Ultraviolet curable resin composition, optical component, method for manufacturing an optical component, light-emitting device, and method for manufacturing a light-emitting device

Abstract

To provide a UV-curable resin composition that is discharged in the form of droplets by inkjet, with reduced defects in the droplets.SOLUTION: The inventive UV-curable resin composition contains a photopolymerizable compound (A) and a photopolymerization initiator (B). For the UV-curable resin composition, a dynamic surface tension γ1 measured by the bubble pressure method at a temperature of 25°C and a surface life of 10 milliseconds and a dynamic surface tension γ2 measured by the bubble pressure method at a temperature of 25°C and a surface life of 1000 milliseconds have the following relation: {(γ2-γ1) / γ1}×100≥6.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an ultraviolet curable resin composition, an optical component, a method for manufacturing an optical component, a light emitting device, and a method for manufacturing a light emitting device. Specifically, the present invention relates to an ultraviolet curable resin composition containing a photopolymerizable compound and a photoinitiator, an optical component produced from the ultraviolet curable resin composition, a method for manufacturing an optical component using the ultraviolet curable resin composition, a light emitting device including the optical component, and a method for manufacturing a light emitting device using the ultraviolet curable resin composition.

Background Art

[0002] In a light emitting device including a light emitting element such as an organic EL element as a light source, for example, an organic EL element is disposed on a support substrate, a transparent substrate is disposed so as to face the support substrate, and a transparent sealing material is filled between the support substrate and the transparent substrate. The sealing material is produced by, for example, an inkjet method.

[0003] For example, Patent Document 1 discloses a sealing agent for an organic EL display element, which contains a polymerizable compound and a polymerization initiator, has a viscosity at 25°C of 5 to 50 mPa·s, a surface tension at 25°C of 15 to 35 mN / m, and a Poisson's ratio of the cured product at 25°C of 0.28 to 0.40 (see Claim 1 of Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] According to the inventors' own research, when ejecting an ultraviolet curable resin composition by an inkjet method, even if the surface tension of the ultraviolet curable resin composition is appropriately adjusted, the droplets of the ultraviolet curable resin composition may not be stable. For example, the accuracy of the droplet arrival position may deteriorate due to, for example, mist separation from the droplets. When the ejection speed of the droplets increases, such defects are more likely to occur.

[0006] An object of the present invention is to provide an ultraviolet curable resin composition in which defects in droplets are less likely to occur when ejecting droplets of the ultraviolet curable resin composition by an inkjet method, an optical component produced from the ultraviolet curable resin composition, a method for manufacturing an optical component using the ultraviolet curable resin composition, a light emitting device including the optical component, and a method for manufacturing a light emitting device using the ultraviolet curable resin composition.

Means for Solving the Problems

[0007] The ultraviolet curable resin composition according to one aspect of the present invention contains a photopolymerizable compound (A) and a photoinitiator (B). The dynamic surface tension γ1 of the ultraviolet curable resin composition measured by the bubble pressure method under the conditions of a temperature of 25°C and a surface lifetime of 10 milliseconds, and the dynamic surface tension γ2 of the ultraviolet curable resin composition measured by the bubble pressure method under the conditions of a temperature of 25°C and a surface lifetime of 1000 milliseconds have the relationship shown by the following formula. {(γ2 - γ1) / γ1}×100 ≧ 6

[0008] The optical component according to one aspect of the present invention includes a cured product of the ultraviolet curable resin composition.

[0009] The method for manufacturing 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 light to cure it.

[0010] The light emitting device according to one aspect of the present invention includes a light source and an optical component that transmits the light emitted by the light source, and the optical component includes a cured product of the ultraviolet curable resin composition.

[0011] A method for manufacturing a light-emitting device according to an aspect of the present invention is a method for manufacturing a light-emitting device including a light source and an optical component that transmits light emitted from the light source, and includes manufacturing the optical component by a method for manufacturing the optical component.

Effect of the Invention

[0012] According to an aspect of the present invention, when droplets of an ultraviolet curable resin composition are ejected by an inkjet method, an ultraviolet curable resin composition in which defects in the droplets are less likely to occur, an optical component produced from the ultraviolet curable resin composition, a method for manufacturing an optical component using the ultraviolet curable resin composition, a light-emitting device including the optical component, and a method for manufacturing a light-emitting device using the ultraviolet curable resin composition can be provided.

Brief Description of the Drawings

[0013]

Figure 1

Mode for Carrying Out the Invention

[0014] Hereinafter, an embodiment of the present invention will be described.

[0015] The ultraviolet curable resin composition (hereinafter also referred to as composition (X)) according to the present embodiment contains a photopolymerizable compound (A) and a photoinitiator (B). The dynamic surface tension γ1 of the composition (X) measured by the bubble pressure method under the conditions of a temperature of 25°C and a surface lifetime of 10 milliseconds, and the dynamic surface tension γ2 of the composition (X) measured by the bubble pressure method under the conditions of a temperature of 25°C and a surface lifetime of 1000 milliseconds have a relationship represented by the following formula. {(γ2 - γ1) / γ1}×100 ≧ 6

[0016] Hereinafter, the value defined by "{(γ2 - γ1) / γ1}×100" is referred to as the change rate of the dynamic surface tension, and its unit is %.

[0017] According to the present embodiment, when ejecting droplets of the composition (X) by an inkjet method, the stability of the droplets is likely to be high. Therefore, defective droplets such as mist and satellites are less likely to occur, and particularly mist is less likely to occur. Note that mist is minute droplets in a mist form that occur when the original droplets are ejected from the nozzle. Also, a satellite is a defective droplet that occurs when a tail-like portion extending from the original droplet separates.

[0018] As described above, the inventor has clarified that the change rate of the dynamic surface tension of the composition (X) correlates with the stability of the droplets ejected by the inkjet method. That is, when measuring the dynamic surface tension of the composition (X) at 25°C by the bubble pressure method, if the change rate of the measured value when the surface lifetime is changed from 10 milliseconds to 1000 milliseconds is 6% or more, the droplets are likely to be stable and defective droplets are less likely to occur. Therefore, when ejecting the droplets of the composition (X) toward an object by the inkjet method, the droplets can be landed on the object with good positional accuracy. The reason why the change rate of the dynamic surface tension affects the stability of the droplets is not clear, but when the composition (X) is ejected at high speed as minute droplets, the state of the composition (X) changes greatly in a very short time. Therefore, it is presumed that the dynamic surface tension affects the behavior of the droplets more than the static surface tension, and the change in the dynamic surface tension corresponding to the change in the state of the droplets particularly has an influence. The details of an example of the method for measuring the dynamic surface tension will be described in detail in the section of the examples described later.

[0019] The change rate of the dynamic surface tension is more preferably 7% or more, and even more preferably 8% or more. Also, the change rate of the dynamic surface tension is, for example, 15% or less.

[0020] In this embodiment, as long as the rate of change of the dynamic surface tension is as described above, there is no limitation on the value of the dynamic surface tension itself of the composition (X), but the dynamic surface tension γ1 measured under the condition of a surface lifetime of 10 milliseconds is preferably 25 mN / m or more. In this case, even if the speed of the droplet is increased, the composition (X) easily separates from the nozzle of the inkjet device, and droplets are easily formed. Also, this dynamic surface tension γ1 is preferably 45 mN / m or less. In this case, even if the speed of the droplet is increased, mist is less likely to occur. It is more preferable that the dynamic surface tension γ1 is 28 mN / m or more, and even more preferable that it is 30 mN / m or more. Also, it is more preferable that the dynamic surface tension γ1 is 43 mN / m or less, and even more preferable that it is 40 mN / m or less.

[0021] It is also preferable that the static surface tension of the composition (X) at 25°C is 35 mN / m or more and 45 mN / m or less. If the static surface tension is 35 mN / m or more, when the droplet of the composition (X) lands and adheres to an object such as a substrate, the composition (X) is less likely to spread excessively by wetting on the surface of the object. Also, if the static surface tension is 45 mN / m or less, a coating film having good smoothness can be easily formed on the object with the composition (X). It is more preferable that the static surface tension is 37 mN / m or more, and even more preferable that it is 38 mN / m or more. Also, it is more preferable that the static surface tension is 43 mN / m or less, and even more preferable that it is 40 mN / m or less.

[0022] A cured product can be produced by ejecting the composition (X) by an inkjet method for molding and then curing it. In this case, since the droplets of the composition (X) can be landed on the object with high positional accuracy as described above, the accuracy of the shape and dimensions of the cured product can be improved. Also, 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, and therefore, the yield in manufacturing optical components is less likely to deteriorate.

[0023] By forming the composition (X) by an inkjet method and then curing it, products such as optical components including the cured product of the composition (X) can be manufactured. Also, a light-emitting device including an optical component can be manufactured. In this case, the dimensional and shape accuracy of the optical component can be enhanced. Note that the use of the composition (X) is not limited to only the manufacture of optical components, and it is applicable for manufacturing various products that utilize the characteristics of the composition (X).

[0024] 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 formed at room temperature, and particularly can be easily formed by an inkjet method. It is more preferably 25 mPa·s or less, still more preferably 20 mPa·s or less, and particularly preferably 15 mPa·s or less. It is also preferably 1 mPa·s or more and preferably 5 mPa·s or more.

[0025] Such a low viscosity of the composition (X) at 25°C can be achieved by the composition of the composition (X) described in detail below. Note that the measurement method and conditions of the viscosity of the composition (X) will be described in detail in the Examples section below.

[0026] The ratio of outgas generated when the cured product of the composition (X) is heated at 80°C for 30 minutes is preferably 500 ppm or less. In this case, outgas is less likely to be generated from the cured product. Therefore, for example, it is possible to make it less likely to generate voids caused by outgas in a light-emitting device including an optical component made of the cured product. Thus, it is less likely that water and oxygen reach the light-emitting element through the voids, and the light-emitting element can be made less likely to deteriorate due to water and oxygen.

