JP2022056388A - Ultraviolet-curable resin composition, optical component, method for manufacturing optical component, light-emitting device, and method for manufacturing light-emitting device - Google Patents

Abstract

To provide an ultraviolet-curable resin composition which prevents generation of stripe irregularities on the surface of a cured product when the cured product is manufactured by curing the resin composition by irradiation with ultraviolet rays.SOLUTION: An ultraviolet-curable resin composition contains a photopolymerizable compound (A) and a photopolymerization initiator (B). A coated film having a thickness of 10 μm from the ultraviolet-curable resin composition is produced, and an absolute value in a difference between a cure shrinkage when the coated film is irradiated with ultraviolet rays in any wavelength region from 385 nm to 405 nm of a peak wavelength under conditions of an illumination intensity of 7 W/cm2 and an integrated light quantity of 2.1 J/cm2, and a cure shrinkage when irradiated with ultraviolet rays under conditions of an illumination intensity of 3 W/cm2 and an integrated light quantity of 0.9 J/cm2 is 2 percentage point or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to an ultraviolet curable resin composition, an optical component, a method for producing an optical component, a light emitting device, and a method for producing a light emitting device. Specifically, the present invention relates to an ultraviolet curable resin containing a photopolymerizable compound and a photopolymerization initiator. The composition, an optical component made from the ultraviolet curable resin composition, a method for manufacturing an optical component using the ultraviolet curable resin composition, a light emitting device provided with the optical component, and the ultraviolet curable resin composition are used. The present invention relates to a method of manufacturing a light emitting device.

In a light emitting device provided with a light emitting element such as an organic EL element as a light source, for example, an organic EL element is arranged on a support substrate, a transparent substrate is arranged so as to face the support substrate, and the transparent substrate is transparent between the support substrate and the transparent substrate. Encapsulant is filled. The encapsulant is produced, for example, by an inkjet method.

For example, Patent Document 1 contains a polymerizable compound and a polymerization initiator, has a viscosity of 5 to 50 mPa · s at 25 ° C., a surface tension of 15 to 35 mN / m at 25 ° C., and 25 of the cured product. A sealant for an organic EL display element, characterized in that the Poisson's ratio at ° C. is 0.28 to 0.40, is disclosed (see claim 1 of Document 1).

International Publication No. 2018/074506

According to the research of the inventor, when a cured product is produced by irradiating an ultraviolet curable resin composition with ultraviolet rays and curing it, streaky irregularities may be formed on the surface of the cured product. In particular, when the surface of the coating film of the ultraviolet curable resin composition is irradiated with ultraviolet rays from a light emitting diode and the irradiation position is moved to cure the coating film, streaky irregularities are likely to occur. Such unevenness deteriorates the light emitting characteristics of the light emitting device.

An object of the present invention is to obtain an ultraviolet curable resin composition and the ultraviolet curable resin composition, which are less likely to have streaky irregularities on the surface of the cured product when the cured product is produced by irradiating with ultraviolet rays to cure the cured product. It is an object of the present invention to provide an optical component to be manufactured, a method for manufacturing an optical component using the ultraviolet curable resin composition, a light emitting device provided with the optical component, and a method for manufacturing a light emitting device using the ultraviolet curable resin composition. ..

The ultraviolet curable resin composition according to one aspect of the present invention contains a photopolymerizable compound (A) and a photopolymerization initiator (B). A coating film having a thickness of 10 μm is prepared from the ultraviolet curable resin composition, and ultraviolet rays having a peak wavelength of 385 nm to 405 nm are applied to the coating film with an irradiation intensity of 7 W / cm ² and an integrated light intensity. The absolute value of the difference between the curing shrinkage rate when irradiated under the condition of 2.1 J / cm ² and the curing shrinkage rate when irradiated under the condition of irradiation intensity 3 W / cm ² and integrated light intensity 0.9 J / cm ² is 2, 2 percentage points or less.

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

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

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

The method for manufacturing a light emitting device according to one aspect of the present invention is a method for manufacturing a light emitting device including a light source and an optical component that transmits light emitted by the light source, and the optical component is used as a method for manufacturing the optical component. Including manufacturing in.

According to one aspect of the present invention, when a cured product is produced by irradiating with ultraviolet rays to cure the cured product, an ultraviolet curable resin composition in which streaky irregularities are less likely to occur on the surface of the cured product, the ultraviolet curable resin composition. It is possible to provide an optical component manufactured from an object, a method for manufacturing an optical component using the ultraviolet curable resin composition, a light emitting device provided with the optical component, and a method for manufacturing a light emitting device using the ultraviolet curable resin composition.

