JP2021123693A - Uv-curable resin composition, optical component, method for producing optical component, light emitting device, and method for producing light emitting device - Google Patents

Abstract

To provide a UV-curable resin composition that readily improves adhesion between a cured product and inorganic material, and readily possesses excellent ultraviolet curability.SOLUTION: A UV-curable resin composition has a polyfunctional acryl compound having a nitrogen atom (Y) and a photopolymerization initiator (B).SELECTED DRAWING: Figure 1

Description

The present invention relates to an ultraviolet curable resin composition, an optical component, a method for producing an optical component, a light emitting device, and a method for producing a light emitting device. The present invention relates to an optical component manufactured from a resin composition, a method for producing an optical component using the ultraviolet curable resin composition, a light emitting device provided with the optical component, and a method for producing a light emitting device using the ultraviolet curable resin composition.

In Patent Document 1, in providing an organic layer that protects a light emitting element from water vapor with a barrier layer (functional layer) of an inorganic compound deposited on a substrate and protects the barrier layer, the organic layer may be acryloyl morpholine or the like. It is disclosed that it is prepared from a photocurable composition containing a cyclic amide monomer, a polyfunctional (meth) acrylate compound, and a photopolymerization initiator. This enhances the adhesion between the functional layer and the organic layer.

Japanese Unexamined Patent Publication No. 2018-127597

According to the inventor's research, it is difficult to enhance the UV curability of a composition containing a cyclic amide monomer such as acryloylmorpholine, and therefore outgas is likely to be generated from the cured product of the composition. It is very difficult to cure the composition sufficiently, especially in the air atmosphere.

An object of the present invention is an ultraviolet curable resin composition that easily enhances the adhesion between a cured product and an inorganic material and easily has good ultraviolet curability, and an optical component produced from the ultraviolet curable resin composition. It is an object of the present invention to provide a method for producing an optical component using the ultraviolet curable resin composition, a light emitting device including the optical component, and a method for producing a light emitting device using the ultraviolet curable resin composition.

The ultraviolet curable resin composition according to one aspect of the present invention contains a polyfunctional acrylic compound (Y1) having a nitrogen atom and a photopolymerization initiator (B).

The optical component according to one aspect of the present invention includes a cured product of the ultraviolet curable resin composition.

The method for producing an optical component according to one aspect of the present invention includes molding the ultraviolet curable resin composition by an inkjet method and then irradiating the ultraviolet curable resin composition with ultraviolet rays to cure the composition.

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

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 source and an optical component that transmits light emitted by the light source. The method includes manufacturing the optical component by the method of manufacturing the optical component.

According to one aspect of the present invention, an ultraviolet curable resin composition that easily enhances the adhesion between a cured product and an inorganic material and that tends to have good ultraviolet curability, a method for producing the ultraviolet curable resin composition, the above. An optical component made from an ultraviolet curable resin composition, a method for manufacturing an optical component using the ultraviolet curable resin composition, a light emitting device provided with the optical component, and a light emitting device using the ultraviolet curable resin composition. Can provide a method.

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

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

The ultraviolet curable resin composition according to the present embodiment (hereinafter, also referred to as composition (X)) contains a polyfunctional acrylic compound (Y1) having a nitrogen atom and a photopolymerization initiator (B).

According to this embodiment, the polyfunctional acrylic compound (Y1) having a nitrogen atom tends to improve the adhesion between the cured product of the composition (X) and the inorganic material. Further, since the polyfunctional acrylic compound (Y1) having a nitrogen atom is polyfunctional, it is easy to increase the reactivity of the composition (X), and therefore the composition (X) has good ultraviolet curability. Cheap.

The composition (X) preferably has UV curability in the atmosphere. Ultraviolet curability in the air atmosphere can be realized by increasing the reactivity of the composition (X). The fact that it has ultraviolet curability in an air atmosphere means that the pencil hardness of the cured product obtained by curing the composition (X) in an air atmosphere is 4B or more, preferably 2B or more. .. The test conditions for confirming the ultraviolet curability in the air atmosphere will be described in detail in the column of Examples described later.

In the present embodiment, the ratio of dissolved oxygen in the composition (X) is preferably 50 mg / L or less with respect to the composition (X). In this case, especially when an optical component is produced from the composition (X), it is difficult for oxygen derived from the optical component to reach the light source in the light emitting device including the optical component. Therefore, even if the composition (X) is applied to produce an optical component in a light emitting device, it is unlikely to cause deterioration of the light source due to oxygen. Further, when the ratio of dissolved oxygen is 50 mg / L or less, oxygen inhibition is less likely to occur when the composition (X) is photocured. Therefore, the ultraviolet curability of the composition (X) in the air atmosphere is more likely to be realized.

70 mg / L or less is preferable, and 50 mg / L is more preferable. The lower the ratio of dissolved oxygen, the more preferable, and ideally, it is 0 mg / L. The ratio of dissolved oxygen is substantially 5 mg / L or more, and it is very difficult to lower the ratio of dissolved oxygen. The method for measuring the ratio of dissolved oxygen will be described in detail in the column of Examples described later.

The optical component can be manufactured from the composition (X) as described above, and a light emitting device including the optical component can also be manufactured. The use of the composition (X) is not limited to the production of optical parts, and can be applied to various uses utilizing the characteristics of the composition (X).

The composition (X) is preferably molded by an inkjet method. In this case, it is easy to prepare a cured product of the composition (X) with high positional accuracy. Further, as compared with the case of molding by a printing method involving contact such as a screen printing method, when the composition (X) is molded by an inkjet method, foreign matter is less likely to be mixed into the composition (X) and its cured product. Therefore, the yield in manufacturing the optical component is unlikely to deteriorate.

The viscosity of the composition (X) at 25 ° C. is preferably 30 mPa · s or less. In this case, the composition (X) can be easily molded at room temperature, and particularly easily by the inkjet method. If the viscosity is 25 mPa · s or less, it is more preferable, if it is 20 mPa · s or less, it is further preferable, and if it is 15 mPa · s or less, it is particularly preferable. This viscosity is preferably 1 mPa · s or more, and preferably 5 mPa · s or more.

It is also preferable that the viscosity of the composition (X) at 40 ° C. is 30 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, if it is heated, the composition (X) can be easily formed, and in particular, it can be easily formed 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). If the viscosity is 25 mPa · s or less, it is more preferable, if it is 20 mPa · s or less, it is further preferable, and if it is 15 mPa · s or less, it is particularly preferable. This viscosity is preferably 1 mPa · s or more, and preferably 5 mPa · s or more.

The low viscosity of such composition (X) at 25 ° C. or 40 ° C. can be achieved by the composition of composition (X) described in detail below. The method and conditions for measuring the viscosity of the composition (X) at 25 ° C. and 40 ° C. will be described in detail in the column of Examples described later.

When the ratio of dissolved oxygen is 50 mg / L or less, molding defects are unlikely to occur when the composition (X) is prepared by the inkjet method. This is because the ratio of dissolved oxygen in the composition (X) is 50 mg / L or less, so that bubbles are unlikely to be generated in the droplets of the composition (X) ejected by the inkjet method, and therefore defects such as satellites and mists are not likely to occur. It is presumed that this is because it is difficult for a large droplet to be generated. The satellite is a droplet that is separated from the original droplet when the droplet is ejected by the inkjet method. A mist is a plurality of small droplets that separate from the original droplet. Satellites and mists tend to adhere to positions different from the original attachment positions of the droplets on the object to be coated, and therefore the dimensional accuracy of the cured product produced from the composition (X) tends to deteriorate.