[0027] The composition (X) preferably does not contain a solvent or has a solvent content of 1% by mass or less. In this case, outgassing derived from the solvent hardly occurs from the composition (X) and the cured product of the composition (X). Further, a drying step for removing the solvent from the composition (X) and the cured product can be eliminated during the production of the optical component and the light-emitting device. 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 reduction of the heating temperature and shortening of the heating time in the drying step can be achieved. Therefore, outgassing hardly occurs from the optical component without reducing the production efficiency of the optical component and the light-emitting device. Further, when the composition (X) is particularly molded by an inkjet method, a decrease in thickness due to volatilization of the solvent from the molded composition (X) hardly occurs, and thus a decrease in the thickness of the optical component hardly occurs. Therefore, the thickness of the optical component can be ensured to be as large as possible while molding by the inkjet method. The solvent content is more preferably 0.5% by mass or less, still more 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 an unavoidably incorporated solvent.

[0028] The glass transition temperature of the cured product of the composition (X) is preferably 80°C or higher. That is, the composition (X) preferably 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 a treatment involving a temperature rise is applied to the cured product, the cured product is less likely to deteriorate. For this reason, for example, when a layer of an inorganic material (for example, the passivation layer 6) overlapping the optical component is formed by a vapor deposition method such as plasma CVD, the optical component is less likely to deteriorate even if it is heated. Further, by enhancing the heat resistance, the optical component can also be adapted to in-vehicle applications where strict requirements are imposed on heat resistance. The glass transition temperature of the cured product is more preferably 90°C or higher, and still more preferably 100°C or higher. The glass transition temperature of this cured product can be achieved by the composition of the composition (X) described in detail below.

[0029] When the composition (X) of 20 mg is heated under the conditions of 100 °C for 30 minutes using a thermogravimetric analyzer, the volatility is preferably 40% or less. The volatility of the composition (X) is defined as the percentage of the weight loss amount of the composition (X) after the treatment (the difference between the weight of the composition (X) before the treatment and the weight after the treatment) with respect to the weight of the composition (X) before the treatment. In this case, by the low volatility of the composition (X), the storage stability of the composition (X) can be enhanced. Also, it becomes difficult for outgassing to occur from the cured product of the composition (X) and the optical component. Therefore, it becomes more difficult for voids caused by outgassing to further occur in the light-emitting device. The volatility of the composition (X) can be determined by subjecting 20 mg of the composition (X) to a treatment of heating under the conditions of 100 °C for 30 minutes using a thermogravimetric analyzer and calculating the weight loss amount of the weight after the treatment with respect to the weight before the treatment. When the composition (X) of 20 mg is heated under the conditions of 100 °C for 30 minutes using a thermogravimetric analyzer, the volatility is more preferably 30% or less, and even more preferably 20% or less. The lower limit of the volatility of the composition (X) is not particularly limited, but for example, it may be 0.1% or more.

[0030] The components contained in the composition (X) will be described in more detail.

[0031] The photopolymerizable compound (A) is a component that can cause a polymerization reaction upon irradiation with ultraviolet rays in the presence or absence of the photoinitiator (B). The photoinitiator (B) may contain a curing catalyst. The photopolymerizable compound (A) contains at least one component selected from the group consisting of, for example, monomers, oligomers, and prepolymers.

[0032] The photopolymerizable compound (A) preferably contains a compound (AX) having an HLB value of 8 or more and 13 or less. The compound (AX) may be a single compound or may contain two or more compounds. When the compound (AX) contains two or more compounds, the HLB value of each compound is 8 or more and 13 or less.

[0033] When the photopolymerizable compound (A) contains the compound (AX), the rate of change of the dynamic surface tension of the composition (X) tends to increase. Therefore, the droplets of the composition (X) are more likely to be stable, and defects such as mist are less likely to occur. This is presumably because the compound (AX) exerts a surface-active effect in the droplets when the droplets are ejected.

[0034] The compound (AX) has a hydrophilic moiety. The hydrophilic moiety contains at least one polar group selected from the group consisting of, for example, (meth)acryloyl group, ester group, aldehyde group, nitro group, hydroxyl group, ethylene oxide group, propylene oxide group, ether group, amide group, cyclic amide group, sulfoxide group, carbonyl group, carboxylic acid group, sulfonic acid group, sulfinyl group, phosphon group, phosphate group, sulfobetaine group, carbobetaine group, and phosphobetaine group. The HLB value of the compound (AX) is calculated by the Griffin method. That is, the HLB value is defined as "20×(sum of formula weights of hydrophilic moieties / molecular weight)".

[0035] The percentage of the compound (AX) with respect to the whole photopolymerizable compound (A) is preferably 60% by mass or more and 100% by mass or less. In this case, the stability of the droplets is more likely to be higher. This percentage is more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0036] The photopolymerizable compound (A) contains at least one of, for example, a radical polymerizable compound (A1) and a cationic polymerizable compound (A2). When the photopolymerizable compound (A) contains the radical polymerizable compound (A1), the photopolymerization initiator (B) preferably contains a photo radical polymerization initiator (B1). When the photopolymerizable compound (A) contains the cationic polymerizable compound (A2), the photopolymerization initiator (B) preferably contains a photo cationic polymerization initiator (B2) (cationic curing catalyst).

[0037] The case where the photopolymerizable compound (A) contains the radical polymerizable compound (A1) will be described.

[0038] The radical polymerizable compound (A1) preferably contains an acrylic compound (Y). The acrylic compound (Y) has one or more (meth)acryloyl groups in one molecule.

[0039] 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 particularly reduce the viscosity of the composition (X). If the viscosity of the entire acrylic compound (Y) is 30 mPa·s or less, it is more preferable, and if it is 20 mPa·s or less, it is particularly preferable. Also, the viscosity of the entire acrylic compound (Y) is, for example, 3 mPa·s or more.

[0040] 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 particularly reduce the viscosity of the composition (X) when heated. If the viscosity of the entire acrylic compound (Y) is 30 mPa·s or less, it is more preferable, and if it is 20 mPa·s or less, it is particularly preferable. Also, the viscosity of the entire acrylic compound (Y) is, for example, 3 mPa·s or more.

[0041] The percentage of components in the acrylic compound (Y) having a boiling point of 270°C or higher 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. If the percentage of components in the acrylic compound (Y) having a boiling point of 280°C or higher is 80% by mass or more, it is more preferable.

[0042] 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.

[0043] The proportion of the component having a viscosity of 20 mPa·s or less at 25°C with respect 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 composition (X) can be made particularly low in viscosity, and the composition (X) can be particularly easily applied by the inkjet method. This proportion is more preferably 60% by mass or more, and still more preferably 70% by mass or more. Also, this proportion is more preferably 95% by mass or less, and still more preferably 90% by mass or less.

[0044] The component having a viscosity of 20 mPa·s or less at 25°C preferably contains a compound having a glass transition temperature of 80°C or higher. In this case, while reducing the viscosity of the composition (X), the glass transition temperature of the cured product can be increased. It is more preferable if this component contains a compound having a glass transition temperature of 90°C or higher, and still more preferable if it contains a compound having a glass transition temperature of 100°C or higher. There is no upper limit to the glass transition temperature of the compound contained in this component, but it is, for example, 150°C or lower.

[0045] The compounds that the acrylic compound (Y) may contain will be described.

[0046] The acrylic compound (Y) preferably contains a polyfunctional acrylic compound (Y1) having two or more radically polymerizable functional groups containing a (meth)acryloyl group in one molecule. In this case, the polyfunctional acrylic compound (Y1) can increase the glass transition temperature of the cured product, and thus can increase the heat resistance of the cured product. The proportion of the polyfunctional acrylic compound (Y1) 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).

[0047] The polyfunctional acrylic compound (Y1) is, for example, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol oligoacrylate, diethylene glycol diacrylate, 1,6-hexanediol oligoacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclohexane dimethanol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A polyethoxydiacrylate, bisphenol F polyethoxydiacrylate, pentaerythritol tetraacrylate, propoxylated(2) neopentyl glycol diacrylate, trimethylolpropane triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated(3) trimethylolpropane triacrylate, propoxylated(3) glyceryl triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated(4) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, hexanediol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol triacrylate, bispentaerythritol hexaacrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, ethoxylated 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,It contains at least one compound selected from the group consisting of 3-propanediol diacrylate, neopentyl glycol diacrylate hydroxy pivalate, trimethylolpropane triacrylate hydroxy pivalate, ethoxylated triacrylate phosphate, ethoxylated tripropylene glycol diacrylate, neopentyl glycol-modified trimethylolpropane diacrylate, stearic acid-modified pentaerythritol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, caprolactone-modified trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxy pentaacrylate, neopentyl glycol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and 2-(2-vinyloxyethoxy)ethyl acrylate.,

[0048] The acrylic equivalent of the polyfunctional acrylic compound (Y1) is preferably 150 g / eq or less, more preferably 90 g / eq or more and 150 g / eq or less. The weight average molecular weight of the polyfunctional acrylic compound (Y1) is, for example, 100 or more and 1000 or less, more preferably 200 or more and 800 or less.,

[0049] It is also preferable that the polyfunctional acrylic compound (Y1) contains a compound (Y11) having a structure represented by the following formula (200).

[0050] CH 2 =CR 1 -COO-(R 3-O)n-CO-CR 2 =CH 2 …(200) In formula (200), R 1 and R 2 each represent hydrogen or a methyl group, n represents 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, a plurality of R 3 in one molecule may be the same as or different from each other.

[0051] Compound (Y11) has the structure shown in formula (200). In particular, since the carbon number of R 3 in formula (200) is 3 or more, it is difficult to enhance the affinity of the cured product with water. 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, compound (Y11) has the structure shown in formula (200). In particular, since it has two (meth)acryloyl groups in one molecule, the glass transition temperature of the cured product can be increased, and thus the heat resistance of the cured product can be increased. Further, n in formula (200) is, for example, an integer of 1 or more and 12 or less.

[0052] The percentage of compound (Y11) with respect to acrylic compound (Y) is preferably 50% by mass or more. In this case, the affinity of the cured product with water is particularly difficult to enhance. The percentage of compound (Y11) with respect to acrylic compound (Y) is, for example, 100% by mass or less, or 95% by mass or less, preferably 80% by mass or less.