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

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

The ultraviolet curable resin composition (hereinafter, also referred to as composition (X)) according to the present embodiment contains a photopolymerizable compound (A) and a photopolymerization initiator (B). A coating film having a thickness of 10 μm is prepared from the composition (X), and ultraviolet rays having a peak wavelength of 385 nm to 405 nm are applied to the coating film with an irradiation intensity of 7 W / cm ² and an integrated light intensity of 2.1 J. Curing shrinkage when irradiated under the condition of / cm ² (hereinafter, also referred to as the first curing shrinkage rate) and curing shrinkage when irradiated under the condition of irradiation intensity 3 W / cm ² and integrated light intensity 0.9 J / cm ² . The absolute value of the difference from the rate (hereinafter, also referred to as the second curing shrinkage rate) (hereinafter, also referred to as the curing shrinkage rate difference) is 2 percentage points or less.

In the present embodiment, when ultraviolet rays having a peak wavelength of one of the wavelength ranges from 385 nm to 405 nm are used, the difference between the first curing shrinkage rate and the second curing shrinkage rate is 2 percentage points or less. If certain things can be realized, the difference between the first curing shrinkage rate and the second curing shrinkage rate is 2 percentage points or less when ultraviolet rays having a peak wavelength of another wavelength in the above wavelength range are used. It does not have to be possible. It is particularly preferable if the difference between the first curing shrinkage rate and the second curing shrinkage rate can be realized to be 2 percentage points or less when ultraviolet rays having a peak wavelength of 395 nm are used. It is also preferable that the difference between the first curing shrinkage rate and the second curing shrinkage rate can be realized to be 2 percentage points or less regardless of the peak wavelength of ultraviolet rays in the wavelength range from 385 nm to 405 nm.

According to this embodiment, when a cured product is produced by irradiating the composition (X) with ultraviolet rays, streaky irregularities are less likely to occur on the surface of the cured product. This is because the absolute value of the difference between the first curing shrinkage rate of the composition (X) and the second term or the shrinkage rate is small, and the difference in the amount of partial shrinkage when the composition (X) is cured is small. It is considered that this is because the composition (X) is less likely to occur, that is, the entire composition (X) is likely to shrink uniformly.

In particular, when the surface of the coating film of the ultraviolet curable resin composition is irradiated with ultraviolet rays from a light emitting diode and the irradiation position of the ultraviolet rays is moved to cure the coating film, the coating film has a line shape of the irradiation position of the ultraviolet rays. A portion where the ultraviolet irradiation amount is relatively high is generated along the locus of the above, and a portion where the ultraviolet irradiation amount is relatively low is likely to occur between these portions. Therefore, usually, the difference in the curing shrinkage rate between the above-mentioned portions tends to cause streaky irregularities in the cured product of the coating film. However, in the present embodiment, as described above, the absolute value of the difference between the first curing shrinkage rate and the second curing shrinkage rate of the composition (X) is small, so that the coating film of the composition (X) is exposed to ultraviolet rays. Even if the difference in the irradiation amount is partially generated, the difference in the amount of shrinkage is less likely to occur, and it is presumed that the cured product is less likely to have irregularities.

The absolute value of the difference between the first curing shrinkage rate and the second curing shrinkage rate is more preferably 1.5 percentage points or less, and even more preferably 1 percentage point or less. The smaller this value is, the more preferable it is, ideally 0 percentage points. Specific measurement methods and measurement conditions for the first curing shrinkage rate and the second curing shrinkage rate of the composition (X) will be described in detail in the section of Examples described later.

A coating film having a thickness of 10 μm is prepared from the composition (X), and the coating film is irradiated with ultraviolet rays having a peak wavelength of 395 nm under the conditions of an irradiation intensity of 3 W / cm ² and an integrated light amount of 0.9 J / cm ² . The reaction rate of the photopolymerizable compound (A) in the substance (X) is preferably 80% or more. In this case, even if there is a partial difference in the irradiation amount of the ultraviolet rays when the composition (X) is irradiated with ultraviolet rays and cured, a difference in the reaction rate of the photopolymerizable compound (A) occurs in the cured product. Hateful. Therefore, the difference in the amount of shrinkage is less likely to occur when the composition (X) is cured, and thus unevenness is less likely to occur in the cured product. Such characteristics of the composition (X) can be realized by increasing the reactivity of the photopolymerizable compound (A) by the composition of the composition (X) described later. The reduction rate of the reactive functional group in the photopolymerizable compound (A) obtained from the result of analyzing the composition (X) by infrared spectroscopy before and after irradiation with ultraviolet rays is determined by the photopolymerizable compound (A). It is defined as the reaction rate. An example of a specific method for determining the reaction rate will be described in the section of Examples described later.