The proportion of outgas generated when the cured product of the composition (X) is heated at 80 ° C. for 30 minutes is preferably 60 ppm or less. In this case, outgas is less likely to be generated from the cured product. Therefore, for example, it is possible to prevent the formation of voids due to outgas in a light emitting device including an optical component made of a cured product. Therefore, it is possible to prevent water and oxygen from reaching the light emitting element through the voids, and it is possible to prevent the light emitting element from being deteriorated by water and oxygen. The method and conditions for measuring the outgas ratio will be described in detail in the column of Examples described later.

Further, when the test was carried out in which the composition (X) was left to stand at a temperature of 60 ° C. for 2 months in a nitrogen atmosphere, the viscosity μ ₀ of the composition (X) before the test and the composition (X) after the test were performed. the viscosity change rate Rμ calculated from viscosity mu ₁ Tokyo by the following formula (M1) in) is preferably less than 20%.
Rμ = {(μ ₁ − _{μ 0} ) / μ ₀ } × 100 (%)… (M1)
In this case, the composition (X) can have particularly good storage stability. The viscosity change rate Rμ is more preferably 10% or less. The lower the viscosity change rate Rμ is, the more preferable it is, and ideally it is 0%.

The composition (X) preferably contains no solvent or has a solvent content of 1% by mass or less. In this case, outgas derived from the solvent is unlikely to be generated from the composition (X) and the cured product of the composition (X). Further, the drying step for removing the solvent from the composition (X) and the cured product at the time of manufacturing the optical component and the light emitting device can be eliminated. There may be a drying step for removing the solvent from at least one of the composition (X) and the cured product, but in this case, at least one of a reduction in the heating temperature and a shortening of the heating time in the drying step is possible. Can be done. Therefore, outgas can be less likely to be generated from the optical component without lowering the manufacturing efficiency of the optical component and the light emitting device. Further, when the composition (X) is molded by the ink jet method, the thickness of the optical component is less likely to be reduced due to the volatilization of the solvent from the molded composition (X). Therefore, the thickness of the optical component can be secured as large as possible while molding by the inkjet method. 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 glass transition temperature of the cured product of the composition (X) is preferably 80 ° C. or higher. That is, it is preferable that the composition (X) has a property of becoming a cured product having a glass transition temperature of 80 ° C. or higher when cured. 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. Therefore, for example, when a layer of an inorganic material (for example, a passivation layer 6) that overlaps an optical component is produced by a vapor deposition method such as a plasma CVD method, the optical component is less likely to deteriorate even if the optical component is heated. Further, by increasing the heat resistance, the optical component can be adapted to an in-vehicle application in which the demand for heat resistance is strict. The glass transition temperature of the cured product is more preferably 90 ° C. or higher, and even more preferably 100 ° C. or higher. The glass transition temperature of this cured product can be achieved by the composition of composition (X) described in detail below.

The volatility of the composition (X) when 20 mg is heated using a thermogravimetric analyzer at 100 ° C. for 30 minutes is preferably 40% or less. The volatility of the composition (X) is the weight loss of the composition (X) after the treatment with respect to the weight of the composition (X) before the treatment (the weight of the composition (X) before the treatment and the weight after the treatment). It is defined as a percentage of the difference from the weight). In this case, since the composition (X) has low volatility, the storage stability of the composition (X) can be enhanced. In addition, outgas is less likely to be generated from the cured product of the composition (X) and the optical components. Therefore, voids due to outgas are less likely to occur in the light emitting device. The volatility of the composition (X) is determined by heating 20 mg of the composition (X) using a thermogravimetric analyzer under the condition of 100 ° C. for 30 minutes, and the amount of weight loss after the treatment with respect to the weight before the treatment. Can be obtained by calculating. The volatility of the composition (X) when 20 mg is heated using a thermogravimetric analyzer at 100 ° C. for 30 minutes is more preferably 30% or less, and further preferably 20% or less. preferable. The lower limit of the volatility of the composition (X) is not particularly limited, but may be, for example, 0.1% or more.

The components contained in the composition (X) will be described in more detail.

The composition (X) contains an acrylic compound (Y) having at least one (meth) acrylic group in one molecule. The acrylic compound (Y) contains at least one component selected from the group consisting of, for example, monomers, oligomers and prepolymers.

The viscosity of the entire acrylic compound (Y) at 25 ° C. is preferably 50 mPa · s or less. In this case, the acrylic compound (Y) can make the composition (X) particularly low in viscosity. The viscosity of the entire acrylic compound (Y) is more preferably 30 mPa · s or less, and particularly preferably 20 mPa · s or less. The viscosity of the entire acrylic compound (Y) is, for example, 3 mPa · s or more.

It is also preferable that the viscosity of the entire acrylic compound (Y) at 40 ° C. is 50 mPa · s or less. In this case, the acrylic compound (Y) can make the composition (X) particularly low in viscosity when heated. The viscosity of the entire acrylic compound (Y) is more preferably 30 mPa · s or less, and particularly preferably 20 mPa · s or less. The viscosity of the entire acrylic compound (Y) is, for example, 3 mPa · s or more.

The percentage of the component having a boiling point of 270 ° C. or higher in the acrylic compound (Y) is preferably 80% by mass or more. In this case, the storage stability of the composition (X) is particularly unlikely to be impaired, and outgas is particularly unlikely to be generated from the cured product. It is more preferable that the percentage of the component in the acrylic compound (Y) having a boiling point of 280 ° C. or higher is 80% by mass or more.

The acrylic compound (Y) preferably contains a component having a viscosity at 25 ° C. of 20 mPa · s or less. In this case, the viscosity of the composition (X) can be reduced.

The ratio of the component having a viscosity of 20 mPa · s or less at 25 ° C. to the total amount of the acrylic compound (Y) is preferably 50% by mass or more and 100% by mass or less. In this case, the viscosity of the composition (X) can be made particularly low, and the composition (X) can be particularly easily applied by the inkjet method. This ratio is more preferably 60% by mass or more, and further preferably 70% by mass or more. Further, this ratio is more preferably 95% by mass or less, and further preferably 90% by mass or less.

The component having a viscosity at 25 ° C. of 20 mPa · s or less preferably contains a compound having a glass transition temperature of 80 ° C. or higher. In this case, the glass transition temperature of the cured product can be increased while reducing the viscosity of the composition (X). This component is more preferably contained if it contains a compound having a glass transition temperature of 90 ° C. or higher, and even more preferably if it contains a compound having a glass transition temperature of 100 ° C. or higher. The upper limit of the glass transition temperature of the compound contained in this component is not limited, but is, for example, 150 ° C. or lower.

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

In the present embodiment, the acrylic compound (Y) contains a polyfunctional acrylic compound (Y1) having a nitrogen atom. That is, as described above, the composition (X) contains the polyfunctional acrylic compound (Y1). The polyfunctional acrylic compound (Y1) has at least one nitrogen atom in the molecular skeleton and has two or more (meth) acryloyl groups in one molecule. Since the polyfunctional acrylic compound (Y1) has a nitrogen atom, it is easy to improve the adhesion between the cured composition (X) and the inorganic material. Further, since the polyfunctional acrylic compound (Y1) has two or more (meth) acryloyl groups in one molecule, it has good reactivity, and therefore, it is easy to enhance the ultraviolet curability of the composition (X).