[0053] Compound (Y11) preferably contains a component having a boiling point of 270 °C or higher. That is, the acrylic compound (Y) preferably has the structure represented by formula (200) and contains a component having a boiling point of 270 °C or higher. In this case, when the composition (X) is stored and when the composition (X) is heated, the acrylic compound (Y) is less likely to volatilize from the composition (X). Therefore, the storage stability of the composition (X) is less likely to be impaired. Further, even if compound (Y11) remains unreacted in the cured product of composition (X), outgas due to compound (Y11) is less likely to be generated from the cured product. Therefore, in the light-emitting device 1, voids due to outgas are less likely to occur. If there are voids in the light-emitting device 1, there is a risk that moisture may enter the light-emitting element 4 through the voids. However, if voids are less likely to occur, moisture is less likely 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 determined by, for example, the method shown in Science of Petroleum, Vol.II. P.1281 (1938). It is more preferable that compound (Y11) contains a component having a boiling point of 280 °C or higher.

[0054] The percentage of compound (Y11) with respect 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 generation of outgas from the cured product is effectively reduced, and furthermore, the affinity of the cured product for water is not particularly enhanced. The percentage of compound (Y11) with respect to the acrylic compound (Y) is, for example, 100% by mass or less, or 95% by mass or less, preferably 80% by mass or less.

[0055] The viscosity of compound (Y11) at 25 °C is preferably 25 mPa·s or less. In this case, compound (Y11) can lower the viscosity of the composition (X). The viscosity of compound (Y11) at 25 °C is more preferably 25 mPa·s or less, still more preferably 20 mPa·s or less, and particularly preferably 15 mPa·s or less. Also, the viscosity of compound (Y11) at 25 °C is, for example, 1 mPa·s or more, preferably 3 mPa·s or more, and still more preferably 5 mPa·s or more.

[0056] The compound (Y11) contains at least one compound selected from the group consisting of, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, and alkylene oxide-modified alkylene glycol di(meth)acrylate.

[0057] Alkylene glycol di(meth)acrylate is a compound in which n is 1 in the formula (200). In this case, the carbon number of R 3 in the formula (200) is preferably 4 to 12. R 3It may be linear or may have a branch. In particular, alkylene glycol di(meth)acrylate preferably contains at least one compound selected from the group consisting of 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, and 1,12-dodecanediol diacrylate. Further, alkylene glycol di(meth)acrylate preferably contains at least one compound selected from the group consisting of product number SR213 manufactured by Sartomer, product number V195 manufactured by Osaka Organic Chemical Industry Co., Ltd., product number SR212 manufactured by Sartomer, product number SR247 manufactured by Sartomer, product name Light Acrylate NP-A manufactured by Kyoei Chemical Industry Co., Ltd., product number SR238NS manufactured by Sartomer, product number V230 manufactured by Osaka Organic Chemical Industry Co., Ltd., product number HDDA manufactured by Daicel Corporation, product number 1,6HX-A manufactured by Kyoei Chemical Industry Co., Ltd., product number V260 manufactured by Osaka Organic Chemical Industry Co., Ltd., product number 1,9-ND-A manufactured by Kyoei Chemical Industry Co., Ltd., product number A-NOD-A manufactured by Shin-Nakamura Chemical Co., Ltd., product number CD595 manufactured by Sartomer, product number SR214NS manufactured by Sartomer, product number BD manufactured by Shin-Nakamura Chemical Co., Ltd., product number SR297 manufactured by Sartomer, product number SR248 manufactured by Sartomer, product name Light Ester NP manufactured by Kyoei Chemical Industry Co., Ltd., product number SR239NS manufactured by Sartomer, product name Light Ester 1,6HX manufactured by Kyoei Chemical Industry Co., Ltd., product number HD-N manufactured by Shin-Nakamura Chemical Co., Ltd., product name Light Ester 1,9ND manufactured by Kyoei Chemical Industry Co., Ltd., product number NOD-N manufactured by Shin-Nakamura Chemical Co., Ltd., product name Light Ester 1,10DC manufactured by Kyoei Chemical Industry Co., Ltd., product number DOD-N manufactured by Shin-Nakamura Chemical Co., Ltd., and product number SR262 manufactured by Sartomer.

[0058] Polyalkylene glycol di(meth)acrylate is, for example, a compound in which n is 2 or more in formula (200). n is, for example, 2 to 10, preferably 2 to 7, also preferably 2 to 6, and also preferably 2 to 3. The carbon number of R 3 is, for example, 2 to 7, preferably 2 to 5. The larger the carbon number, the higher the hydrophobicity of the cured product, and the more difficult it is for the cured product to permeate water. Polyalkylene glycol di(meth)acrylate preferably contains at least one compound selected from the group consisting of diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, tritetramethylene glycol diacrylate, polyethylene glycol 200 dimethacrylate, and polyethylene glycol 200 diacrylate. Further, polyalkylene glycol di(meth)acrylate preferably contains at least one compound selected from the group consisting of Sartomer product number SR230, Sartomer product number SR508NS, Daicel product number DPGDA, Sartomer product number SR306NS, Daicel product number TPGDA, Osaka Organic Chemical Industry product number V310HP, Shin-Nakamura Chemical product number APG200, Kyoei Chemical Industry Co., Ltd. product name Light Acrylate PTMGA-250, Sartomer product number SR231NS, Kyoei Chemical Industry Co., Ltd. product name Light Ester 2EG, Sartomer product number SR205NS, Kyoei Chemical Industry Co., Ltd. product name Light Ester 3EG, Sartomer product number SR210NS, Kyoei Chemical Industry Co., Ltd. product name Light Ester 4EG, Mitsubishi Chemical product name Acrylate HX, and Shin-Nakamura Chemical product number 3PG.

[0059] 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, product number EBECRYL145 manufactured by Daicel Corporation.

[0060] When the acrylic compound (Y) contains the compound (Y11) having the structure represented by the formula (200), it is preferable that the compound (Y11) does not contain a compound in which the value of n in the formula (200) is 5 or more. (R 3 -O)n is a polyethylene glycol skeleton, it is particularly preferable that the compound (Y11) does not contain a compound in which the value of n in the formula (200) is greater than 5. Even when the compound (Y11) contains a compound in which the value of n in the formula (200) is greater than 5, the percentage of the compound in which the value of n in the formula (200) is greater than 5 with respect to the acrylic compound (Y) is preferably 20% by mass or less. Further, even when the compound (Y11) contains a compound in which the value of n in the formula (200) is greater than 5, the compound (Y11) preferably does not contain a compound in which the value of n is greater than 9, and more preferably does not contain a compound in which the value of n is greater than 7. In these cases, the increase in the viscosity of the composition (X) is particularly unlikely to occur.

[0061] It is particularly preferable that the polyfunctional acrylic compound (Y1) contains polyalkylene glycol di(meth)acrylate. Since polyalkylene glycol di(meth)acrylate has a low viscosity and is difficult to volatilize, it can contribute to reducing the viscosity of the composition (X), and can contribute to improving the storage stability of the composition (X) and reducing outgas from the cured product.

[0062] When the polyfunctional acrylic compound (Y1) contains a polyalkylene glycol di(meth)acrylate, the proportion of the polyalkylene glycol di(meth)acrylate in the acrylic compound (Y) is preferably 40% by mass or more and 80% by mass or less. 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 glass transition temperature of the cured product can be increased. This proportion is more preferably 42% by mass or more and 75% by mass or less, and even more preferably 45% by mass or more and 70% by mass or less.

[0063] The polyfunctional acrylic compound (Y1) 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 (Y1) can contain at least one selected from the group consisting of 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 thus the heat resistance of the cured product can be particularly increased.

[0064] The polyfunctional acrylic compound (Y1) preferably contains pentaerythritol tetra(meth)acrylate in particular. 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 environment containing oxygen such as an air atmosphere.

[0065] When the polyfunctional acrylic compound (Y1) contains pentaerythritol tetra(meth)acrylate, the proportion of pentaerythritol tetra(meth)acrylate in the acrylic compound (Y) is preferably 0.5% by mass or more and 10% by mass or less. In this case, it is possible to achieve both high reactivity and low viscosity of the composition (X). If this proportion is 1% by mass or more and 9% by mass or less, it is more preferable, and if it is 2% by mass or more and 8% by mass or less, it is even more preferable.

[0066] The polyfunctional acrylic compound (Y1) may have at least one of a benzene ring, an alicyclic ring, and a polar group. The polar group is, for example, at least one of an OH group and an NHCO group. In this case, the shrinkage when the composition (X) cures can be particularly reduced. Furthermore, the adhesion between the cured product and an inorganic compound such as silicon nitride or silicon oxide can also be enhanced. The polyfunctional acrylic compound (Y1) preferably contains at least one compound selected from the group consisting of tricyclodecane dimethanol diacrylate, bisphenol A polyethoxydiacrylate, bisphenol F polyethoxydiacrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate. These compounds can particularly reduce the shrinkage when 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.

[0067] When the adhesion between the cured product and the inorganic material is enhanced, when an optical component is overlaid with a film made of an inorganic material such as a SiN film (inorganic film), high adhesion between the optical component and the inorganic film is likely to be obtained.

[0068] The polyfunctional acrylic compound (Y1) may contain polyalkylene glycol di(meth)acrylate and pentaerythritol tetra(meth)acrylate. In this case, the composition (X) has a low viscosity and excellent reactivity. Therefore, even in an environment containing oxygen such as an air atmosphere, the composition (X) can be easily cured.

[0069] The acrylic compound (Y) preferably contains a monofunctional acrylic compound (Y2) in which the radically polymerizable functional group in one molecule is only one (meth)acryloyl group. The monofunctional acrylic compound (Y2) can suppress the shrinkage during curing of the composition (X).