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

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

It is preferable that at least one of the viscosity of the composition (X) at 25 ° C. and the viscosity at 40 ° C. is 30 mPa · s or less.

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

When the viscosity of the composition (X) at 40 ° C. is 30 mPa · s or less, the viscosity of the composition (X) can be reduced by slightly heating the composition (X) regardless of the viscosity at room temperature. It is possible to make it. Therefore, if it is heated, the composition (X) can be easily formed, and in particular, it can be easily formed by an inkjet method. Further, since the composition (X) can be reduced in viscosity without being significantly heated, it is possible to prevent the composition (X) from changing due to volatilization of the components in the composition (X). If the viscosity is 25 mPa · s or less, it is more preferable, if it is 20 mPa · s or less, it is further preferable, and if it is 15 mPa · s or less, it is particularly preferable. It is preferable that the viscosity is 1 mPa · s or more, and it is also preferable that the viscosity is 5 mPa · s or more.

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

The proportion of outgas produced 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 prevent the formation of voids due to outgas in a light emitting device including an optical component made of a cured product. Therefore, it is difficult for water and oxygen to reach the light emitting element through the void, and the light emitting element can be less likely to be deteriorated by water and oxygen.

The composition (X) preferably contains no solvent or has a solvent content of 1% by mass or less. In this case, outgas derived from the solvent is unlikely to be generated from the composition (X) and the cured product of the composition (X). Further, it is possible to eliminate the need for a drying step for removing the solvent from the composition (X) and the cured product at the time of manufacturing the optical component and the light emitting device. 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 is possible. Can be done. Therefore, outgas can be less likely to be generated from the optical component without lowering the manufacturing efficiency of the optical component and the light emitting device. Further, when the composition (X) is molded by the ink jet method in particular, the thickness of the composition (X) after molding is less likely to decrease due to the volatilization of the solvent, and therefore the thickness of the optical component is less likely to decrease. Therefore, it is possible to secure the thickness of the optical component as large as possible while molding by the inkjet method. The content of the solvent is more preferably 0.5% by mass or less, further preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. It is particularly preferable that the composition (X) does not contain a solvent or contains only a solvent that is inevitably mixed.

The glass transition temperature of the cured product of the composition (X) is preferably 80 ° C. or higher. That is, it is preferable that the composition (X) has a property of becoming a cured product having a glass transition temperature of 80 ° C. or higher when cured. In this case, the cured product can have good heat resistance. Therefore, for example, when the cured product is subjected to a treatment accompanied by a temperature rise, the cured product is less likely to deteriorate. Therefore, for example, when a layer of an inorganic material (for example, a passivation layer 6) overlapping an optical component is manufactured by a vapor deposition method such as a plasma CVD method, the optical component is less likely to deteriorate even if the optical component is heated. Further, by increasing the heat resistance, the optical component can be adapted to the in-vehicle application where the demand for heat resistance is strict. The glass transition temperature of the cured product is more preferably 90 ° C. or higher, and even more preferably 100 ° C. or higher. The glass transition temperature of this cured product can be achieved by the composition of the composition (X) described in detail below.

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

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

The photopolymerizable compound (A) is a component capable of causing a polymerization reaction by being irradiated with ultraviolet rays in the presence or absence of the photopolymerization initiator (B). The photopolymerization initiator (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.

The photopolymerizable compound (A) contains, for example, at least one of a radically polymerizable compound (A1) and a cationically polymerizable compound (A2). When the photopolymerizable compound (A) contains a radically polymerizable compound (A1), the photopolymerization initiator (B) preferably contains a photoradical polymerization initiator (B1). When the photopolymerizable compound (A) contains the cationically polymerizable compound (A2), the photopolymerization initiator (B) preferably contains the photocationic polymerization initiator (B2) (cationic curing catalyst).

The case where the photopolymerizable compound (A) contains the radically polymerizable compound (A1) will be described.

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

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

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

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

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

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

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

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

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 ratio 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).