The polyfunctional acrylic compound (Y1) preferably has a nitrogen atom by having at least one amide group in one molecule. In this case, it is particularly easy to improve the adhesion between the cured product and the inorganic material. The acrylic compound (Y1) may have a plurality of amide groups in one molecule. In that case, it is particularly easy to improve the adhesion between the cured product and the inorganic material. The amide group may contain at least one of a secondary amide group and a tertiary amide group. The polyfunctional acrylic compound (Y1) is, for example, a compound having two amide groups in one molecule, a compound having three amide groups in one molecule, and a compound having four amide groups in one molecule. , Contains at least one type. The polyfunctional acrylic compound (Y1) may contain a compound having five or more amide groups in one molecule.

The polyfunctional acrylic compound (Y1) is a polyfunctional acrylamide compound (Y11) having two or more (meth) acrylamide groups in one molecule, that is, N-CO-CR = CH ₂ groups (R is H or CH _3). It is preferable to contain it. In this case, the adhesion between the cured product and the inorganic material is particularly easy to be enhanced, and the reactivity of the composition (X) is particularly likely to be enhanced. The polyfunctional acrylamide compound (Y11) is, for example, a bifunctional compound having two (meth) acrylamide groups in one molecule, a trifunctional compound having three (meth) acrylamide groups in one molecule, and one molecule. Contains at least one of the group consisting of tetrafunctional compounds having four (meth) acrylamide groups.

The bifunctional compound contains, for example, a compound represented by the following formula (51).

The trifunctional compound contains, for example, a compound represented by the following formula (52).

The tetrafunctional compound contains, for example, at least one of a compound represented by the following formula (53) and a compound represented by the formula (54).

The compound that can be contained in the polyfunctional acrylamide compound (Y11) is not limited to the above. Further, the polyfunctional acrylamide compound (Y11) may contain a compound having five or more functions.

The ratio of the polyfunctional acrylic compound (Y1) to the entire acrylic compound (Y) is preferably 3% by mass or more and 40% by mass or less. When the proportion of the polyfunctional acrylic compound (Y1) is 3% by mass or more, the adhesion between the cured product and the inorganic material and the reactivity of the composition (X) are particularly likely to increase. Further, when the proportion of the polyfunctional acrylic compound (Y1) is 40% by mass or less, precipitation does not occur and the storage stability is improved. This ratio is more preferably 35% by mass or less, further preferably 30% by mass or less, and further preferably 25% by mass or less. Further, this ratio is more preferably 5% by mass or more, and further preferably 10% by mass or more.

The acrylic compound (Y) may further contain an acrylic compound (Y2) other than the polyfunctional acrylic compound (Y1).

The acrylic compound (Y2) preferably contains a polyfunctional acrylic compound (Y21) having two or more radically polymerizable functional groups containing a (meth) acryloyl group in one molecule. In this case, the polyfunctional acrylic compound (Y21) can increase the glass transition temperature of the cured product, and thus can increase the heat resistance of the cured product. The total ratio of the polyfunctional acrylamide compound (Y1) and the polyfunctional acrylic compound (Y21) is preferably 50% by mass or more and 100% by mass or less with respect to the entire acrylic compound (Y). The acrylic compound (Y) may contain only the polyfunctional acrylic compound (Y1), or may contain only the polyfunctional acrylic compound (Y1) and the polyfunctional acrylic compound (Y21).

The polyfunctional acrylic compound (Y21) 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) Glyceryltriacrylate, pentaerythritol tetraacrylate, ditrimethylolpropanetetraacrylate, 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 Glycol diacrylate, trimethylol propanylated hydroxypivalate, triacrylate ethoxylated phosphate, tripropylene glycol diacrylate ethoxylated, neopentyl glycol-modified trimethylol propane diacrylate, stearic acid-modified pentaerythritol diacrylate, tetramethylol propanetri Acrylate Relate, tetramethylol methanetriacrylate, caprolactone-modified trimethylolpropantriacrylate, propoxylate glyceryl triacrylate, tetramethylolmethanetetraacrylate, 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 trimethylol propanetriacrylates, propoxylated trimethylol propanetriacrylates, and 2- (2-vinyloxyethoxy) ethyl acrylate.

The acrylic equivalent of the polyfunctional acrylic compound (Y21) 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 (Y21) is, for example, 100 or more and 1000 or less, and more preferably 200 or more and 800 or less.

The polyfunctional acrylic compound (Y21) preferably contains a compound (Y211) having a structure represented by the following formula (200).

CH ₂ = CR ^1- COO- (R ^3- O) _n- CO-CR ² = CH ₂ ... (200)
In formula (200), ^{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 1 or more carbon atoms, and when n is 2 or more, it is in one molecule. a plurality of R ³ may be be the same or different from each other.

Compound (Y211), it having a structure represented by the formula (200), in particular by the number of carbon atoms of ^{R 3} of formula (200) is 3 or more, difficult to increase the affinity for water of the cured product. The carbon number of R ³ is, for example, 1 or more and 15 or less, preferably 3 or more and 15 or less. Further, the compound (Y211) has a structure represented by the formula (200), and in particular, by having two (meth) acryloyl groups in one molecule, the glass transition temperature of the cured product can be increased, and therefore the glass transition temperature of the cured product can be increased. , The heat resistance of the cured product can be improved. Further, n in the formula (200) is, for example, an integer of 1 or more and 12 or less.

The percentage of the compound (Y211) to the acrylic compound (Y) 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 cured product is effectively reduced, and the affinity of the cured product with water is particularly difficult to be enhanced. The percentage of the compound (Y211) to the acrylic compound (Y) is, for example, 70% by mass or less, or 60% by mass or less, preferably 50% by mass or less.

The compound (Y211) preferably contains a component having a boiling point of 270 ° C. or higher. That is, the acrylic compound (Y) preferably contains a component having a structure represented by the formula (200) and having a boiling point of 270 ° C. or higher. In this case, the acrylic compound (Y) 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 (Y211) remains unreacted in the cured product of the composition (X), outgas caused by the compound (Y211) is unlikely to be generated from the cured product. 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). It is more preferable that the compound (Y211) contains a component having a boiling point of 280 ° C. or higher.

The viscosity of compound (Y211) at 25 ° C. is preferably 25 mPa · s or less. In this case, the compound (Y211) can reduce the viscosity of the composition (X). The viscosity of compound (Y211) 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 (Y211) 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 (Y211) is, for example, at least one compound selected from the group consisting of an alkylene glycol di (meth) acrylate, a polyalkylene glycol di (meth) acrylate, and an alkylene oxide-modified alkylene glycol di (meth) acrylate. contains.