[0070] When the acrylic compound (Y) contains the monofunctional acrylic compound (Y2), the amount of the monofunctional acrylic compound (Y2) relative to the total amount of the acrylic compound (Y) is preferably more than 0% by mass and 50% by mass or less. If the amount of the monofunctional acrylic compound (Y2) is more than 0% by mass, the shrinkage during curing of the composition (X) can be suppressed. Also, if the amount of the monofunctional acrylic compound (Y2) is 50% by mass or less, the amount of the polyfunctional acrylic compound (Y1) can be 50% by mass or more, whereby the heat resistance of the cured product can be particularly improved. It is more preferable that the amount of the monofunctional acrylic compound (Y2) is 5% by mass or more. It is also more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

[0071] The monofunctional acrylic compound (Y2) is, for example, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, ethyldiglycol acrylate, cyclic trimethylolpropane formal monoacrylate, imide acrylate, isoamyl acrylate, ethoxylated succinic acid acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, cyclohexyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, isodecyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl acrylate, octyl / decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated (4) nonylphenol 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, acryloylmorpholine, morpholin-4-yl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,It contains at least one compound selected from the group consisting of 4-cyclohexanedimethanol monoacrylate, 3-methacryloyloxymethylcyclohexene oxide, and 3-acryloyloxymethylcyclohexene oxide.,

[0072] The monofunctional acrylic compound (Y2) 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.,

[0073] The compound having an alicyclic structure contains at least one compound selected from the group consisting of, for example, 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, an ethylene oxide adduct of 2-phenoxyethyl acrylate, a propylene oxide adduct of 2-phenoxyethyl acrylate, acryloylmorpholine, morpholin-4-yl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate.,

[0074] The number of ring members of the cyclic ether structure in the compound having a cyclic ether structure is preferably 3 or more, more preferably 3 or more and 4 or less. The number of carbon atoms contained in the cyclic ether structure is preferably 2 or more and 9 or less, more preferably 2 or more and 6 or less. The compound having a cyclic ether structure contains at least one compound selected from the group consisting of, for example, 3-methacryloyloxymethylcyclohexene oxide and 3-acryloyloxymethylcyclohexene oxide.,

[0075] The acrylic compound (Y) may contain a compound having silicon in its molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. The compound having silicon in its molecular skeleton contains, for example, at least one compound selected from the group consisting of 3-(trimethoxysilyl)propyl acrylate (for example, product number KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) and (meth)acrylic group-containing alkoxysilane oligomer (for example, product number KR-513 manufactured by Shin-Etsu Chemical Co., Ltd.).

[0076] The acrylic compound (Y) may contain a compound having phosphorus in its molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. The compound having phosphorus in its molecular skeleton includes acid phosphoxy(meth)acrylate such as acid phosphoxypolyoxypropylene glycol monomethacrylate.

[0077] The acrylic compound (Y) may contain a compound having nitrogen in its molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. Also, the reactivity of the acrylic compound (Y) is likely to be improved, and therefore outgas is less likely to occur from the cured product. The compound having nitrogen in its molecular skeleton includes, for example, at least one compound selected from the group consisting of compounds having a morpholine skeleton such as acryloylmorpholine and 4-morpholinyl acrylate, diethylacrylamide, dimethylaminopropylacrylamide, and pentamethylpiperidyl methacrylate.

[0078] It is particularly preferable that the acrylic compound (Y) contains a compound having a morpholine skeleton. In this case, the reactivity of the composition (X) can be further improved, and the curability of the composition (X) can be further enhanced even in an air atmosphere. It is particularly preferable that the acrylic compound (Y) contains at least one of acryloylmorpholine and morpholin-4-yl acrylate. In this case, shrinkage during curing of the composition (X) can be suppressed. Further, the viscosities of acryloylmorpholine and morpholin-4-yl acrylate are low, and therefore these compounds are less likely to increase the viscosity of the composition (X). Furthermore, since these compounds are less volatile, it is easy to improve the storage stability of the composition (X).

[0079] The ratio of the compound having a morpholine skeleton to the acrylic compound (Y) is preferably 5% by mass or more and 50% by mass or less. In this case, there is an advantage that outgas is less likely to be generated from the cured product of the composition (X). This ratio is more preferably 7% by mass or more and 45% by mass or less, and still more preferably 10% by mass or more and 40% by mass or less.

[0080] The acrylic compound (Y) 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.

[0081] The acrylic compound (Y) may contain a component composed of a compound having at least one skeleton selected from the group consisting of a dicyclopentadiene skeleton, a dicyclopentanyl skeleton, a dicyclopentenyl skeleton, and a bisphenol skeleton. Specifically, the acrylic compound (Y) may contain, for example, at least one compound selected from the group consisting of tricyclodecane dimethanol diacrylate, bisphenol A polyethoxy diacrylate, and bisphenol F polyethoxy diacrylate. In this case, the adhesion between the cured product and the inorganic material can be enhanced.

[0082] The acrylic compound (Y) may contain a compound represented by the following formula (100). In this case, the reactivity of the composition (X) can be increased, and the adhesion between the cured product and the inorganic material can be improved.

[0083]

Chemical formula

[0084] In formula (100), R 0 is H or a methyl group. X is a single bond or a divalent hydrocarbon group. Each of R 1 to R 11 is H, an alkyl group or -R 12 -OH, R 12 is an alkylene group and at least one of R 1 to R 11 is an alkyl group or -R 12 -OH. R 1 to R 11 are not chemically bonded to each other.

[0085] Specifically, for example, the acrylic compound (Y) may contain at least one compound selected from the group consisting of a compound represented by the following formula (110), a compound represented by formula (120), and a compound represented by formula (130).

[0086]

Chemical formula

[0087] The polyfunctional acrylic compound (Y1) preferably contains at least one compound selected from the group consisting of tripropylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, 1,12 - dodecanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, and 1,10 - decanediol di(meth)acrylate. Since the HLB values of these compounds are all 8 or more and 13 or less, these compounds can be included in the above - mentioned compound (AX). Therefore, the droplets of the composition (X) are more likely to be stable, and defects such as mist are less likely to occur further.

[0088] The monofunctional radically polymerizable compound (Y2) preferably contains at least one compound selected from the group consisting of acryloylmorpholine, diethylacrylamide, 2 - phenoxyethyl acrylate, and 2 - phenylphenoxyethyl acrylate. Since the HLB values of these compounds are all 8 or more and 13 or less, these compounds can be included in the above - mentioned compound (AX). Therefore, the droplets of the composition (X) are more likely to be stable, and defects such as mist are less likely to occur further.

[0089] The radical polymerizable compound (A1) may contain a radical polymerizable compound (Z) other than the acrylic compound (Y). The amount of the radical polymerizable compound (Z) relative to the total amount of the acrylic compound (Y) and the radical polymerizable compound (Z) is, for example, 10% by mass or less. The radical polymerizable compound (Z) can contain either or both of a polyfunctional radical polymerizable compound (Z1) having two or more radical polymerizable functional groups in one molecule and a monofunctional radical polymerizable compound (Z2) having only one radical polymerizable functional group in one molecule. The polyfunctional radical polymerizable compound (Z1) may contain, for example, at least one compound selected from the group consisting of an aromatic urethane oligomer, an aliphatic urethane oligomer, an epoxy acrylate oligomer, a polyester acrylate oligomer, and other special oligomers having two or more ethylenic double bonds in one molecule. Note that the components that the polyfunctional radical polymerizable compound (Z1) can contain are not limited to the above. The monofunctional radical polymerizable compound (Z2) contains, for example, at least one compound selected from the group consisting of N-vinylformamide, vinyl caprolactam, vinyl pyrrolidone, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene oxide, N-vinyl pyrrolidone, and N-vinyl caprolactam. Note that the components that the monofunctional radical polymerizable compound (Z2) can contain are not limited to the above.

[0090] When the radically polymerizable compound (A1) contains the radically polymerizable compound (Z), the radically polymerizable compound (Z) may contain a compound having nitrogen in its molecular skeleton. The compound having nitrogen in its molecular skeleton includes, for example, at least one compound selected from the group consisting of N-vinylformamide, N-vinylpyrrolidone, and N-vinylcaprolactam. In this case, similar to the case where the acrylic compound (Y) contains a compound having nitrogen in its molecular skeleton, the adhesion between the cured product and the inorganic material is improved.

[0091] In other words, the radically polymerizable compound (A1) preferably contains a compound having nitrogen in its molecular skeleton. The compound having nitrogen in its molecular skeleton may contain the compound contained in the acrylic compound (Y) or may contain the compound contained in the radically polymerizable compound (Z). In this case, the adhesion between the cured product and the inorganic material is improved. The proportion of the compound having nitrogen in its molecular skeleton with respect to the whole radically polymerizable compound (A1) is preferably 5% by mass or more and 80% by mass or less. When this proportion is 5% by mass or more, the adhesion between the cured product and the inorganic material is particularly likely to be improved. When this proportion is 80% by mass or less, the compound having nitrogen in its molecular skeleton is less likely to inhibit the storage stability of the composition (X), and it is less likely to generate satellites when the composition (X) is ejected by the inkjet method. Therefore, the inkjet property of the composition (X) is less likely to be inhibited. Furthermore, it is possible to hardly generate outgas caused by the compound having nitrogen in its molecular skeleton. This proportion is more preferably 10% by mass or more and 70% by mass or less, still more 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.

[0092] The proportion of the total of the monofunctional compounds in the radically polymerizable compound (A1) (that is, the total of the monofunctional acrylic compound (Y2) and the monofunctional radically polymerizable compound (Z2)) with respect to the radically polymerizable compound (A1) is preferably 70% by mass or less. In this case, the generation of outgas caused by the monofunctional compound is less likely to occur. This proportion is more preferably 60% by mass or less, and still more preferably 50% by mass or less.

[0093] The photo radical polymerization initiator (B1) is not particularly limited as long as it is a compound that generates radical species when irradiated with ultraviolet rays. The photo radical polymerization initiator (B1) contains, for example, at least one compound selected from the group consisting of aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (such as thioxanthone compounds and thiophenyl group-containing compounds), hexaarylbiimidazole compounds, oxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

[0094] The photo radical polymerization initiator (B1) preferably contains a component having a sensitizer skeleton in the molecule. The sensitizer skeleton contains, for example, at least one of a 9H-thioxanthen-9-one skeleton and an anthracene skeleton. That is, the photo radical polymerization initiator (B) preferably contains a component having at least one of a 9H-thioxanthen-9-one skeleton and an anthracene skeleton.

[0095] The photo radical polymerization initiator (B1) preferably contains an oxime ester-based photoinitiator. 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 the generation of outgas from the cured product can be reduced.

[0096] The oxime ester-based photoinitiator preferably contains a compound having an aromatic ring in order to reduce the contamination of the composition (X) and the manufacturing apparatus caused by the generation of decomposition products from the composition (X), and to further reduce the generation of outgas from the cured product. More preferably, it contains a compound having a condensed ring containing an aromatic ring, and even more preferably, it contains a compound having a condensed ring containing a benzene ring and a hetero ring.