The polyfunctional acrylic compound (Y1) is, for example, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol oligo acrylate, diethylene glycol diacrylate, 1,6-hexanediol oligo acrylate, neopentyl glycol diacrylate, Triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclohexanedimethanol diacrylate, tricyclodecanedimethanol diacrylate, bisphenol A polyethoxydiacrylate, bisphenol F polyethoxydiacrylate, pentaerythritol tetraacrylate , Propoxylation (2) Neopentyl glycol diacrylate, Trimethylol propantriacrylate, Tris (2-hydroxyethyl) isocyanurate triacrylate, Pentaerythritol triacrylate, ethoxylated (3) Trimethylol propoxytriacrylate, Propoxylation (3) ) Glyceryltriacrylate, pentaerythritol tetraacrylate, ditrimethylolpropanetetraacrylate, ethoxylated (4) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, hexadiol diacrylate, polyethylene Glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol triacrylate, bispentaerythritol hexaacrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, ethoxylated 1,6-hexanediol diacrylate, polypropylene glycol diacrylate , 1,4-Butanediol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, neopentyl glycol hydroxypivalate Diacrylate, hydroxypivalic acid trimethylolpropane triacrylate, ethoxylated phosphate triacrylate, ethoxylated tripropylene glycol diacrylate, neopentyl glycol-modified trimethylol propanediacrylate, stearate-modified pentaerythritol diacrylate, tetramethylol propanetriacrylate Rate, tetramethylolmethane triacrylate, caprolactone-modified trimethylolpropane triacrylate, propoxylate glyceryl triacrylate, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, di Pentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di ( It contains at least one compound selected from the group consisting of meth) acrylates, ethoxylated trimethylolpropane triacrylates, propoxylated trimethylolpropane triacrylates, and 2- (2-vinyloxyethoxy) ethyl acrylate.

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

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

CH ₂ = CR ¹ -COO- (R ³ -O) n-CO-CR ² = CH ₂ ... (200)
In formula (200), each of R ¹ and R ² is a hydrogen or methyl group, n is an integer of 1 or more, R ³ is an alkylene group having 1 or more carbon atoms, and when n is 2 or more, it is in one molecule. The plurality of ^R3s may be the same as or different from each other.

Since the compound (Y11) has the structure represented by the formula (200), and particularly the carbon number of R3 of the formula (200) is ³ or more, it is difficult to increase 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, the compound (Y11) has a structure represented by the formula (200), and in particular, by having two (meth) acryloyl groups in one molecule, the glass transition temperature of the cured product can be increased, and therefore the glass transition temperature can be increased. , The heat resistance of the cured product can be improved. Further, n in the equation (200) is, for example, an integer of 1 or more and 12 or less.

The percentage of the compound (Y11) to the acrylic compound (Y) is preferably 50% by mass or more. In this case, it is difficult to increase the affinity of the cured product for water. The percentage of the compound (Y11) 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.

The compound (Y11) preferably contains a component having a boiling point of 270 ° C. or higher. That is, the acrylic compound (Y) preferably contains a component having a structure represented by the formula (200) and having a boiling point of 270 ° C. or higher. In this case, the acrylic compound (Y) is less likely to volatilize from the composition (X) during storage of the composition (X) and when the composition (X) is heated. Therefore, the storage stability of the composition (X) is not easily impaired. Further, even if the compound (Y11) remains unreacted in the cured product of the composition (X), outgas caused by the compound (Y11) is unlikely to be generated from the cured product. Therefore, voids due to outgas are unlikely to occur in the light emitting device 1. If there is a void in the light emitting device 1, moisture may enter the light emitting element 4 through the void, but if the void is less likely to occur, it is difficult for water to enter the light emitting element 4. The boiling point is the boiling point under normal pressure obtained by converting the boiling point under reduced pressure, and is obtained by, for example, the method shown in Science of Petroleum, Vol.II. P.1281 (1938). It is more preferable that the compound (Y11) contains a component having a boiling point of 280 ° C. or higher.

The percentage of the compound (Y11) to the acrylic compound (Y) is preferably 50% by mass or more. In this case, the storage stability of the composition (X) is effectively enhanced, the outgas generation from the cured product is effectively reduced, and the affinity of the cured product with water is particularly difficult to be enhanced. The percentage of the compound (Y11) 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.

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

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

The alkylene glycol di (meth) acrylate is a compound in which n is 1 in the formula (200). In this case ^, the carbon number of R3 in the formula (200) is preferably 4 to 12. ^R3 may be linear or may have a branch. In particular, the alkylene glycol di (meth) acrylate is 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol di. Acrylic, 1,10-decanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol It preferably contains at least one compound selected from the group consisting of dimethacrylate, 1,10-decanediol dimethacrylate, and 1,12-dodecanediol dimethacrylate. In addition, the alkylene glycol di (meth) acrylate has a product number SR213 manufactured by Sartmer, a product number V195 manufactured by Osaka Organic Chemical Industry Co., Ltd., a product number SR212 manufactured by Sartmer Co., Ltd., a product number SR247 manufactured by Sartmer Co., Ltd., and a product name light manufactured by Kyoei Chemical Industry Co., Ltd. Acrylate NP-A, product number SR238NS manufactured by Sartmer, product number V230 manufactured by Osaka Organic Chemical Industry Co., Ltd., product number HDDA manufactured by Daicel Co., Ltd., product number 1,6HX-A manufactured by Kyoei Chemical Industry Co., Ltd., product number manufactured by Osaka Organic Chemical Industry Co., Ltd. V260, product number 1,9-ND-A manufactured by Kyoei Chemical Industry Co., Ltd., product number A-NOD-A manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product number CD595 manufactured by Sartmer Co., Ltd., product number SR214NS manufactured by Sartmer Co., Ltd. Product number BD, product number SR297 manufactured by Sartmer, product number SR248 manufactured by Sartmer, product name Light Ester NP manufactured by Kyoei Chemical Industry Co., Ltd., product number SR239NS manufactured by Sartmer Co., Ltd., product name Light Ester 1,6HX manufactured by Kyoei Chemical Industry Co., Ltd. Product number HD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name Light Ester 1,9ND manufactured by Kyoei Chemical Industry Co., Ltd., product number NOD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name Light Ester 1,10DC manufactured by Kyoei Chemical Industry Co., Ltd. It is preferable to contain at least one compound selected from the group consisting of the product number DOD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd. and the product number SR262 manufactured by Sartmer Co., Ltd.