The alkylene glycol di (meth) acrylate is a compound in which n is 1 in the formula (200). In this case, the number of carbon atoms of ^{R 3} in the formula (200) is preferably 4 to 12. R ³ may be linear or may have a branch. In particular, the alkylene glycol di (meth) acrylates are 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, and 1,9-nonanediol di. Aacrylate, 1,10-decanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol It preferably contains at least one compound selected from the group consisting of dimethacrylate, 1,10-decanediol dimethacrylate and 1,12-dodecanediol dimethacrylate. The alkylene glycol di (meth) acrylate 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 Co., Ltd., a product number SR247 manufactured by Sartmer Co., Ltd., and a product name light manufactured by Kyoei Chemical Industry Co., Ltd. Ester 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., product number manufactured by Osaka Organic Chemical Industry Co., Ltd. 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 BD, product number SR297 manufactured by Sartmer, product number SR248 manufactured by Sartmer, product name Light Ester NP manufactured by Kyoei Chemical Industry Co., Ltd., product number SR239NS manufactured by Sartmer Co., Ltd., product name Light Ester 1,6HX manufactured by Kyoei Chemical Industry Co., Ltd. Product number HD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Product name Light Ester 1,9ND manufactured by Kyoei Chemical Industry Co., Ltd., Product number NOD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Product name Light Ester 1,10DC manufactured by Kyoei Chemical Industry Co., Ltd. It preferably contains at least one compound selected from the group consisting of product number DOD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd. and product number SR262 manufactured by Sartmer Co., Ltd.

The polyalkylene glycol di (meth) acrylate is, for example, a compound in which n is 2 or more in the formula (200). n is, for example, 2 to 10, preferably 2 to 7, preferably 2 to 6, and preferably 2 to 3. The number of carbon atoms in R ³ is 2 to 7 for example, and preferably 2-5. The higher the number of carbon atoms, the higher the hydrophobicity of the cured product, and the more difficult it is for the cured product to permeate moisture. Polyalkylene glycol di (meth) acrylates include, in particular, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and tri. It preferably contains at least one compound selected from the group consisting of propylene glycol dimethacrylate, tritetramethylene glycol diacrylate, polyethylene glycol 200 dimethacrylate and polyethylene glycol 200 diacrylate. Further, the polyalkylene glycol di (meth) acrylate 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, the product number TPGDA manufactured by Daicel, and Osaka Organic. Product number V310HP manufactured by 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 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. It preferably contains at least one compound selected from the group consisting of product number 3PG manufactured by the company.

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

When the acrylic compound (Y) contains a compound (Y211) having a structure represented by the formula (200), the compound (Y211) preferably does not contain a compound having an n value of 5 or more in the formula (200). .. If ^(R 3 _{-O) n} is a polyethylene glycol skeleton, it is particularly preferable that the value of n in the formula (200) contains no greater than 5. Compound. Even when the compound (Y211) contains a compound having an n value greater than 5 in the formula (200), the percentage of the compound having an n value greater than 5 in the formula (200) to the acrylic compound (Y) is 20. It is preferably mass% or less. Further, even when the compound (Y211) contains a compound having an n value greater than 5 in the formula (200), the compound (Y211) preferably does not contain a compound having an n value greater than 9. It is more preferred that it does not contain compounds with a value greater than 7. In these cases, the increase in viscosity of the composition (X) is particularly unlikely to occur.

It is particularly preferable that the polyfunctional acrylic compound (Y21) contains a polyalkylene glycol di (meth) acrylate. Since the polyalkylene glycol di (meth) acrylate has a low viscosity and is hard to volatilize, it can contribute to lowering the viscosity of the composition (X), improve the storage stability of the composition (X), and be used from the cured product. It can contribute to the reduction of outgas.

When the polyfunctional acrylic compound (Y21) contains a polyalkylene glycol di (meth) acrylate, the ratio of the polyalkylene glycol di (meth) acrylate to the acrylic compound (Y) is 40% by mass or more and 80% by mass or less. Is preferable. When the proportion of the polyalkylene glycol di (meth) acrylate is 40% by mass or more, the viscosity of the composition (X) can be effectively reduced. When the proportion of the polyalkylene glycol di (meth) acrylate is 80% by mass or less, the proportion of the compound having three or more (meth) acryloyl groups in the molecule increases, and the reactivity of the composition (X) and the reactivity of the composition (X) are increased. The glass transition temperature of the cured product can be increased. This ratio is more preferably 42% by mass or more and 75% by mass or less, and further preferably 45% by mass or more and 70% by mass or less.

The polyfunctional acrylic compound (Y21) may contain a compound having three or more radically polymerizable functional groups containing a (meth) acryloyl group in one molecule. In this case, the polyfunctional acrylic compound (Y21) can contain at least one selected from the group consisting of, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and pentaerythritol tetra (meth) acrylate. In this case, the glass transition temperature of the cured product can be particularly increased, and therefore the heat resistance of the cured product can be particularly increased.

The polyfunctional acrylic compound (Y21) preferably contains pentaerythritol tetra (meth) acrylate. In this case, the glass transition temperature of the cured product can be particularly increased, and the reactivity of the composition (X) can be improved. When the reactivity of the composition (X) is improved, the composition (X) can be easily cured even in an oxygen-containing environment such as an air atmosphere.

When the polyfunctional acrylic compound (Y21) contains pentaerythritol tetra (meth) acrylate, the ratio of pentaerythritol tetra (meth) acrylate to the acrylic compound (Y) shall be 0.5% by mass or more and 10% by mass or less. Is preferable. In this case, both the high reactivity of the composition (X) and the low viscosity can be achieved at the same time. This ratio is more preferably 1% by mass or more and 9% by mass or less, and further preferably 2% by mass or more and 8% by mass or less.

The polyfunctional acrylic compound (Y21) may have at least one of a benzene ring, an alicyclic ring and a polar group. The polar group is, for example, an OH group. In this case, shrinkage when the composition (X) is cured can be particularly reduced. Further, it is possible to enhance the adhesion between the cured product and an inorganic compound such as silicon nitride or silicon oxide. The polyfunctional acrylic compound (Y21) is at least selected from the group consisting of tricyclodecanedimethanol diacrylate, bisphenol A polyethoxydiacrylate, bisphenol F polyethoxydiacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate. It preferably contains one type of compound. These compounds can particularly reduce shrinkage as the composition (X) cures. Furthermore, these compounds can also enhance the adhesion between the cured product and an inorganic compound such as silicon nitride or silicon oxide.

When the adhesion between the cured product and the inorganic material is increased, when the optical component is overlapped with a film made of an inorganic material such as a SiN film (inorganic film), a high adhesion between the optical component and the inorganic film can be obtained. Easy to get rid of.

It is particularly preferable that the polyfunctional acrylic compound (Y21) contains a polyalkylene glycol di (meth) acrylate and a pentaerythritol tetra (meth) acrylate. In this case, the composition (X) has a low viscosity and is excellent in reactivity. Therefore, the composition (X) can be easily cured even in an environment containing oxygen such as an air atmosphere.

The acrylic compound (Y2) also preferably contains a monofunctional acrylic compound (Y22) in which the radically polymerizable functional group in one molecule is only one (meth) acryloyl group. The monofunctional acrylic compound (Y22) can suppress shrinkage of the composition (X) during curing.

When the acrylic compound (Y2) contains the monofunctional acrylic compound (Y22), the amount of the monofunctional acrylic compound (Y22) with respect to the total amount of the acrylic compound (Y) is preferably more than 0% by mass and 50% by mass or less. .. When the amount of the monofunctional acrylic compound (Y22) is more than 0% by mass, the shrinkage of the composition (X) at the time of curing can be suppressed. Further, when the amount of the monofunctional acrylic compound (Y22) is 50% by mass or less, the total amount of the polyfunctional acrylic compound (Y1) and the polyfunctional acrylic compound (Y21) can be 50% by mass or more, so that the curing can be performed. The heat resistance of an object can be particularly improved. The amount of the monofunctional acrylic compound (Y22) is more preferably 5% by mass or more, further preferably 30% by mass or less, and particularly preferably 20% by mass or less.