[0097] The oxime ester-based photoinitiator can contain at least one compound selected from the group consisting of oxime ester-based photoinitiators such as 1,2-octadione-1-[4-(phenylthio)-,2-(o-benzoyloxime)], and ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(o-acetoxime), and those described in JP-A-2000-80068, JP-A-2001-233842, JP-T-2010-527339, JP-T-2010-527338, JP-A-2013-041153, and JP-A-2015-93842. The oxime ester-based photoinitiator may contain at least one compound selected from the group consisting of commercially available Irgacure OXE-02 (manufactured by BASF), Adeka Arcles NCI-831, N-1919 (manufactured by ADEKA), and TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) having a carbazole skeleton, Irgacure OXE-01, Adeka Arcles NCI-930 (manufactured by ADEKA), TR-PBG-345, and TR-PBG-3057 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) having a diphenyl sulfide skeleton, and TR-PBG-365 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) and SPI-04 (manufactured by Sanso) having a fluorene skeleton. In particular, when the oxime ester-based photoinitiator contains a compound having a diphenyl sulfide skeleton or a fluorene skeleton, it is preferable in that the cured product is less likely to be colored by photobleaching. It is also preferable that the oxime ester-based photoinitiator contains a compound having a carbazole skeleton in that the exposure sensitivity is likely to increase.

[0098] 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 radical photoinitiator (B) while maintaining good exposure sensitivity, so that outgas is less likely to be generated from the cured product.

[0099] The proportion of the photoinitiator (B1) to the radically polymerizable compound (A1) is preferably 6% by mass or more. In this case, the composition (X) can have good ultraviolet curability and may also have good ultraviolet curability in a good atmosphere. If this proportion is 7% by mass or more, it is more preferable, and if it is 8% by mass or more, it is even more preferable. Also, this proportion is, for example, 30% by mass or less, preferably 20% by mass or less, and even more preferably 18% by mass or less.

[0100] The radical polymerization initiator (B) preferably contains a radical polymerization initiator (B3) having photobleaching properties. For example, the photoinitiator (B1) preferably contains a photoinitiator (B31) having photobleaching properties as the photoinitiator (B3). The photoinitiator (B3) having photobleaching properties can enhance the transparency of the composition (X) and its cured product when the composition (X) is irradiated with ultraviolet light. Therefore, when the composition (X) is irradiated with ultraviolet light, the ultraviolet light easily reaches the inside of the composition (X). As a result, the composition (X) is likely to be cured efficiently.

[0101] The percentage of the photoinitiator (B3) to the photoinitiator (B) is preferably 50% by mass or more. If this percentage is 60% by mass or more, it is more preferable, and if it is 75% by mass or more, it is even more preferable. The upper limit of this percentage is not particularly defined and may be 100% by mass. That is, this percentage is, for example, 100% by mass or less.

[0102] When the photoinitiator (B1) contains the photoinitiator (B31), the photoinitiator (B31) contains, for example, at least one of an acylphosphine oxide-based photoinitiator and a compound having photobleaching properties among oxime ester-based photoinitiators.

[0103] The oxime ester compound having photo-bleaching property contains at least one of, for example, the compound represented by the following formula (401) and the compound represented by the following formula (402). Among these, since the compound represented by formula (402) is particularly highly sensitive, it is particularly easy to enhance the photocurability of the composition (X), and therefore it is easy to realize the ultraviolet curability of the composition (X) in an air atmosphere.

[0104] [Chemical formula]

[0105] [Chemical formula]

[0106] The acylphosphine oxide compound contains at least one selected from the group consisting of, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0107] In addition to the photoinitiator (B1), the composition (X) may further contain a polymerization accelerator. The polymerization accelerator contains, for example, amine compounds such as ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and butoxyethyl p-dimethylaminobenzoate. Note that the components that the polymerization accelerator can contain are not limited to the above.

[0108] When the photopolymerizable compound (A) contains a cationic photopolymerizable compound (A2), the cationic photopolymerizable compound (A2) contains at least one of, for example, a polyfunctional cationic photopolymerizable compound (W1) and a monofunctional cationic photopolymerizable compound (W2).

[0109] The polyfunctional cationic polymerizable compound (W1) can contain either one or both of a polyfunctional cationic polymerizable compound (W11) having no siloxane skeleton and a polyfunctional cationic polymerizable compound (W12) having a siloxane skeleton.

[0110] The polyfunctional cationic polymerizable compound (W11) has no siloxane skeleton and has two or more cationic polymerizable functional groups per molecule. The number of cationic polymerizable functional groups per molecule of the polyfunctional cationic polymerizable compound (W11) is preferably 2 to 4, more preferably 2 to 3.

[0111] The cationic polymerizable functional group is at least one group selected from the group consisting of, for example, an epoxy group, an oxetane group, and a vinyl ether group.

[0112] The polyfunctional cationic polymerizable compound (W11) contains at least one compound selected from the group consisting of, for example, a polyfunctional alicyclic epoxy compound, a polyfunctional heterocyclic epoxy compound, a polyfunctional oxetane compound, an alkylene glycol diglycidyl ether, and an alkylene glycol monovinyl monoglycidyl ether.

[0113] The polyfunctional alicyclic epoxy compound contains either one or both of, for example, the compound represented by the following formula (1) and the compound represented by the following formula (20).

[0114]

Chemical formula

[0115] In formula (1), R 1 ~R 18Each of them is independently a hydrogen atom, a halogen atom, or a hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably in the range of 1 to 20. The hydrocarbon group is, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, or a propyl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group or an allyl group; or an alkylidene group having 2 to 20 carbon atoms such as an ethylidene group or a propylidene group. The hydrocarbon group may contain an oxygen atom or a halogen atom. R 1 ~R 18 Each of them is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

[0116] In formula (1), X is a single bond or a divalent organic group, and the organic group is, for example, -CO-O-CH 2 -.

[0117] Examples of the compound represented by formula (1) include the compound represented by the following formula (1a) and the compound represented by the following formula (1b).

[0118]

Chemical formula

[0119]

Chemical formula

[0120]

Chemical formula

[0121] In formula (20), R 1 ~R 12Each of them is independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The hydrocarbon group having 1 to 20 carbon atoms is, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, or a propyl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group or an allyl group; or an alkylidene group having 2 to 20 carbon atoms such as an ethylidene group or a propylidene group. The hydrocarbon group having 1 to 20 carbon atoms may contain an oxygen atom or a halogen atom.

[0122] R 1 ~R 12 Each of them is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

[0123] Examples of the compound represented by the formula (20) include the tetrahydroinden diepoxide represented by the following formula (20a).

[0124]

Chemical formula

[0125] The polyfunctional heterocyclic epoxy compound contains, for example, a trifunctional epoxy compound as represented by the following formula (2).

[0126]

Chemical formula

[0127] The polyfunctional oxetane compound contains, for example, a difunctional oxetane compound as represented by the following formula (3).

[0128]

Chemical formula

[0129] Alkylene glycol diglycidyl ether contains at least one compound selected from the group consisting of compounds represented by the following formulas (4) to (7).

[0130]

Chemical formula

[0131]

Chemical formula

[0132]

Chemical formula

[0133]

Chemical formula

[0134] Alkylene glycol monovinyl monoglycidyl ether contains, for example, the compound represented by the following formula (8).

[0135]

Chemical formula

[0136] More specifically, the polyfunctional cationic polymerizable compound (W11) can contain at least one component selected from the group consisting of, for example, Celloxide 2021P and Celloxide 8010 manufactured by Daicel, TEPIC-VL manufactured by Nissan Chemical Industries, Ltd., OXT-221 manufactured by Toagosei Co., Ltd., and 1,3-PD-DEP, 1,4-BG-DEP, 1,6-HD-DEP, NPG-DEP, and butylene glycol monovinyl monoglycidyl ether manufactured by Yokkaichi Gosei Co., Ltd.

[0137] The polyfunctional cationically polymerizable compound (W12) has a siloxane skeleton and two or more cationically polymerizable functional groups per molecule. The number of cationically polymerizable functional groups per molecule of the polyfunctional cationically polymerizable compound (W12) is preferably 2 to 6, more preferably 2 to 4. The polyfunctional cationically polymerizable compound (W12) can contribute to the improvement of the cationic polymerization reactivity of the composition (X), and can also contribute to the improvement of the heat discoloration resistance of the cured product and the optical component. The polyfunctional cationically polymerizable compound (W12) can also contribute to the reduction of the elastic modulus of the cured product and the optical component. When the composition (X) contains a moisture absorbent, the polyfunctional cationically polymerizable compound (W12) can also contribute to the improvement of the dispersibility of the moisture absorbent in the composition (X) and the cured product.

[0138] The polyfunctional cationically polymerizable compound (W12) is preferably a liquid at 25°C. In particular, the viscosity of the polyfunctional cationically polymerizable compound (W12) at 25°C is preferably in the range of 10 to 300 mPa·s. In this case, an increase in the viscosity of the composition (X) can be suppressed.

[0139] The cationically polymerizable functional group of the polyfunctional cationically polymerizable compound (W12) is at least one group selected from the group consisting of, for example, an epoxy group, an oxetane group, and a vinyl ether group.

[0140] The siloxane skeleton of the polyfunctional cationically polymerizable compound (W12) may be linear, branched, or cyclic. The number of Si atoms in the siloxane skeleton is preferably in the range of 2 to 14. In this case, the composition (X) can have a particularly low viscosity. The number of these Si atoms is more preferably in the range of 2 to 10, still more preferably in the range of 2 to 7, and particularly preferably in the range of 3 to 6.

[0141] The polyfunctional cationically polymerizable compound (W12) contains at least one of, for example, the compound represented by formula (10) and the compound represented by formula (11).

[0142]

Chemical formula

[0143]

Chem.

[0144] In each of formula (10) and formula (11), R is a single bond or a divalent organic group, preferably an alkylene group. Y is a siloxane skeleton, which may be linear, branched or cyclic, and the number of its Si atoms is preferably in the range of 2 to 14, more preferably in the range of 2 to 10, still more preferably in the range of 2 to 7, and particularly preferably in the range of 3 to 6. n is an integer of 2 or more, and preferably in the range of 2 to 4.

[0145] More specifically, for example, the polyfunctional cationic polymerizable compound (W12) contains a compound represented by the following formula (10a).

[0146]

Chem.

[0147] In formula (10a), R is a single bond or a divalent organic group, preferably an alkylene group having 1 to 4 carbon atoms. n in formula (10a) is an integer of 0 or more. n is preferably in the range of 0 to 12, more preferably in the range of 0 to 8, still more preferably in the range of 0 to 5, and particularly preferably in the range of 1 to 4.