The polyalkylene glycol di (meth) acrylate is, for example, a compound in which n is 2 or more in the formula (200). n is, for example, 2 to 10, preferably 2 to 7, preferably 2 to 6, and preferably 2 to 3. The carbon number of R3 is ^, for example, 2 to 7, preferably 2 to 5. The higher the number of carbon atoms, the higher the hydrophobicity of the cured product, and the more difficult it is for the cured product to permeate moisture. Polyalkylene glycol di (meth) acrylates include, in particular, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and tri. It preferably contains at least one compound selected from the group consisting of propylene glycol dimethacrylate, tritetramethylene glycol diacrylate, polyethylene glycol 200 dimethacrylate and polyethylene glycol 200 diacrylate. Further, the polyalkylene glycol di (meth) acrylate is particularly the product number SR230 manufactured by Sartmer, the product number SR508NS manufactured by Sartmer, the product number DPGDA manufactured by Dycel, the product number SR306NS manufactured by Sartmer, the product number TPGDA manufactured by Dysel, and Osaka Organic. Product number V310HP manufactured by Chemical Industry Co., Ltd., Product number APG200 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Product name Light Acrylate PTMGA-250 manufactured by Kyoei Chemical Industry Co., Ltd., Product number SR231NS manufactured by Sartmer Co., Ltd., Product name Light Ester 2EG manufactured by Kyoei Chemical Industry Co., Ltd. Product number SR205NS manufactured by Sartmer, product name Light Ester 3EG manufactured by Kyoei Chemical Industry Co., Ltd., product name SR210NS manufactured by Sartmer Co., Ltd., product name Light Ester 4EG manufactured by Kyoei Chemical Industry Co., Ltd. It is preferable to contain at least one compound selected from the group consisting of product number 3PG manufactured by the company.

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

When the acrylic compound (Y) contains a compound (Y11) having a structure represented by the formula (200), the compound (Y11) preferably does not contain a compound having an n value of 5 or more in the formula (200). .. When (R3 ^- O) n is a polyethylene glycol skeleton, it is particularly preferable that the compound having a value of n greater than 5 in the formula (200) is not contained. Even when compound (Y11) contains a compound having a value of n greater than 5 in the formula (200), the percentage of the compound having a value of n greater than 5 in the formula (200) to the acrylic compound (Y) is 20. It is preferably mass% or less. Further, even when the compound (Y11) contains a compound having an n value greater than 5 in the formula (200), the compound (Y11) preferably does not contain a compound having an n value greater than 9. It is more preferred that it does not contain compounds with a value greater than 7. In these cases, the increase in viscosity of the composition (X) is particularly unlikely to occur.

It is particularly preferable that the polyfunctional acrylic compound (Y1) contains a polyalkylene glycol di (meth) acrylate. Since the polyalkylene glycol di (meth) acrylate has a low viscosity and is hard to volatilize, it can contribute to lowering the viscosity of the composition (X), and the storage stability of the composition (X) is improved and the cured product is used. It can contribute to the reduction of outgas.

When the polyfunctional acrylic compound (Y1) contains a polyalkylene glycol di (meth) acrylate, the ratio of the polyalkylene glycol di (meth) acrylate to the acrylic compound (Y) is 40% by mass or more and 80% by mass or less. Is preferable. When the proportion of the polyalkylene glycol di (meth) acrylate is 40% by mass or more, the viscosity of the composition (X) can be effectively reduced. When the proportion of the polyalkylene glycol di (meth) acrylate is 80% by mass or less, the proportion of the compound having three or more (meth) acryloyl groups in the molecule increases, and the reactivity of the composition (X) and the reactivity of the composition (X) are increased. The glass transition temperature of the cured product can be increased. This ratio is more preferably 42% by mass or more and 75% by mass or less, and further preferably 45% by mass or more and 70% by mass or less.