The monofunctional acrylic compound (Y22) 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, 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 Morphorine, Morforin 4-yl acrylate, Dicyclopentanyl acrylicate, Phenoxydiethylene glycol acrylate, 2-Hydroxy-3-phenoxypropylacryllate Contains at least one compound selected from the group consisting of, 1,4-cyclohexanedimethanol monoacrylate, 3-methacryloyloxymethylcyclohexene oxide and 3-acryloyloxymethylcyclohexene oxide.

The monofunctional acrylic compound (Y22) 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, Acryloyl morpholine, morpholine 4-yl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate Contains at least one compound selected from the group consisting 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 (Y2) may contain a compound having silicon in the molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. Compounds having silicon in the molecular skeleton include, 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, manufactured by Shin-Etsu Chemical Co., Ltd.). It contains at least one compound selected from the group consisting of product number KR-513).

The acrylic compound (Y2) may contain a compound having phosphorus in the molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. Compounds having phosphorus in the molecular skeleton include acid phosphoxy (meth) acrylates, such as acid phosphooxypolyoxypropylene glycol monomethacrylate.

The monofunctional acrylic compound (Y22) may contain a monofunctional acrylic compound (Y222) having a nitrogen atom. That is, the composition (X) may contain a monofunctional acrylic compound (Y222) having a nitrogen atom. In this case, the monofunctional acrylic compound (Y222), like the polyfunctional acrylic compound (Y1), can improve the adhesion between the cured product and the inorganic material. Further, by improving the adhesion, the composition (X) can easily follow the unevenness of the substrate, and the flatness of the film produced from the composition (X) can be sufficiently improved. Further, the viscosity of the composition (X) can be sufficiently lowered, and the inkjet property can be improved. The monofunctional acrylic compound (Y222) is selected from the group consisting of compounds having a morpholine skeleton such as acryloyl morpholine and morpholine 4-yl acrylate, diethyl acrylamide, dimethylaminopropyl acrylamide and pentamethylpiperidyl methacrylate. Contains at least one compound.

The ratio of the monofunctional acrylic compound (Y222) to the entire acrylic compound (Y) is preferably 5% by mass or more and 60% by mass or less. When this ratio is 5% by mass or more, the composition (X) is easily sufficiently cured in the atmosphere. When this ratio is 50% by mass or less, the outgas is small, and the reliability of a device such as a light emitting device manufactured by using the composition (X) is improved. This ratio is more preferably 10% by mass or more and 55% by mass or less, and more preferably 20% by mass or more and 50% by mass or less.

Further, the ratio of the compound having a nitrogen atom in the acrylic compound (Y) to the entire acrylic compound (Y) is preferably 5% by mass or more and 80% by mass or less. When this ratio is 5% by mass or more, the adhesion between the cured product and the inorganic material is particularly likely to be improved. When this ratio is 80% by mass or less, the compound having nitrogen in the molecular skeleton is less likely to impair the storage stability of the composition (X), and the satellite when the composition (X) is jetted by the inkjet method can be used. Hard to cause. Therefore, the inkjet property of the composition (X) is not easily impaired. Further, outgas caused by a compound having nitrogen in the molecular skeleton can be less likely to be generated. This ratio is more preferably 10% by mass or more and 70% by mass or less, further preferably 20% by mass or more and 60% by mass or less, and particularly preferably 25% by mass or more and 50% by mass or less. The compound having a nitrogen atom includes a polyfunctional acrylic compound (Y1). When the acrylic compound (Y) contains a monofunctional acrylic compound (Y222), the compound having a nitrogen atom also includes a monofunctional acrylic compound (Y222).

The acrylic compound (Y2) 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 (Y2) may contain a component 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. Specifically, the acrylic compound (Y) may contain at least one compound selected from the group consisting of, for example, tricyclodecanedimethanol diacrylate, bisphenol A polyethoxydiacrylate and bisphenol F polyethoxydiacrylate. good. In this case, the adhesion between the cured product and the inorganic material can be improved.

The acrylic compound (Y2) may contain a compound represented by the following formula (100). In this case, the reactivity of the composition (X) can be enhanced, and the adhesion between the cured product and the inorganic material can be improved.

In formula (100), R ⁰ is an H or 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.

Specifically, for example, the acrylic compound (Y2) contains at least one compound selected from the group consisting of the compound represented by the following formula (110), the compound represented by the formula (120) and the compound represented by the formula (130). You may.

The composition (X) may further contain a radically polymerizable compound (Z) other than the acrylic compound (Y). The amount of the radically polymerizable compound (Z) with respect to the total amount of the acrylic compound (Y) and the radically polymerizable compound (Z) is, for example, 10% by mass or less. The radically polymerizable compound (Z) is a polyfunctional radically polymerizable compound (Z1) 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 (Z2) can be contained. The polyfunctional radical polymerizable compound (Z1) 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 components that can be contained in the polyfunctional radically polymerizable compound (Z1) are not limited to the above. The monofunctional radical polymerizable compound (Z2) includes, for example, N-vinylformamide, vinylcaprolactam, vinylpyrrolidone, phenylglycidyl ether, p-tert-butylphenylglycidyl ether, butylglycidyl ether, 2-ethylhexylglycidyl ether, allylglycidyl 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 oxide, N-vinylpyrrolidone and N-vinylcaprolactam. The components that can be contained in the monofunctional radically polymerizable compound (Z2) are not limited to the above.

When the composition (X) contains a radically polymerizable compound (Z), the radically polymerizable compound (Z) may contain a compound having nitrogen in the molecular skeleton. Compounds having nitrogen in the molecular skeleton include, for example, at least one compound selected from the group consisting of N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam. In this case, the adhesion between the cured product and the inorganic material is improved.

The compound having nitrogen in the molecular skeleton in the acrylic compound (Y) and having nitrogen in the molecular skeleton in the radically polymerizable compound (Z) with respect to the total of the acrylic compound (Y) and the radically polymerizable compound (Z). The ratio of the compound to the total is preferably 5% by mass or more and 80% by mass or less. When this ratio is 5% by mass or more, the adhesion between the cured product and the inorganic material is particularly likely to be improved. When this ratio is 80% by mass or less, the compound having nitrogen in the molecular skeleton is less likely to impair the storage stability of the composition (X), and the satellite when the composition (X) is jetted by the inkjet method can be used. Hard to cause. Therefore, the inkjet property of the composition (X) is not easily impaired. Further, outgas caused by a compound having nitrogen in the molecular skeleton can be less likely to be generated. This ratio is more preferably 10% by mass or more and 70% by mass or less, further preferably 20% by mass or more and 60% by mass or less, and particularly preferably 25% by mass or more and 50% by mass or less.

