (X). Therefore, the storage stability of the composition (X) is not easily lowered by the hygroscopic agent (E). Furthermore, the adhesiveness between the cured product and silicon nitride and silicon oxide is not easily lowered by the dispersant (F). This is because the dispersant (F) is easily adsorbed to the moisture absorbent (E) as described above, and the dispersant (F) hardly affects the interface between the cured product, silicon nitride and silicon oxide. It is believed that there is. For this reason, the sealing material 5 can have high adhesiveness with a glass-made base material. Silicon nitride and silicon oxide may be used as a material for the passivation layer 6 in the organic EL light emitting device 1. For this reason, when the passivation layer 6 is made of silicon nitride or silicon oxide, the sealing material 5 can have high adhesion to the passivation layer 6.

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

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

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

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

  The basic polar functional group in the dispersant (F1) having a basic polar functional group is, for example, at least one selected from the group consisting of an amino group, an imino group, an amide group, an imide group, and a nitrogen-containing heterocyclic group. Including the group When the dispersant (F1) has a basic polar functional group, the dispersant (F1) is likely to be adsorbed on the hygroscopic agent (E), so that the dispersibility of the hygroscopic agent (E) can be improved. The basic polar functional group can particularly enhance the adsorption ability of the dispersant (F1) to the moisture absorbent (E), can particularly improve the dispersibility of the moisture absorbent (E), and the composition (X). An amino group is preferably included because the viscosity can be particularly reduced.

  Examples of the dispersant (F1) having a basic polar functional group include trade name: Solsperse 24000 (amine value: 41.6 mgKOH / g), trade name: Solsperse 32000 (amine value: 31.2 mgKOH / g), trade name. : Solsperse 39000 (amine value: 25.7 mgKOH / g), trade name: Solsperse J100, trade name: Solsperse series manufactured by Japan Louvre Resol Co., Ltd .; trade name: DISPERBYK-108, DISPERBYK-2013, DISPERBYK -180, DISPERBYK-106, DISPERBYK-162 (amine value: 13 mgKOH / g), trade name: DISPERBYK-163 (amine value: 10 mgKOH / g), trade name: DISPERBYK-168 (amine value: 1 mgKOH / g), trade name: DISPERBYK-2050 (amine value: 30.7 mgKOH / g), trade name: DISPERBYK-2150 (amine value: 56.7 mgKOH / g), etc. Product name: BYKJET-9151 (amine value: 17.2 mgKOH / g), product name: BYKJET-9152 (amine value: 27.3 mgKOH / g), etc. BYKJET Japan made BYKJET series; and product name: Ajinomoto Fine Techno Co., Ltd., such as Ajisper PB821 (amine value: 11.2 mgKOH / g), trade name: Azisper PB822 (amine value: 18.2 mgKOH / g), trade name: Azisper PB881 (amine value: 17.4 mgKOH / g) Company made Including di-spar series.

  The amine value of the dispersant (F1) is preferably 10 mgKOH / g or more, more preferably 10 mgKOH / g or more and 30 mgKOH / g or less, and further preferably 15 mgKOH / g or more and 30 mgKOH / g or less. Moreover, it is preferable that a dispersing agent (F1) does not have a phosphate group. When the dispersant (F1) has a phosphoric acid group, the acid value derived from the phosphoric acid group is preferably not more than the amine value. In this case, the dispersant (F1) can disperse the hygroscopic agent (E) particularly well, can particularly enhance the storage stability of the composition (X), and particularly enhance the transparency of the cured product. In addition, the adhesion between the cured product and silicon nitride and silicon oxide can be particularly enhanced. Of the components that can be contained in the dispersant (F1), examples of the dispersant having an amino group and not having a phosphate group include DISPERBYK-108 manufactured by BYK Chemie. Examples of the dispersant having an amino group and a phosphate group and having an acid value derived from the phosphate group equal to or less than the amine value include DISPERBYK-2013 manufactured by BYK Chemie and DISPERBYK-180 manufactured by BYK.