The polyfunctional acrylic compound (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, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and pentaerythritol tetra (meth) acrylate. In this case, the glass transition temperature of the cured product can be particularly increased, and therefore the heat resistance of the cured product can be particularly increased.

The polyfunctional acrylic compound (Y1) preferably contains pentaerythritol tetra (meth) acrylate. In this case, the glass transition temperature of the cured product can be particularly increased, and the reactivity of the composition (X) can be improved. When the reactivity of the composition (X) is improved, the composition (X) can be easily cured even in an environment containing oxygen such as an atmospheric atmosphere.

When the polyfunctional acrylic compound (Y1) contains pentaerythritol tetra (meth) acrylate, the ratio of pentaerythritol tetra (meth) acrylate to the acrylic compound (Y) shall be 0.5% by mass or more and 10% by mass or less. Is preferable. In this case, it is possible to achieve both high reactivity and low viscosity of the composition (X). This ratio is more preferably 1% by mass or more and 9% by mass or less, and further preferably 2% by mass or more and 8% by mass or less.

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

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

It is particularly preferable that the polyfunctional acrylic compound (Y1) contains a polyalkylene glycol di (meth) acrylate and a pentaerythritol tetra (meth) acrylate. In this case, the composition (X) has a low viscosity and is excellent in reactivity. Therefore, the composition (X) can be easily cured even in an environment containing oxygen such as an atmospheric atmosphere.

The acrylic compound (Y) also 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 shrinkage of the composition (X) during curing.

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

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. , Methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydixyl ethyl acrylate, ethyl diglycol acrylate, cyclic trimethyl propaneformal monoacrylate, Iimide 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, Morpholine-4-yl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate , 1,4-Cyclohexanedimethanol monoacrylate, 3-methacryloyloxymethylcyclohexene oxide and 3-acryloyloxymethylcyclohexene oxide, which contain at least one compound selected from the group.

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.

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

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

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

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

The acrylic compound (Y) may contain a compound having nitrogen in the molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. In addition, the reactivity of the acrylic compound (Y) is likely to be improved, and therefore outgas is less likely to be generated from the cured product. The compound having nitrogen in the molecular skeleton is selected from the group consisting of compounds having a morpholine skeleton such as acryloyl morpholine and morpholine-4-yl acrylate, diethylacrylamide, dimethylaminopropylacrylamide and pentamethylpiperidylmethacrylate. Contains at least one compound.

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 improved even in an air atmosphere. It is particularly preferable that the acrylic compound (Y) contains at least one of acryloyl morpholine and morpholine-4-yl acrylate. In this case, shrinkage of the composition (X) during curing can be suppressed. In addition, the viscosities of acryloyl morpholine and morpholine-4-yl acrylate are low, so that these compounds do not easily increase the viscosity of the composition (X). Furthermore, since these compounds are less likely to volatilize, it is easy to improve the storage stability of the composition (X).

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 further preferably 10% by mass or more and 40% by mass or less.

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.

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

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

In formula (100), ^R0 is an H or a methyl group. X is a single bond or 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.

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

The radically polymerizable compound (A1) may contain a radically polymerizable compound (Z) other than the acrylic compound (Y). The amount of the radically polymerizable compound (Z) with respect to the total amount of the acrylic compound (Y) and the radically polymerizable compound (Z) is, for example, 10% by mass or less. The radically polymerizable compound (Z) is a polyfunctional radically polymerizable compound (Z1) having two or more radically polymerizable functional groups in one molecule, and a monofunctional compound having only one radically polymerizable functional group in one molecule. One or both of the radically polymerizable compound (Z2) can be contained. The polyfunctional radically polymerizable compound (Z1) is, for example, a group consisting of aromatic urethane oligomers, aliphatic urethane oligomers, epoxy acrylate oligomers, polyester acrylate oligomers and other special oligomers having two or more ethylenic double bonds in one molecule. It may contain at least one compound selected from. The components that can be contained in the polyfunctional radically polymerizable compound (Z1) are not limited to the above. The monofunctional radically polymerizable compound (Z2) includes, for example, N-vinylformamide, vinylcaprolactum, vinylpyrrolidone, phenylglycidyl ether, p-tert-butylphenylglycidyl ether, butylglycidyl ether, 2-ethylhexylglycidyl ether, allylglycidyl ether, and the like. 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene It contains at least one compound selected from the group consisting of oxide, N-vinylpyrrolidone and N-vinylcaprolactam. The components that can be contained in the monofunctional radically polymerizable compound (Z2) are not limited to the above.