The ratio of the total number of monofunctional compounds in the radically polymerizable compound (Z) to the radically polymerizable compound (Z) (that is, the total of the monofunctional acrylic compound (Y22) and the monofunctional radically polymerizable compound (Z2)) is It is preferably 70% by mass or less and preferably 70% by mass or less. In this case, the generation of outgas due to the monofunctional compound is less likely to occur. This ratio is more preferably 60% by mass or less, and even more preferably 50% by mass or less. The photopolymerization initiator (B) preferably contains a photoradical polymerization initiator (B1). The photoradical polymerization initiator is not particularly limited as long as it is a compound that produces radical species when irradiated with ultraviolet rays. The photoradical polymerization initiator (B1) 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, an oxime 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 (B1) with respect to the acrylic compound (Y) (the total of the acrylic compound (Y) and the radically polymerizable compound (Z) when the composition (X) contains the radically polymerizable compound (Z)). The ratio is preferably 6% by mass or more. In this case, the composition (X) can have good UV curability and can also have UV curability in a good atmosphere. This ratio is more preferably 7% by mass or more, and further preferably 8% by mass or more. Further, this ratio is, for example, 30% by mass or less, preferably 20% by mass or less, and further preferably 18% by mass or less.

The photoradical polymerization initiator (B1) preferably contains a component having photobleaching properties. In this case, the cured product of the composition (X) tends to have good light transmission. The ratio of the component having photobleaching property to the radically polymerizable compound (A1) is preferably 6% by mass or more. This ratio is more preferably 7% by mass or more, and further preferably 8% by mass or more. Further, this ratio is, for example, 30% by mass or less, preferably 20% by mass or less, and further preferably 18% by mass or less.

The component having photobleaching property contains, for example, at least one of an acylphosphine oxide-based photoinitiator and a compound having photobleaching property among oxime ester-based photoinitiators.

The photoradical polymerization initiator (B1) 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 (B1) preferably contains a component having at least one of a 9H-thioxanthene-9-one skeleton and an anthracene skeleton.

The photoradical polymerization initiator (B1) preferably contains an oxime ester-based photoinitiator regardless of the presence or absence of photobleaching property. The oxime ester-based photoinitiator can improve the curability of the composition (X). Therefore, the composition (X) can be easily cured even in an environment containing oxygen such as an air atmosphere, and outgas can be less likely to be generated from the cured product.

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 ethanone, 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. It can contain at least one compound selected from the group consisting of oxime ester-based photoinitiators described in Table 2010-527338, 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 Powerful Electronics New Materials Co., Ltd.) , And at least one compound selected from the group consisting of TR-PBG-365 (manufactured by Joshu 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 oxime ester compound having photobleaching property contains, for example, at least one of a compound represented by the following formula (401) and a compound represented by the following formula (402). Of these, the compound represented by the formula (402) has particularly high sensitivity, so that it is easy to particularly enhance the photocurability of the composition (X), and therefore it is easy to realize the ultraviolet curability of the composition (X) in the atmospheric atmosphere. ..

The acylphosphine oxide compound is, for example, at least one selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) diphenylphosphine oxide. contains.

The photoradical polymerization initiator (B1) may contain a sensitizer as a part of the photoradical polymerization initiator (B1). The sensitizer can accelerate the radical production reaction of the photoradical polymerization initiator (B1) to 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 components that the sensitizer can contain are not limited to the above.

The content of the sensitizer in the composition (X) 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 (X). It is 3 parts or more and 3 parts by mass or less. When the content of the sensitizer is within such a range, the composition (X) can be cured in air, and the composition (X) needs to be cured in an inert atmosphere such as a nitrogen atmosphere. It disappears.

The composition (X) may contain a polymerization accelerator in addition to the photoradical polymerization initiator (B1). 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 components that can be contained in the polymerization accelerator are not limited to the above.

The composition (X) may further contain the cationically polymerizable compound (W). In this case, the composition (X) may further contain a photocationic polymerization initiator (B2).

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 crushed 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 measuring device. 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, 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 the 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 less likely 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 is attached 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 component 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, Solspers series manufactured by Nippon Louvre Resol Co., Ltd., DISPERBYK series manufactured by Big Chemie Japan Co., Ltd., and 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. Further, 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 method for producing the composition (X) will be described.

First, a mixture (X1) is prepared. The mixture (X1) contains at least an acrylic compound (Y) and a photopolymerization initiator (B) among the components of the composition (X). The mixture (X1) may contain only the acrylic compound (Y) and the photopolymerization initiator (B). The mixture (X1) may contain some or all of the remaining components of the composition (X) in addition to the acrylic compound (Y) and the photopolymerization initiator (B). That is, the mixture (X1) may have the same composition as the composition (X) except that the oxygen scavenging treatment described later has not been performed.

It is preferable that the mixture (X1) is deoxidized. Thereby, it is easy to realize that the ratio of the composition (X) is 50 mg / L or less. The deoxidizing treatment is a treatment for removing oxygen in the mixture (X1) to reduce the oxygen content in the mixture (X1).

There are no particular restrictions on the specific content of the deoxidizing treatment. For example, the mixture (X1) can be deoxidized by exposing the mixture (X1) to an atmosphere having an oxygen concentration lower than that of the atmosphere (hereinafter referred to as a hypoxic atmosphere). In this case, the volume concentration of oxygen in a low oxygen atmosphere is preferably 100 ppm or less. That is, it is preferable to expose the mixture (X1) to an atmosphere having a volume concentration of oxygen of 100 ppm or less. In this case, the proportion of dissolved oxygen in the composition (X) can be efficiently reduced. The volume concentration of oxygen in a low oxygen atmosphere is more preferably 1% or less, and even more preferably 0.1% or less. The lower the volume concentration of oxygen in the low oxygen atmosphere, the more preferable, and ideally it is 0 ppm. The time for exposing the mixture (X1) to a hypoxic atmosphere in the deoxidizing treatment is preferably 1 hour or longer. In this case, it is particularly easy to reduce the proportion of dissolved oxygen in the composition (X). This time is, for example, 1 hour or more and 72 hours or less.

Further, by reducing the dissolved gas in the mixture (X1) by using a vacuum degassing device, the ratio of the dissolved oxygen in the composition (X) can be reduced. Oxygen can also be removed from the mixture (X1) by exposing the mixture (X1) to an air stream of an inert gas such as nitrogen gas. Further, oxygen can be removed from the mixture (X1) by substituting the oxygen in the mixture with the inert gas by blowing the inert gas into the mixture (X1).

After the deoxidizing treatment of the mixture (X1), the composition (X) can be prepared by adding the remaining components of the composition (X) to the mixture (X1), if necessary. When the mixture (X1) contains all the components of the composition (X), the composition (X) is prepared by deoxidizing the mixture (X1). The composition (X) is preferably placed in a sealed container to make it difficult for the composition (X) to absorb oxygen between the time the composition (X) is prepared and the time it is used.

The structure of the light emitting device 1 will be described. The light emitting device 1 includes a light source and an optical component that transmits light emitted by the light source. For example, the light emitting device 1 includes a light emitting element 4, a sealing material 5 that covers the light emitting element 4, and a passivation layer 6. In this case, the light emitting element 4 is a light source, the sealing material 5 is an optical component, and the passivation layer 6 is an inorganic layer. The sealing material 5 and the passivation layer 6 overlap each other.

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. In addition, EL is an abbreviation for electroluminescence.

An 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 a surface of the support substrate 2 facing the transparent substrate 3, and a passivation layer covering the light emitting element 4. 6 and a sealing material 5 are provided.