[0148] The compound represented by formula (10a) preferably contains a compound represented by the following formula (30). That is, the polyfunctional cationic polymerizable compound (W12) preferably contains a compound represented by the following formula (30).

[0149] More specifically, the polyfunctional cationically polymerizable compound (W12) preferably contains at least one component selected from the group consisting of, for example, product numbers X-40-2669, X-40-2670, X-40-2715, X-40-2732, X-22-169AS, X-22-169B, X-22-2046, X-22-343, X-22-163, and X-22-163B manufactured by Shin-Etsu Chemical Co., Ltd.

[0150] The monofunctional cationically polymerizable compound (W2) has only one cationically polymerizable functional group per molecule. The cationically polymerizable functional group is, for example, at least one group selected from the group consisting of an epoxy group, an oxetane group, and a vinyl ether group.

[0151] The viscosity of the monofunctional cationically polymerizable compound (W2) at 25°C is preferably 8 mPa·s or less. In this case, even if the composition (X) does not contain a solvent, the monofunctional cationically polymerizable compound (W2) can reduce the viscosity of the composition (X). In particular, the viscosity of the monofunctional cationically polymerizable compound (W2) at 25°C is preferably in the range of 0.1 to 8 mPa·s.

[0152] The monofunctional cationically polymerizable compound (W2) can contain, for example, at least one compound selected from the group consisting of the compounds represented by the following formulas (12) to (17) and limonene oxide.

[0153]

Chemical formula

[0154]

Chemical formula

[0155]

Chemical formula

[0156]

Chemical formula

[0157] [Chemistry]

[0158] [Chemistry]

[0159] The cationic polymerizable compound (A2) preferably contains a compound (f1) represented by the following formula (30) (hereinafter, also referred to as an aromatic epoxy compound (f1)).

[0160] [Chemistry]

[0161] In formula (30), X is at least one selected from the group consisting of a halogen, H, a hydrocarbon group, and an alkylene glycol group, and when there are a plurality of Xs in one molecule, they may be the same or different from each other. The hydrocarbon group is, for example, an alkyl group or an aryl group. When X is a hydrocarbon group, the number of carbon atoms of X is, for example, in the range of 1 to 10. R is a single bond or a divalent organic group. When R is a divalent organic group, the divalent organic group is, for example, an alkylene group, an oxyalkylene group, a carbonyloxyalkylene group (for example, -CO-O-CH 2 -), or -C(Ph) 2 -O-CH 2 - group. Y is H or a monovalent organic group. When Y is a monovalent organic group, the monovalent organic group is, for example, an alkyl group or an aryl group.

[0162] It is preferable that R in formula (30) is a single bond or an alkylene group. When n in formula (30) is 2 or 3, it is preferable that at least one of the plurality of Rs in formula (30) is a single bond or an alkylene group. In these cases, the reactivity of the aromatic epoxy compound (f1) tends to be high, and therefore the curability of the composition (X) when the composition (X) is irradiated with ultraviolet light tends to be high.

[0163] The aromatic epoxy compound (f1) preferably contains at least one compound selected from the group consisting of compounds represented by the following formulas (301) to (318), for example.

[0164] [Chemical formula]

[0165] The photo cationic polymerization initiator (B2) is not particularly limited as long as it is a catalyst that generates a protonic acid or a Lewis acid upon light irradiation. The photo cationic polymerization initiator (B2) can contain at least one of an ionic photoacid-generating type cationic curing catalyst and a non-ionic photoacid-generating type cationic curing catalyst.

[0166] The ionic photoacid-generating type cationic curing catalyst can contain at least one of onium salts and organometallic complexes. Examples of onium salts include aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts. Examples of organometallic complexes include iron-allyl complexes, titanocene complexes, and arylsilanol-aluminum complexes. The ionic photoacid-generating type cationic curing catalyst can contain at least one of these components.

[0167] The non-ionic photoacid-generating type cationic curing catalyst can contain at least one component selected from the group consisting of, for example, nitrobenzyl esters, sulfonic acid derivatives, phosphate esters, phenol sulfonic acid esters, diazonaphthoquinones, and N-hydroxyimide phosphonates. Note that the components that the non-ionic photoacid-generating type cationic curing catalyst can contain are not limited to the above.

[0168] More specific examples of the compounds that can contain the photo cationic polymerization initiator (B2) include the DPI series (such as 105, 106, 109, 201, etc.), BI-105, MPI series (such as 103, 105, 106, 109, etc.), BBI series (such as 101, 102, 103, 105, 106, 109, 110, 200, 210, 300, 301, etc.), TSP series (such as 102, 103, 105, 106, 109, 200, 300, 1000, etc.), HDS-109, MDS series (such as 103, 105, 109, 203, 205, 209, etc.), BDS-109, MNPS-109, DTS series (such as 102, 103, 105, 200, etc.), NDS series (such as 103, 105, 155, 165, etc.), DAM series (such as 101, 102, 103, 105, 201, etc.), SI series (such as 105, 106, etc.), PI-106, NDI series (such as 105, 106, 109, 1001, 1004, etc.), PAI series (such as 01, 101, 106, 1001, 1002, 1003, 1004, etc.), MBZ-101, PYR-100, NB series (such as 101, 201, etc.), NAI series (such as 100, 1002, 1003, 1004, 101, 105, 106, 109, etc.), TAZ series (such as 100, 101, 102, 103, 104, 107, 108, 109, 110, 113, 114, 118, 122, 123, 203, 204, etc.), NBC-101, ANC-101, TPS-Acetate, DTS-Acetate, Di-Boc Bisphinol A, tert-Butyl lithocholate, tert-Butyl deoxycholate, tert-Butyl cholate, BX, BC-2, MPI-103, BDS-105, TPS-103, NAT-103, BMS-105, and TMS-105; Silicyure UVI-6970, Silicyure UVI-6974, Silicyure UVI-6990, and Silicyure UVI-950 manufactured by Union Carbide Corporation of the United States; Irgacure 250, Irgacure 261, and Irgacure 264 manufactured by BASF; CG-24-61 manufactured by Ciba-Geigy; ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-151, ADEKA OPTOMER SP-170, and ADEKA OPTOMER SP-171 manufactured by ADEKA CORPORATION; DAICAT II manufactured by Daicel Corporation; UVAC1590 and UVAC1591 manufactured by Daicel Cytec Co., Ltd.; CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758, and CIT-1682 manufactured by Nippon Soda Co., Ltd.; PI-2074, which is tetrakis(pentafluorophenyl)borate tolylcumyliodonium salt manufactured by Rhodia; FFC509 manufactured by 3M Company; CD-1010, CD-1011, and CD-1012 manufactured by Sartomer Company, USA; CPI-100P, CPI-101A, CPI-110P, CPI-110A, and CPI-210S manufactured by San-Apro Limited; and UVI-6992 and UVI-6976 manufactured by The Dow Chemical Company. The photo cationic polymerization initiator (B2) can contain at least one compound selected from the group consisting of these compounds.

[0169] The ratio of the photo cationic polymerization initiator (B2) to the cationically polymerizable compound (A2) is preferably in the range of 1 to 4% by mass. When this ratio is 1% by mass or more, the composition (X) can have particularly good cationic polymerization reactivity. Also, when this ratio is 4% by mass or less, the composition (X) can have good storage stability, and the manufacturing cost can be reduced by not containing an excessive amount of the photo cationic polymerization initiator (B2).

[0170] The composition (X) may contain a sensitizer (C). In this case, the sensitizer (C) can promote the reaction of the photoinitiator (B).

[0171] The sensitizer (C) can contain at least one compound selected from the group consisting of, for example, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9-hydroxymethylanthracene, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, anthraquinone, 1,2-dihydroxyanthraquinone, 2-ethylanthraquinone, 1,4-diethoxynaphthalene, p-dimethylaminoacetophenone, p-diethylaminoacetophenone, p-dimethylaminobenzophenone, p-diethylaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, p-dimethylaminobenzaldehyde, and p-diethylaminobenzaldehyde. Note that the components that the sensitizer (C) can contain are not limited to those described above.

[0172] The sensitizer (C) preferably contains at least one of anthracene-based compounds and anthraquinone-based compounds. The anthracene-based compound contains at least one selected from the group consisting of, for example, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, and 9-hydroxymethylanthracene. The thioxanthone-based compound contains at least one selected from the group consisting of, for example, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone.

[0173] The sensitizer (C) particularly preferably contains an anthracene-based compound. In this case, since the transparency of the composition (X) is hardly inhibited, the coating film of the composition (X) is likely to cure uniformly from the surface layer to the deep part, and thus unevenness is particularly unlikely to occur in the cured product.

[0174] The percentage of the sensitizer (C) with respect to the composition (X) is preferably 0.05% by mass or more. In this case, the reactivity of the composition (X) is particularly likely to be high. If this percentage is 0.1% by mass or more, it is more preferable, and if it is 0.3% by mass or more, it is even more preferable. Also, the percentage of the sensitizer (C) is preferably 1.5% by mass or less. In this case, the coating film of the composition (X) is likely to cure uniformly from the surface layer to the deep part, and therefore, unevenness is particularly unlikely to occur in the cured product. If this percentage is 1.0% by mass or less, it is even more preferable.

[0175] The composition (X) may contain a leveling agent (D). The leveling agent (D) can appropriately adjust the static surface tension of the composition (X) and easily smooth the surface of the coating film. Therefore, when the coating film is irradiated with ultraviolet rays, the coating film is likely to cure uniformly, and thus unevenness is particularly unlikely to occur in the cured product.

[0176] The leveling agent (D) preferably contains a silane compound (D1). The silane compound (D1) preferably contains a silane compound (D11) having a nitrogen atom and an alkoxysilyl group. In this case, since the affinity between the composition (X) and the cured product and an inorganic material such as silicon nitride increases, the smoothness of the coating film and the cured film is particularly likely to increase. The silane compound (D11) preferably contains a silane compound (D12) having an azacyclopentane skeleton (pyrrolidine skeleton) in particular. In this case, the smoothness of the coating film and the cured film is particularly likely to increase. The silane compound (D12) has a structure in which, for example, an alkoxy group is bonded to Si in the azacyclopentane skeleton and an organic group such as a hydrocarbon group is bonded to nitrogen in the azacyclopentane skeleton. The hydrocarbon group is, for example, an aryl group, an alkyl group, an alkenyl group, or an alkynyl group.