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

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

  The viscosity at 25 ° C. of the composition (X) is preferably 50 mPa · s or less. In this case, the composition (X) can be easily molded by a method such as a casting method at room temperature, and the composition (X) can also be molded by an inkjet method at room temperature. The composition (X) contains the compound (A1), in particular, the compound represented by the above formula (11), the compound represented by the formula (12), and at least one compound selected from the group consisting of morpholine acrylate, Such composition (X) can be reduced in viscosity. The viscosity at 25 ° C. of the composition (X) is more preferably 20 mPa · s or less, and particularly preferably 13 mPa · s or less. Further, the viscosity of the composition (X) is, for example, 1 mPa · s or more, 5 mPa · s or more, or 10 mPa · s or more.

  It is also preferable that the viscosity at 40 ° C. of the composition (X) is 1 mPa · s or more and 50 mPa · s or less. In this case, even if the viscosity of the composition (X) at normal temperature is any value, the viscosity can be lowered by slightly heating the composition (X). Therefore, if heated, the composition (X) can be easily molded by a method such as a casting method, and the composition (X) can also be molded by an ink jet method. The viscosity is more preferably 20 mPa · s or less, and particularly preferably 13 mPa · s or less. Moreover, the viscosity at 40 ° C. of the composition (X) is, for example, 1 mPa · s or more, 5 mPa · s or more, or 10 mPa · s or more.

  The composition (X) is preferably cured to become a cured product having a glass transition temperature of 90 ° C. or higher. That is, it is preferable that the glass transition temperature of the hardened | cured material of composition (X) and the glass transition temperature of the sealing material 5 produced from composition (X) are 90 degreeC or more. In this case, the sealing material 5 produced from the composition (X) can have heat resistance. Therefore, for example, when a high-temperature treatment is performed at the time of manufacturing the organic EL light-emitting device 1, for example, when the passivation layer 6 is formed on the sealing material 5 by a plasma CVD method, or when the organic EL light-emitting device 1 is used. When exposed to high temperatures, the sealing material 5 is unlikely to deteriorate. The glass transition temperature is more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. In particular, when the composition (X) contains a polyfunctional compound such as an acrylic component (A23), the molecular structure of the cured product can be easily made three-dimensional, so that the glass transition temperature of such a cured product can be achieved. It is.

  When the thickness of the cured product of the composition (X) is 10 μm, the total light transmittance is preferably 90% or more. In this case, when the cured product is applied to the sealing material 5 in the organic EL light-emitting device 1, it is possible to particularly improve the extraction efficiency of light that passes through the sealing material 5 and is emitted to the outside. Such a high light transmittance of the cured product can be achieved by the composition of the composition (X) described in detail above.

3. Manufacturing method of sealing material, and manufacturing method of organic EL light-emitting device The manufacturing method of the sealing material 5 using composition (X) and the manufacturing method of the organic EL light-emitting device 1 are demonstrated.

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

  In applying the composition (X) by the inkjet method, when the composition (X) has a sufficiently low viscosity at room temperature, for example, when the viscosity at 25 ° C. is 50 mPa · s or less, particularly 20 mPa · s or less. Can be formed by applying the composition (X) by an inkjet method without heating.

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

  A method for producing the organic EL light emitting device 1 of the first example shown in FIG. 1 will be described. For example, first, the support substrate 2 is prepared. An organic EL element 4 is provided on one surface of the support substrate 2. The organic EL element 4 can be produced by an appropriate method such as a vapor deposition method or a coating method. In particular, the organic EL element 4 is preferably produced by a coating method such as an inkjet method.

  Next, a passivation layer 6 is provided. The passivation layer 6 can be produced by, for example, a vapor deposition method.

  Next, the composition (X) is molded by an inkjet method so as to cover one surface of the support substrate 2 and the organic EL element 4. In the case where the passivation layer 6 is provided, the composition (X) is formed so as to cover the passivation layer 6. If the inkjet method is applied to both the formation of the organic EL element 4 and the application of the composition (X), the production efficiency of the organic EL light-emitting device 1 can be particularly improved.

  Next, the transparent substrate 3 is overlaid on the composition (X). The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate.

  Next, ultraviolet rays are irradiated from the outside toward the transparent substrate 3. The ultraviolet rays pass through the transparent substrate 3 and reach the composition (X). Thereby, radical polymerization reaction advances in composition (X), composition (X) hardens | cures, and the sealing material 5 which consists of hardened | cured material is produced. The thickness of the sealing material 5 is, for example, 5 μm or more and 50 μm or less.