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. The light emitting 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, 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 to each other. The connection wiring 8 is provided on the partition wall 7.

The passivation layer 6 is preferably made of silicon nitride or silicon oxide, and particularly preferably made of silicon nitride. In the example shown in FIG. 1, 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.

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

In the present embodiment, it is preferable to prepare the sealing material 5 by molding the composition (X) by an inkjet method and then irradiating the composition (X) with ultraviolet rays to cure it. In the present embodiment, the composition (X) can be applied and molded by an inkjet method. In the present embodiment, as described above, since the oxygen ratio of the composition (X) is 75% by mass or less, defects are unlikely to occur when the composition (X) is molded by the 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 20 mPa · s or less, particularly 15 mPa · s or less. Can be molded by applying the composition (X) by an 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 20 mPa · s or less, particularly 15 mPa · s or less, the viscosity of the composition (X) can be reduced by slightly heating, and the viscosity is reduced. The composition (X) can be ejected by an inkjet method. The heating temperature of the composition (X) is, for example, 20 ° C. or higher and 50 ° C. or lower.

More specifically, for example, first, the support substrate 2 is prepared. A partition wall 7 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 of the composition (X) 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.

When irradiating the composition (X) with ultraviolet rays, the composition (X) may be irradiated with ultraviolet rays in an atmosphere containing oxygen such as an atmospheric atmosphere, or the composition (X) may be irradiated with ultraviolet rays in an inert atmosphere such as a nitrogen atmosphere. May be irradiated with ultraviolet rays. In the present embodiment, as described above, since the oxygen ratio of the composition (X) is 75% by mass or less, even if the photopolymerizable compound (A) contains the radically polymerizable compound (A1), oxygen is produced. Inhibition is unlikely to occur. Therefore, even if the composition (X) is irradiated with ultraviolet rays in an atmosphere containing oxygen, the composition (X) is easily cured.

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.

In the present embodiment, as described above, it is possible to prevent a decrease in luminous efficiency due to the passivation layer 6 and the sealing material 5 in the light emitting device 1.

The thickness of the sealing material 5 is, for example, 1 μm or more and 20 μm or less. The thickness of the sealing material 5 may be 15 μm or less. In this case, by thinning the sealing material 5, the light emitting device 1 can be thinned, and the light emitting device 1 having flexibility can be obtained. Further, even if the thickness of the sealing material 5 is 10 μm or less, in the present embodiment, it is possible to prevent a decrease in luminous efficiency due to the passivation layer 6 and the sealing material 5 in the light emitting device 1. It is more preferable that the thickness of the sealing material 5 is 8 μm or less. Further, in order for the sealing material 5 to effectively suppress the water content to the light emitting element 4, the thickness of the sealing material 5 is preferably 3 μm or more, and more preferably 5 μm or more.

The thickness of the passivation layer 6 overlapping the sealing material 5 is, for example, 0.1 μm or more and 2 μm or less. When the passivation layer 6 includes the first passivation layer 61 and the second passivation layer 62 as described above, the thickness of each of the first passivation layer 61 and the second passivation layer 62 is 0.1 μm or more and 2 μm or less. Is preferable.

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 make various optical components that transmit the light emitted by the light source. For example, the optical component may be a color resist. That is, for example, the composition (X) may contain a phosphor to prepare a color resist in a color filter from the composition (X). This color filter can be provided in a display device such as an organic EL display or a micro LED display which is a light emitting device.

1. 1. Preparation of Composition The compositions of Examples and Comparative Examples were prepared by mixing the components shown in Tables 1 to 3 below.

The details of the components shown in Tables 1 to 3 are as follows. The viscosities of the following components are values measured using a rheometer (manufactured by Anton Pearl Japan, model number DHR-2) under the conditions of ^{a temperature of 25 ° C. and a shear rate of 1000 s -1.}
-ACMO: Acryloylmorpholine, boiling point 265 ° C., viscosity 12 mPa · s, glass transition temperature 145 ° C.
-Morphorin 4-yl acrylate: boiling point 290 ° C., viscosity 16 mPa · s, glass transition temperature 115 ° C.
-N-vinyl-ε-caprolactam: manufactured by BASF, boiling point 245 ° C., viscosity 6 mPa · s, glass transition temperature 90 ° C.
-Isobornyl acrylate: Boiling point 245 ° C., viscosity 8 mPa · s, glass transition temperature 97 ° C.
-Phenoxyethyl acrylate: boiling point 290 ° C., viscosity 13 mPa · s, glass transition temperature 2 ° C.
-FAM201: Made by Fujifilm, a polyfunctional acrylic compound represented by the formula (51), solid at a boiling point of 300 ° C. or higher and at room temperature.
-FAM301: Made by Fujifilm, a polyfunctional acrylic compound represented by the formula (52), solid at a boiling point of 300 ° C. or higher and at room temperature.
-FAM401: Made by Fujifilm, a polyfunctional acrylic compound represented by the formula (53), solid at a boiling point of 300 ° C. or higher and at room temperature.
-FAM402: Made by Fujifilm, a polyfunctional acrylic compound represented by the formula (54), solid at a boiling point of 300 ° C. or higher and at room temperature.
-3G: Triethylene glycol dimethacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd., boiling point 290, viscosity 8 mPa · s.
-BD: 1,4-butanediol dimethacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd., boiling point 280, viscosity 7 mPa · s.
-SR351S: Trimethylolpropane triacrylate, boiling point 300 ° C. or higher, viscosity 106 mPa · s.
-Irgacure TPO: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide manufactured by BASF.

2. Evaluation test The following evaluation test was carried out for Examples and Comparative Examples. The results are shown in Tables 1 to 3.

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

(2) Viscosity at 40 ° C. The viscosity of the composition was measured using a rheometer (manufactured by Anton Pearl Japan, model number DHR-2) under ^{the conditions of a temperature of 40 ° C. and a shear rate of 1000 s -1.}

(3) UV curability in the atmosphere (touch test)
The composition was applied to prepare a coating film. This coating film is coated by irradiating this coating film with ultraviolet rays using a model number Unijet E075IIHD (peak wavelength 395 nm) manufactured by Ushio, Inc. under the conditions of an ^{irradiation intensity of 5 W / cm 2} and an integrated light intensity of 1500 mJ / cm ^2. The film was photocured to prepare a film having a thickness of 10 μm. A film was produced in the same manner when the ultraviolet irradiation conditions were changed to an irradiation intensity of 0.5 W / cm ² and an integrated light intensity of 1500 mJ / cm ^2.

A touch test of the film was performed, ^{and when no tack was observed in either the case where the irradiation intensity was 5 W / cm 2} or 0.5 W / cm ² , the case where no tack was observed was "A", and the irradiation intensity was 5 W / cm ² . In the case, tack was observed, but in ^{the case of 0.5 W / cm 2} , the case where no tack was observed was "B", and the irradiation intensity was either ^{5 W / cm 2} or 0.5 W / cm ^2. In addition, the case where the tack was recognized was evaluated as "C".

(4) UV curability in the atmosphere (pencil strength)
The composition was applied to prepare a coating film. This coating film is coated by irradiating this coating film with ultraviolet rays using a model number Unijet E075IIHD (peak wavelength 395 nm) manufactured by Ushio, Inc. under the conditions of an ^{irradiation intensity of 5 W / cm 2} and an integrated light intensity of 1500 mJ / cm ^2. The film was photocured to prepare a film having a thickness of 10 μm. The pencil hardness of this film was measured by the scratch hardness (pencil method) of JIS K5600-5-4: 1999.