[0177] The silane compound (D12) preferably contains an azasilacyclopentane-type silane. The azasilacyclopentane-type silane has a structure shown by, for example, the following formula (4).

[0178]

Chemical formula

[0179] In formula (4), R 1 and R 2 each is an alkyl group. X is an organic group, for example, a hydrocarbon group.

[0180] R 1 and R 2 each preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 to 2 carbon atoms.

[0181] When X is a hydrocarbon group, the hydrocarbon group is, for example, an aryl group, an alkyl group, an alkenyl group, or an alkynyl group. The hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 4 to 17 carbon atoms, and even more preferably 6 to 14 carbon atoms. Specifically, the hydrocarbon group is, for example, a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, an octyl group, or a tetradecyl group; a branched alkyl group such as an isopropyl group, a tertiary butyl group, or an isobutyl group; a cyclic alkyl group such as a cyclohexyl group; an aryl group such as a phenyl group, a tolyl group, or a xylyl group; an aralkyl group such as a phenethyl group or a diphenylmethyl group.

[0182] The silane compound (D11) contains at least one selected from the group consisting of, for example, 2,2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-octyl-1-aza-2-silacyclopentane, and 2,2-dimethoxy-1-tetradecyl-1-aza-2-silacyclopentane.

[0183] The compounds that the silane compound (D1) can contain are not limited to the above silane compound (D11). The silane compound (D1) can contain an appropriate organic alkoxysilane. For example, the silane compound (D1) can contain at least one compound selected from the group consisting of N-phenyl-3-aminopropyltrimethoxysilane, phenyltrimethoxysilane, and hexyltrimethoxysilane.

[0184] In addition, the compounds that the leveling agent (D) may contain are not limited to silane compounds (D1). For example, the leveling agent (D) can contain at least one compound selected from the group consisting of fluorine compounds, acrylic copolymers, and alcohol alkoxylate compounds.

[0185] The percentage of the leveling agent (D) with respect to the composition (X) is preferably 0.1% by mass or more. In this case, it becomes more difficult for unevenness to occur in the cured product. This percentage is more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more. Also, the percentage of the leveling agent (D) is preferably 3.0% by mass or less. In this case, there is an advantage that it is possible to prevent the deterioration of the inkjet ejection property due to an excessive decrease in the static surface tension. This percentage is more preferably 2.5% by mass or less, and even more preferably 2.0% by mass or less.

[0186] The composition (X) may further contain a moisture absorbent (E). When the composition (X) contains the moisture absorbent (E), the cured product of the composition (X) and the sealing material 5 can have moisture absorption properties. Therefore, the sealing material 5 can make it more difficult for moisture to further penetrate into the light-emitting element 4 in the light-emitting device 1. The average particle size of the moisture absorbent (E) is preferably 200 nm or less. In this case, the cured product can have high transparency.

[0187] The moisture absorbent (E) is preferably inorganic particles having moisture absorption properties. For example, it preferably contains at least one component selected from the group consisting of zeolite particles, silica gel particles, calcium chloride particles, and titanium oxide nanotube particles. It is particularly preferable that the moisture absorbent (E) contains zeolite particles.

[0188] Zeolite particles with an average particle size of 200 nm or less can be produced, for example, by pulverizing common industrial zeolites. When producing zeolite particles, the zeolites may be pulverized and then crystallized by hydrothermal synthesis or the like. In this case, the zeolite particles can have particularly high hygroscopicity. Examples of such methods for producing zeolite particles are disclosed in JP-A-2016-69266, JP-A-2013-049602, and the like.

[0189] The zeolite particles preferably contain sodium ions. For this reason, the zeolite particles are preferably produced from at least one selected from the group consisting of type A zeolite, type X zeolite, and type Y zeolite. It is particularly preferable that the zeolite particles are produced from 4A zeolite among type A zeolites. In these cases, the zeolite particles have a crystal structure suitable for adsorbing moisture.

[0190] 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, and thus the sealant produced from the composition (X) containing the zeolite particles can have particularly high hygroscopicity. Further, when the pH of the zeolite particles is 10 or less, the zeolite particles are less likely to inhibit the curing when the composition (X) is cured. The pH of the zeolite particles is a value obtained by measuring the pH of the supernatant of the dispersion obtained by putting 0.05 g of zeolite particles in 99.95 g of ion-exchanged water, heating the dispersion at 90 ° C. for 24 hours, and then measuring the pH with a pH meter. As the pH meter, for example, a compact pH meter manufactured by Horiba, Ltd. <laquatwin>B-711 can be used.

[0191] The average particle size of the moisture absorbent (E) is preferably 10 nm or more and 200 nm or less. If this average particle size is 200 nm or less, the cured product can have particularly high transparency. Further, if this average particle size is 10 nm or more, good moisture absorbency of the moisture absorbent (E) can be maintained. The average particle size is the median diameter, that is, the cumulative 50% diameter (D50) calculated from the measurement results by the dynamic light scattering method. As the measuring device, the Nanotrac Wave series of Microtrac Bell Co., Ltd. can be used.

[0192] The average particle size of the moisture absorbent (E) is more preferably 150 nm or less, still more preferably 100 nm or less, and particularly preferably 70 nm or less. Further, the average particle size of the moisture absorbent (E) 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 moisture absorbency.

[0193] It is also preferable that the cumulative 90% diameter (D90) of the moisture absorbent (E) is 100 nm or less. In this case, the cured product can have particularly high transparency.

[0194] When the composition (X) contains the moisture absorbent (E), the ratio of the moisture absorbent (E) to the total amount of the composition (X) is preferably 1% by mass or more and 20% by mass or less. If the ratio of the moisture absorbent (E) is 1% by mass or more, the cured product can have particularly high moisture absorbency. Further, if the ratio of the moisture absorbent (E) is 20% by mass or less, the viscosity of the composition (X) can be particularly reduced, and the composition (X) can also have a sufficiently low viscosity such that it can be applied by the inkjet method. The ratio of the moisture absorbent (E) is more preferably 3% by mass or more, and particularly preferably 5% by mass or more. Further, the ratio of the moisture absorbent (E) is more preferably 15% by mass or less, and particularly preferably 13% by mass or less.

[0195] The composition (X) may further contain an inorganic filler other than the moisture absorbent (E). In particular, the composition (X) preferably contains nano-sized high refractive index particles. Examples of the high refractive index particles include zirconia particles. When the composition (X) contains high refractive index particles, the refractive index of the cured product can be increased while maintaining good transparency of the cured product. Therefore, when the cured product is applied to the encapsulant 5 in the light-emitting device 1, the light extraction efficiency of the light transmitted through the encapsulant 5 and emitted to the outside can be improved. The average particle size of the high refractive index particles is preferably in the range of 5 to 30 nm, and more preferably in the range of 10 to 20 nm.

[0196] The ratio of the high refractive index particles in the composition (X) is appropriately designed so that the cured product has a desired refractive index. In particular, the high refractive index particles are preferably contained in the composition (X) 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.

[0197] When the composition (X) contains the moisture absorbent (E), the composition (X) preferably further contains a dispersant (F). In this case, the dispersant (F) can improve the dispersibility of the moisture absorbent (E) in the composition (X). Therefore, in the composition (X), an increase in viscosity and a decrease in storage stability due to the moisture absorbent (E) are less likely to occur.

[0198] The dispersant (F) is a surfactant that can adsorb onto the particles. The dispersant (F) has an adsorption group (generally also referred to as an anchor) that can adsorb onto the particles and a molecular backbone (generally also referred to as a tail) that adheres to the particles when the adsorption group adsorbs onto the particles. The dispersant (F) contains at least one component selected from the group consisting of, for example, an acrylic dispersant in which the tail is an acrylic molecular chain, a urethane dispersant in which the tail is a urethane molecular chain, and a polyester dispersant in which the tail is a polyester molecular chain. The adsorption group contains at least one of, for example, a basic polar functional group and an acidic polar functional group. The basic polar functional group contains at least one group selected from the group consisting of, for example, an amino group, an imino group, an amide group, an imide group, and a nitrogen-containing heterocyclic group. The acidic polar functional group contains at least one group selected from the group consisting of, for example, a carboxyl group and a phosphate group. The dispersant (F) can contain at least one compound selected from the group consisting of, for example, the Solsperse series manufactured by Lubrizol Japan Ltd., the DISPERBYK series manufactured by BYK-Chemie Japan Co., Ltd., and the AJISPER series manufactured by Ajinomoto Fine-Techno Co., Inc.

[0199] When the composition (X) contains the moisture absorbent (E), the amount of the dispersant (F) relative to 100 parts by mass of the moisture absorbent (E) is preferably 5 parts by mass or more and 60 parts by mass or less. When the amount of the dispersant (F) is 5 parts by mass or more, the function of the dispersant (F) can be effectively exhibited, and when it is 60 parts by mass or less, it is possible to suppress the free molecules of the dispersant (F) in the sealing material 5 from inhibiting the adhesion between the sealing material 5 and the member made of an inorganic material. Further, the amount of the dispersant (F) is more preferably 15 parts by mass or more, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less.

[0200] 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 the 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 the light source, the sealing material 5 is the optical component, and the passivation layer 6 is an inorganic layer. The sealing material 5 and the passivation layer 6 overlap each other.

[0201] The light-emitting element 4 includes, for example, a light-emitting diode. The light-emitting diode includes, for example, at least one of an organic EL element (organic light-emitting diode) and a micro light-emitting diode. When the light-emitting element 4 includes an organic light-emitting diode, the light-emitting device 1 including the light-emitting element 4 is, for example, an organic EL display. When the light-emitting element 4 includes a micro light-emitting diode, the light-emitting device 1 including the light-emitting element 4 is, for example, a micro LED display. Note that EL is an abbreviation for electroluminescence.

[0202] An example of the structure of the light-emitting device 1 will be described with reference to FIG. 1. 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 with a gap therebetween, a light-emitting element 4 on a surface of the support substrate 2 facing the transparent substrate 3, and a passivation layer 6 and a sealing material 5 that cover the light-emitting element 4.

[0203] 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 material having light transmittance. 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.