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

In other words, the radically polymerizable compound (A1) preferably contains a compound having nitrogen in the molecular skeleton. The compound having nitrogen in the 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 ratio of the compound having nitrogen in the molecular skeleton to the entire radically polymerizable compound (A1) is preferably 5% by mass or more and 80% by mass or less. When this ratio is 5% by mass or more, the adhesion between the cured product and the inorganic material is particularly likely to be improved. When this ratio is 80% by mass or less, the compound having nitrogen in the molecular skeleton does not easily impair the storage stability of the composition (X), and the satellite when the composition (X) is jetted by the inkjet method can be used. Hard to cause. Therefore, the inkjet property of the composition (X) is less likely to be impaired. Further, it is possible to reduce the generation of outgas caused by the compound having nitrogen in the molecular skeleton. This ratio is more preferably 10% by mass or more and 70% by mass or less, further preferably 20% by mass or more and 60% by mass or less, and particularly preferably 25% by mass or more and 50% by mass or less.

The ratio of the total number of monofunctional compounds in the radically polymerizable compound (A1) to the radically polymerizable compound (A1) (that is, the total of the monofunctional acrylic compound (Y2) and the monofunctional radically polymerizable compound (Z2)) is It is preferably 70% by mass or less. In this case, the generation of outgas due to the monofunctional compound is less likely to occur. This ratio is more preferably 60% by mass or less, and even more preferably 50% by mass or less.

The radically polymerizable compound (A1) preferably contains at least one selected from the group consisting of acroylmorpholine, morpholine-4-yl acrylate, diethylacrylamide, and dimethylacrylamide. In this case, the absolute value of the difference between the first curing shrinkage rate and the second curing shrinkage rate tends to be small. The total percentage of acroylmorpholine, morpholine-4-yl acrylate, diethylacrylamide, and dimethylacrylamide to the radically polymerizable compound (A1) is preferably 15% by mass or more. In this case, the above-mentioned difference in curing shrinkage rate is particularly likely to be realized. This percentage is more preferably 25% by mass or more, further preferably 35% by mass or more. The upper limit of this percentage is not particularly specified, but is, for example, 100% by mass or less. This percentage is preferably 85% by mass or less, and in this case, it is easy to adjust the hardness of the cured film to improve the flexibility. It is more preferable that the percentage is 70% by mass or less. Further, in order to reduce the absolute value of the difference between the first curing shrinkage rate and the second curing shrinkage rate, the radically polymerizable compound (A1) contains isobornyl methacrylate, lauryl methacrylate, and 1,6 hexanediol methacrylate. , Are preferably not contained.

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

It is also preferable that the photoradical polymerization initiator (B1) contains a component having a sensitizer skeleton in the molecule. The sensitizer skeleton comprises, for example, at least one of a 9H-thioxanthene-9-one skeleton and an anthracene skeleton. That is, the photoradical polymerization initiator (B) preferably contains a component having at least one of a 9H-thioxanthene-9-one skeleton and an anthracene skeleton.

The photoradical polymerization initiator (B1) also 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 atmospheric atmosphere, and outgas can be less likely to be generated from the cured product.

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

Oxime ester-based photoinitiators include, for example, 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], and etanone, 1- [9-ethyl-6- (2-). Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime), and Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2001-233842, Japanese Patent Laid-Open No. 2010-527339, Japanese Patent Laid-Open No. 2010- It can contain at least one compound selected from the group consisting of oxime ester-based photoinitiators described in 527338, JP2013-041153A, JP2015-93842A, and the like. The oxime ester-based photoinitiators are commercially available Irgacure OXE-02 (manufactured by BASF), ADEKA Arklus NCI-831, N-1919 (manufactured by ADEKA) and TR-PBG-304 (manufactured by Changzhou Strong Electronics) having a carbazole skeleton. New Materials Co., Ltd.), Irgacure OXE-01 with diphenyl sulfide skeleton, ADEKA Arklus NCI-930 (manufactured by ADEKA), TR-PBG-345 and TR-PBG-3057 (manufactured by Joshu Strong Electronics New Materials Co., Ltd.) , And at least one compound selected from the group consisting of TR-PBG-365 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.) and SPI-04 (manufactured by Sanyo) having a fluorene skeleton. In particular, when the oxime ester-based photoinitiator contains a compound having a diphenylsulfide skeleton or a fluorene skeleton, it is preferable because the cured product is less likely to be colored by photobleaching. It is also preferable that the oxime ester-based photoinitiator contains a compound having a carbazole skeleton because the exposure sensitivity tends to increase.

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

The ratio of the photoradical polymerization initiator (B1) to the radically polymerizable compound (A1) is preferably 6% by mass or more. In this case, the composition (X) can have good UV curability and can also have UV curability in a good air atmosphere. This ratio is more preferably 7% by mass or more, and further preferably 8% by mass or more. Further, this ratio is, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 18% by mass or less.