  The composition (X) may be formed by a method other than the ink jet method, for example, a casting method.

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

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

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

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

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

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

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

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

1. Preparation of composition The composition of an Example and a comparative example was prepared by mixing the component shown in the following table | surface. The details of the components shown in the table are as follows.
TBCHA: 4-tertiarybutylcyclohexyl acrylate which is a compound represented by the formula (11), a viscosity at 25 ° C. of 7 mPa · s, a glass transition temperature of 77 ° C., and a boiling point of 265 ° C.
-Biscote # 196: 3,3,5-trimethylcyclohexyl acrylate which is a compound represented by the formula (12), viscosity at 25 ° C. 3 mPa · s, glass transition temperature 52 ° C., boiling point 234 ° C., manufactured by Osaka Organic Chemical Industries, Ltd. .
CHDMMA: cyclohexanedimethanol monoacrylate which is a compound represented by the formula (13), viscosity at 25 ° C. 88 mPa · s, glass transition temperature 18 ° C., boiling point 294 ° C.
ACMO: morpholine acrylate, viscosity at 25 ° C. 12 mPa · s, glass transition temperature 145 ° C.
IBXA: isobornyl acrylate, viscosity at 25 ° C. 8 mPa · s, glass transition temperature 97 ° C.
TMPTA: trimethylolpropane triacrylate, viscosity at 25 ° C. 106 mPa · s.
Polyethylene glycol 200 dimethacrylate: manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 330, viscosity at 25 ° C .: 14 mPa · s, glass transition temperature: 41 ° C.
Polyethylene glycol 200 diacrylate, manufactured by Osaka Organic Chemical Co., Ltd., molecular weight 308, viscosity at 25 ° C., 17 mPa · s, glass transition temperature 41 ° C.
Bisphenol A polyethoxydiacrylate: Nippon Kayaku, product number R551, viscosity at 25 ° C., 800 mPa · s.
Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF, product name Irgacure 184.
Irgacure TPO: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, manufactured by BASF, product name Irgacure TPO.
Adsorbent: Zeolite particles produced by the following method, having a D50 of 60 nm, a D90 of 110 nm, and a pH of 11.

4A-type zeolite sodium ions having an average particle diameter of 5 μm were prepared as the starting material zeolite powder, and 100 g of this zeolite powder and 100 g of ion-exchanged water were mixed to prepare a slurry. The zeolite powder in this slurry was pulverized with a bead mill pulverizer such that the average particle size was 60 nm. Subsequently, the slurry was allowed to stand at a temperature of 180 ° C. for 2 to 3 hours to obtain finely pulverized zeolite powder. The zeolite powder was crushed with a mortar and then passed through a mesh to adjust the particle size to obtain zeolite particles. The pH of the zeolite particles was measured by the following method. After putting 0.05 g of zeolite particles and 99.95 g of ion-exchanged water in a polyethylene bottle, the bottle was put in a thermostatic bath and heated at 90 ° C. for 24 hours. Subsequently, the pH of the supernatant in the bottle was measured using a compact pH meter <LAQUATwin> B-711 manufactured by Horiba.
Dispersant: Comb-type resin dispersant of fatty acid amine having polyethyleneimine as the main skeleton, amine value 31 mgKOH / g, acid value 15 mgKOH / g, boiling point 200 ° C. or higher, manufactured by Lubrizol, product name Solsperse 32000.

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

(1) Transmittance The composition was applied to prepare a coating film, and this coating film was subjected to a condition of about 100 mW / cm ² using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works Co., Ltd. A film having a thickness of 10 μm was produced by photo-curing by irradiating with ultraviolet rays for 15 seconds. The total light transmittance of this film was measured according to JIS K7361-1.

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

(3) Glass transition temperature A coating film was prepared by applying the composition, and this coating film was subjected to a condition of about 100 mW / cm ² using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works Co., Ltd. Was cured by irradiating with ultraviolet rays for 15 seconds to produce a film having a thickness of 100 μm.

  The glass transition temperature of the film obtained above was measured using a viscoelastic spectrometer “DMS6100” manufactured by Seiko Instruments Inc. At this time, dynamic viscoelasticity measurement (DMA) is performed with a tensile module at a frequency of 10 Hz, and the temperature at which tan δ is maximized when the temperature is raised from room temperature to 200 ° C. at a temperature increase rate of 5 ° C./min is a glass transition. It was temperature.