(5) Glass transition temperature A coating film is prepared by applying the composition, and the coating film is subjected to ultraviolet rays of 5 W / cm ² in an air atmosphere using a model number Unijet E075IIHD (peak wavelength 395 nm) manufactured by Ushio, Inc. The coating film was photocured by irradiation under the condition of an integrated light amount of 1500 mJ / cm ² , and a film having a thickness of 200 μm was prepared. The glass transition temperature of the sample cut out from this film was measured using a viscoelasticity measuring device (manufactured by Hitachi High-Tech Science Co., Ltd., model number DMA7100).

(6) Adhesion The composition was applied onto a quartz glass piece (dimensions 50 mm × 25 mm × 1 mm) to prepare a coating film having a thickness of 50 μm. On top of this coating film, another piece of quartz glass was laminated so that the size of the region where the two came into contact was 12.5 mm × 25 mm. The composition was photocured by irradiating the composition with ultraviolet rays using a model number Unijet E075IIHD (peak wavelength 395 nm) manufactured by Ushio, Inc. under an atmospheric atmosphere under the conditions of an irradiation ^{intensity of 5 W / cm 2} and an integrated light amount of ^{3000 mJ / cm 2.} ..

Next, the adhesion strength between the two quartz glass pieces was measured by performing a tensile shear (tensile speed 5 mm / min) test according to JIS K6850. The results were evaluated according to the following criteria.
A: 15 MPa or more.
B: Less than 15 MPa.

(7) Outgas evaluation The outgas when the cured product of the composition was heated was sampled by the headspace method and measured by a gas chromatograph. Specifically, first, 100 mg of the composition was placed in a headspace vial having a volume of 22 mL. Subsequently, the composition is irradiated with ultraviolet rays in an atmospheric atmosphere using a model number Unijet E075IIHD (peak wavelength 395 nm) manufactured by Ushio, Inc. under the conditions of an irradiation ^{intensity of 5 W / cm 2} and an integrated light intensity of 1500 mJ / cm ^2. After curing the composition, the vial was sealed. Subsequently, the composition was heated at 80 ° C. for 30 minutes, and then the gas phase portion in the vial was introduced into a gas chromatograph for analysis. As a result, the concentration of outgas generated from the composition was specified based on the peak area of the obtained gas chromatogram. The outgas concentration is the volume fraction of outgas in the gas phase of the vial with respect to the volume of the vial (22 mL).

The concentration of outgas was specified using toluene as a reference substance. Specifically, by volatilizing toluene in a vial, two reference samples having a toluene concentration of 1000 ppm and 100 ppm were prepared. Each reference sample was introduced into a gas chromatograph and analyzed. From the peak areas of the two chromatograms obtained thereby, the relationship between the peak area and the concentration was defined, and based on this result, the above-mentioned outgas concentration was specified.

As a result, when the outgas concentration (volume fraction) was 60 ppm or less, it was "A", when it was more than 60 ppm and 100 ppm or less, it was "B", and when it was more than 100 ppm and 200 ppm or less, it was "C". , The case exceeding 200 ppm was evaluated as “D”.

(8) Inkjet The composition was placed in a cartridge of an inkjet printer (manufactured by Fujifilm, type DMP2831), and droplets of the composition were ejected from the nozzle of the inkjet printer under the conditions of a temperature of 30 ° C. and a frequency of 1 kHz. The droplets were observed with a high-speed camera and evaluated as "A" when neither mist nor satellite was observed, and as "B" when at least one of mist and satellite was observed.

(9) Storage stability A test was conducted in which the composition was left to stand at a temperature of 60 ° C. for 2 months in a nitrogen atmosphere. In this case, the viscosity change rate Rμ was calculated from _{the viscosity μ 0} of the composition before the test _{and the viscosity μ 1} of the composition after the test by the following formula (M1). When the rate of change was less than 10%, it was evaluated as "A", when it was 10% or more and less than 20%, it was evaluated as "B", and when it was 20% or more, it was evaluated as "C".
Rμ = {(μ ₁ − _{μ 0} ) / μ ₀ } × 100 (%)… (M1)

Claims (18)

It contains a polyfunctional acrylic compound (Y1) having a nitrogen atom and a photopolymerization initiator (B).
UV curable resin composition. Has UV curability in the atmosphere,
The ultraviolet curable resin composition according to claim 1. For producing optical components that transmit the light emitted by a light source,
The ultraviolet curable resin composition according to claim 1 or 2. Molded by inkjet method,
The ultraviolet curable resin composition according to any one of claims 1 to 3. No solvent or solvent content is 1% by mass or less.
The ultraviolet curable resin composition according to any one of claims 1 to 4. At least one of the viscosity at 25 ° C. and the viscosity at 40 ° C. is 30 mPa · s or less.
The ultraviolet curable resin composition according to any one of claims 1 to 5. The glass transition temperature of the cured product is 80 ° C. or higher.
The ultraviolet curable resin composition according to any one of claims 1 to 6. The proportion of outgas generated when the cured product is heated at 80 ° C. for 30 minutes is 60 ppm or less.
The ultraviolet curable resin composition according to any one of claims 1 to 7. _{The viscosity μ 0} of the ultraviolet-curable resin composition before the test and the viscosity μ of the ultraviolet-curable resin composition after the test when the test was performed in a nitrogen atmosphere at a temperature of 60 ° C. for 2 months. _The viscosity change rate Rμ calculated from 1 and the following formula (M1) is less than 20%.
Rμ = {(μ ₁ − _{μ 0} ) / μ ₀ } × 100 (%)… (M1)
The ultraviolet curable resin composition according to any one of claims 1 to 8. The polyfunctional acrylic compound (Y1) contains a compound having at least one amide group in one molecule.
The ultraviolet curable resin composition according to any one of claims 1 to 9. The polyfunctional acrylic compound (Y1) contains a polyfunctional acrylamide compound (Y11) having two or more (meth) acrylamide groups in one molecule.
The ultraviolet curable resin composition according to any one of claims 1 to 10. Further containing a monofunctional acrylic compound (Y222) having a nitrogen atom,
The ultraviolet curable resin composition according to any one of claims 1 to 11. The photopolymerization initiator (B) contains a photopolymerization initiator having photobleaching properties.
The ultraviolet curable resin composition according to any one of claims 1 to 12. The cured product of the ultraviolet curable resin composition according to any one of claims 1 to 13 is included.
Optical parts. The ultraviolet curable resin composition according to any one of claims 1 to 14 is molded by an inkjet method, and then the ultraviolet curable resin composition is irradiated with ultraviolet rays to be cured.
Manufacturing method of optical parts. Irradiate the ultraviolet curable resin composition with ultraviolet rays in an air atmosphere.
The method for manufacturing an optical component according to claim 15. The optical component includes a light source and an optical component that transmits light emitted by the light source, and the optical component includes a cured product of the ultraviolet curable resin composition according to any one of claims 1 to 14.
Light emitting device. It is a method of manufacturing a light emitting device including a light source and an optical component that transmits light emitted by the light source.
The optical component is manufactured by the method according to claim 15 or 16.
Manufacturing method of light emitting device.

Images