[0204] 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 the element array 9) on the support substrate 2. The element array 9 also includes partition walls 7. The partition walls 7 are on the support substrate 2 and partition between two adjacent light-emitting elements 4. The partition walls 7 are produced, for example, by molding a photosensitive resin material by photolithography. The element array 9 also includes connection wirings 8 that electrically connect the electrodes 43 and the electron transport layers 424 of adjacent light-emitting elements 4. The connection wirings 8 are provided on the partition walls 7.

[0205] 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 element array 9 in a state of being in direct contact with the element array 9, thereby covering the light-emitting element 4. The second passivation layer 62 is disposed on the side opposite to the element array 9 with respect to the first passivation layer 61, and there is a gap between the second passivation layer 62 and the first passivation layer 61. 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.

[0206] Furthermore, a second sealing material 52 is filled between the second passivation layer 62 and the transparent substrate 3. The second sealing material 52 is made of, for example, a transparent resin material. The material of the second sealing material 52 is not particularly limited. The material of the second sealing material 52 may be the same as or different from that of the sealing material 5.

[0207] A method for producing the sealing material 5 using the composition (X) and a method for manufacturing the light-emitting device 1 will be described.

[0208] In this embodiment, it is preferable to produce the sealing material 5 by forming the composition (X) by an inkjet method and then irradiating the composition (X) with ultraviolet rays for curing. In this embodiment, it is possible to apply and form the composition (X) by an inkjet method.

[0209] When applying the composition (X) by an inkjet method, if the composition (X) has a sufficiently low viscosity at room temperature, for example, when the viscosity at 25°C is 30 mPa·s or less, particularly 15 mPa·s or less, it can be formed by applying the composition (X) by an inkjet method without heating.

[0210] When the composition (X) has the property of reducing its viscosity when heated, the composition (X) may be heated and then applied and formed by an inkjet method. When the viscosity of the composition (X) at 40°C is 30 mPa·s or less, particularly 15 mPa·s or less, the composition (X) can be reduced in viscosity by only slightly heating it, and this viscosity-reduced composition (X) can be ejected by an inkjet method. The heating temperature of the composition (X) is, for example, 20°C or more and 50°C or less.

[0211] More specifically, for example, first, the support substrate 2 is prepared. On one surface of this support substrate 2, the partition wall 7 is produced 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 produced by an appropriate method such as an evaporation method or a coating method. In particular, it is preferable to produce the light-emitting element 4 by a coating method such as an inkjet method. Thereby, the element array 9 is produced on the support substrate 2.

[0212] Next, a first passivation layer 61 is provided on the element array 9. The first passivation layer 61 can be produced by a vapor deposition method such as a plasma CVD method.

[0213] Next, the composition (X) is formed on the first passivation layer 61, for example, by an inkjet method to form a coating film. If the inkjet method is applied to both the formation of the light-emitting element 4 and the coating of the composition (X), the manufacturing 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 produce the encapsulant 5. The thickness of the encapsulant 5 is, for example, 5 μm or more and 50 μm or less.

[0214] 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 air atmosphere, or the composition (X) may be irradiated with ultraviolet rays in an inert atmosphere such as a nitrogen atmosphere. 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) particularly contains the radical polymerizable compound (A1), oxygen inhibition hardly occurs. Therefore, even when the composition (X) is irradiated with ultraviolet rays in an atmosphere containing oxygen, the composition (X) is easily cured.

[0215] Next, a second passivation layer 62 is provided on the encapsulant 5. The second passivation layer 62 can be formed by a vapor deposition method such as a plasma CVD method.

[0216] Next, an ultraviolet-curable resin material is provided on one surface of the support substrate 2 so as to cover the second passivation layer 62, and then the transparent substrate 3 is overlaid on this resin material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate.

[0217] Next, ultraviolet rays are irradiated from the outside toward the transparent substrate 3. The ultraviolet rays pass through the transparent substrate 3 and reach the ultraviolet-curable resin material. Thereby, the ultraviolet-curable resin material is cured to produce the second encapsulant 52.

[0218] In the present embodiment, as described above, it is possible to hardly cause a decrease in the light-emitting efficiency due to the passivation layer 6 and the encapsulant 5 in the light-emitting device 1.

[0219] 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 reducing the thickness of the sealing material 5, the light-emitting device 1 can be made thinner, and it is also possible to obtain a flexible light-emitting device 1. Further, even if the thickness of the sealing material 5 is 10 μm or less, in the present embodiment, it is possible to less likely cause 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 to effectively suppress moisture from reaching the light-emitting element 4 by the sealing material 5, the thickness of the sealing material 5 is preferably 3 μm or more, and more preferably 5 μm or more.

[0220] 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, it is preferable that 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.

[0221] Note that the use of the composition (X) according to the present embodiment is not limited to the production of the sealing material 5 for the light-emitting element 4. The composition (X) can be used to produce various optical components that transmit light emitted from a light source. For example, the optical component may be a color resist. That is, for example, a phosphor may be contained in the composition (X), and a color resist in a color filter may be produced from this composition (X). This color filter can be provided in a display device such as an organic EL display or a micro LED display that is a light-emitting device.

Examples

[0222] Hereinafter, specific examples of the present embodiment will be presented. However, the present embodiment is not limited only to the following examples.

[0223] 1. Preparation of Composition The compositions of the examples and comparative examples were prepared by mixing the components shown in the following table. The viscosities of the components shown in the table were measured using a rheometer (manufactured by Anton Paar Japan, model number DHR-2) under the conditions of a temperature of 25 °C and a shear rate of 1000 s -1 The values were measured under the conditions of. Also, the HLB values were calculated by the Griffin method. The details of the photoinitiator, sensitizer, and leveling agent are as follows. - Irgacure TPO: Manufactured by BASF, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, with photo bleaching property. - UVS-581: An anthracene-based sensitizer, manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name Anthracure® UVS-581. - X-88-398: 2,2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane, manufactured by Shin-Etsu Chemical Co., Ltd., product number X-88-398. - KBM103: Phenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., product number KBM103. - KBM3063: n-Hexyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., product number KBM3063.

[0224] 2. Evaluation Tests The following evaluation tests were carried out on the examples and comparative examples. The results are shown in the table.

[0225] (1) Viscosity The viscosity of the composition was measured using a rheometer (manufactured by Anton Paar Japan, model number DHR-2) under the conditions of a temperature of 25 °C and a shear rate of 1000 s -1 under the conditions of.

[0226] (2) Static Surface Tension The static surface tension of the composition was measured by the Wilhelmy method. In the measurement, a surface tensiometer (manufactured by Kyowa Interface Science, model: CBVP-Z) was used, and a platinum plate was used for measurement at a measurement temperature of 25 °C.

[0227] (3) Rate of Change of Dynamic Surface Tension Using a bubble pressure type dynamic surface tension meter (Model PB100, manufactured by KRUSS, sold by Sanyo Trading Co., Ltd.), the dynamic surface tension γ1 of the composition at a temperature of 25°C and a surface lifetime of 10 milliseconds and the dynamic surface tension γ2 of the composition at a temperature of 25°C and a surface lifetime of 1000 milliseconds were measured by the bubble pressure method. From these measurement results, the change rate of the dynamic surface tension "{(γ2 - γ1) / γ1}×100" was calculated.

[0228] (4) Transmittance The composition was applied to form a coating film with a thickness of 10 μm. Using an LED-UV irradiator (Model No. E075IIHD, peak wavelength 395 nm) manufactured byUSHIO Inc., ultraviolet rays were irradiated onto this coating film in the atmosphere at an irradiation intensity of 3 W / cm 2 for 5.3 seconds, and then the film was produced by heating at 100°C for 5 minutes. The total light transmittance of this film was measured according to JIS K7361-1.

[0229] (5) Inkjet property The composition was put into the cartridge of an inkjet printer (manufactured by Fujifilm, model DMP2831), and droplets of the composition were ejected from the nozzles of the inkjet printer under the conditions of a temperature of 30°C and a frequency of 1 kHz. These droplets were observed with a high-speed camera. As a result, If neither mist nor satellite was observed, it was evaluated as "A"; if satellite generation was observed but mist was not observed, it was evaluated as "B"; if mist was observed, it was evaluated as "C".

[0230]

Table 1

[0231]

Table 2

Claims

1. An ultraviolet curable resin composition containing a photopolymerizable compound (A), a photoinitiator (B), and a leveling agent (D), wherein the photopolymerizable compound (A) contains a compound (AX) having an HLB value of 8 or more and 13 or less, the compound (AX) contains at least one compound selected from the group consisting of tripropylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, 1,12 - dodecanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, acryloylmorpholine, diethylacrylamide, 2 - phenoxyethyl acrylate, and 2 - phenylphenoxyethyl acrylate, the percentage of the compound (AX) with respect to the whole photopolymerizable compound (A) is 60% by mass or more and 100% by mass or less, the leveling agent (D) contains an azasilacyclopentane - type silane, the viscosity of the ultraviolet curable resin composition at 25°C is 30 mPa·s or less, the static surface tension of the ultraviolet curable resin composition at 25°C is 35 mN / m or more and 45 mN / m or less, the dynamic surface tension γ1 measured by the bubble - pressurer method at a temperature of 25°C and a surface lifetime of 10 milliseconds and the dynamic surface tension γ2 measured by the bubble - pressurer method at a temperature of 25°C and a surface lifetime of 1000 milliseconds of the ultraviolet curable resin composition have a relationship represented by the following formula, {(γ2 - γ1) / γ1}×100≧6 An ultraviolet curable resin composition.

2. For producing an optical component that transmits light emitted by a light source, the ultraviolet curable resin composition according to Claim 1.

3. Molded by an ink - jet method, the ultraviolet curable resin composition according to Claim 1 or 2.

4. An optical component comprising a cured product of the ultraviolet curable resin composition according to any one of Claims 1 to 3,

5. A method for manufacturing an optical component, comprising molding the ultraviolet curable resin composition according to any one of Claims 1 to 3 by an ink - jet method and then irradiating the ultraviolet curable resin composition with ultraviolet rays for curing.

6. ​ A light-emitting device comprising a light source and an optical component that transmits light emitted by the light source, wherein the optical component includes a cured product of the ultraviolet curable resin composition according to any one of claims 1 to 3. Light-emitting device.

7. A method for manufacturing a light-emitting device including a light source and an optical component that transmits light emitted by the light source, including manufacturing the optical component by the method according to claim 5. Method for manufacturing a light-emitting device.

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