(4) Ink-jet property The composition is put into a cartridge of an ink-jet printer (manufactured by MicroJet, “NanoPrinter300”), and after confirming that the composition in the cartridge can be discharged from the nozzle in the ink-jet printer, the composition from the nozzle The test pattern was continuously printed by discharging the ink. As a result, “A” when the composition can be discharged for 1 hour and the discharge operation is stable, “B” when the composition can be discharged for 1 hour but the discharge operation becomes intermittently unstable. The case where the nozzle was clogged 1 hour after the start of discharge and the composition could not be discharged was evaluated as “C”.

(5) Adhesion Two substrates were produced by forming a SiON film having a thickness of 100 nm on each of two slide glasses (dimensions 76 mm × 52 mm × 1 mm). The composition was applied to the SiON film of one substrate to form a 50 μm-thick coating film, and the SiON film formation of the other substrate was overlaid on this coating film. Subsequently, the coating film was cured by UV irradiation for 20 seconds under the condition of about 30 mW / cm ² using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works Co., Ltd. Next, the adhesion strength between the two substrates was evaluated by performing a T-peel test based on JIS K6854.

(6) Storage property (storage stability)
The composition was left for 1 month at a temperature of 40 ° C. under a nitrogen atmosphere. The viscosity of the composition before the test and the viscosity of the composition after the test were measured using a rheometer (manufactured by Anton Paar Japan, model number DHR-2) at a temperature of 25 ° C. and a shear rate of 1000 s ^−1. From the results, the rate of change in viscosity was calculated. The case where this change rate was less than 5% was evaluated as “A”, the case where it was 5% or more and less than 10% was evaluated as “B”, and the case where it was 10% or more was evaluated as “C”.

Claims (9)

Containing an acrylic compound (A), a photopolymerization initiator (B), and a hygroscopic agent (E) having an average particle size of 200 nm or less,
The acrylic compound (A) contains a compound (A1) represented by the following formula (1),
In the formula (1), R ⁰ is H or a methyl group, X is a single bond or a divalent hydrocarbon group, and each of R ¹ to R ¹¹ is H, an alkyl group, or —R ¹² —OH, R ¹² is an alkylene group and at least one of R ¹ to R ¹¹ is an alkyl group or —R ¹² —OH, and R ¹ to R ¹¹ are not chemically bonded to each other;
An ultraviolet curable resin composition for sealing an organic EL element. The compound (A1) includes at least one compound selected from the group consisting of a compound represented by the following formula (11), a compound represented by the following formula (12), and a compound represented by the following formula (13).
The ultraviolet curable resin composition for sealing an organic EL device according to claim 1. Molded by inkjet method,
The ultraviolet curable resin composition for organic EL element sealing of Claim 1 or 2. The compound (A1) contains only the compound represented by the formula (1),
The acrylic compound (A) does not contain a compound having a nitrogen atom,
The ultraviolet curable resin composition for organic EL element sealing as described in any one of Claim 1 to 3. By curing, it becomes a cured product having a glass transition temperature of 90 ° C. or higher.
The ultraviolet curable resin composition for organic electroluminescent element sealing as described in any one of Claim 1 to 4. The viscosity at 25 ° C. is 20 mPa · s or less,
The ultraviolet curable resin composition for sealing an organic EL element according to any one of claims 1 to 5. The hygroscopic agent (E) contains zeolite particles,
The ultraviolet curable resin composition for organic EL element sealing as described in any one of Claims 1-6. An organic EL light emitting device comprising an organic EL element and a sealing material covering the organic EL element,
The ultraviolet curable resin composition for sealing an organic EL element according to any one of claims 1 to 7 is molded by an ink jet method, and ultraviolet rays are then applied to the ultraviolet curable resin composition for sealing an organic EL element. Including producing the sealing material by irradiation and curing;
Manufacturing method of organic EL light-emitting device. An organic EL element and a sealing material covering the organic EL element, wherein the sealing material is an ultraviolet curable resin composition for sealing an organic EL element according to any one of claims 1 to 7. Is a cured product,
Organic EL light emitting device.