The radical polymerization initiator (B) preferably contains a radical polymerization initiator (B3) having a photobleaching property. For example, the photoradical polymerization initiator (B1) preferably contains a photoradical polymerization initiator (B31) having a photobleaching property as the photopolymerization initiator (B3). The photopolymerization initiator (B3) having a photobleaching property can enhance the transparency of the composition (X) and its cured product when the composition (X) is irradiated with ultraviolet rays. Therefore, when the composition (X) is irradiated with ultraviolet rays, the ultraviolet rays easily reach the inside of the composition (X). Therefore, the composition (X) tends to be cured efficiently, and the difference between the first curing shrinkage rate and the second curing shrinkage rate tends to be small.

The percentage of the photopolymerization initiator (B3) to the photopolymerization initiator (B) is preferably 50% by mass or more. In this case, the difference between the first curing shrinkage rate and the second curing shrinkage rate tends to be particularly small. This percentage is more preferably 60% by mass or more, and even more preferably 75% by mass or more. The upper limit of this percentage is not particularly specified, and may be 100% by mass. That is, this percentage is, for example, 100% by mass or less.

When the photoradical polymerization initiator (B1) contains a photoradical polymerization initiator (B31), the photoradical polymerization initiator (B31) is, for example, an acylphosphine oxide-based photoinitiator and an oxime ester-based photoinitiator. It contains at least one of the compounds having photobleaching property.

The oxime ester compound having photobleaching property contains, for example, at least one of a compound represented by the following formula (401) and a compound represented by the following formula (402). Of these, the compound represented by the formula (402) has particularly high sensitivity, so that it is easy to particularly enhance the photocurability of the composition (X), and therefore, it is easy to realize the ultraviolet curability of the composition (X) in the atmospheric atmosphere. ..

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

The radical polymerization initiator (B) preferably contains a photopolymerization initiator (B4) having an extinction coefficient of light having a wavelength of 405 nm of 5 ml / g · cm or more. For example, the photoradical polymerization initiator (B1) may contain, as the photopolymerization initiator (B4), a photoradical polymerization initiator (B41) having an absorption coefficient of light having a wavelength of 405 nm of 5 ml / g · cm or more. preferable. The photopolymerization initiator (B4) can enhance the reactivity of the composition (X) when the composition (X) is irradiated with ultraviolet rays. Therefore, the difference between the first curing shrinkage rate and the second curing shrinkage rate tends to be small.

The percentage of the photopolymerization initiator (B4) to the photopolymerization initiator (B) is preferably 50% by mass or more. In this case, the difference between the first curing shrinkage rate and the second curing shrinkage rate tends to be particularly small. This percentage is more preferably 60% by mass or more, and even more preferably 75% by mass or more. The upper limit of this percentage is not particularly specified, and may be 100% by mass. That is, this percentage is, for example, 100% by mass or less.

When the photoradical polymerization initiator (B1) contains a photoradical polymerization initiator (B41), the photoradical polymerization initiator (B41) may be, for example, 2-benzyl-2- (dimethylamino) -1- (4-morpholino). Phenyl) -1-butanone (eg, BASF's Radical 369), phenylbis (2,4,6-trimethylbenzoyl) phosphinoxide (eg, BASF's Radical819), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. (For example, Radical TPO manufactured by BASF), and bis (2,4-cyclopentadienyl) bis [2,6-difluoro-3- (1-pyryl) phenyl] titanium (IV) (for example, Radical 784 manufactured by BASF). Contains at least one selected from the group consisting of.

The compound contained in the photopolymerization initiator (B3) and the compound contained in the photoradical polymerization initiator (B4) may overlap. That is, when the composition (X) contains the photopolymerization initiator (B3), at least a part of the photoradical polymerization initiator (B4) may be contained in the photopolymerization initiator (B3). Further, when the composition (X) contains the photopolymerization initiator (B4), at least a part of the photoradical polymerization initiator (B3) may be contained in the photopolymerization initiator (B4).

The composition (X) may further contain a polymerization accelerator in addition to the photoradical polymerization initiator (B1). Examples of the polymerization accelerator include ethyl p-dimethylaminobenzoate, -2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, -2-dimethylaminoethyl benzoate, and butoxy p-dimethylaminobenzoate. Contains amine compounds such as ethyl. The components that can be contained in the polymerization accelerator are not limited to the above.

When the photopolymerizable compound (A) contains the cationically polymerizable compound (A2), the cationically polymerizable compound (A2) may be, for example, a polyfunctional cationically polymerizable compound (W1) and a monofunctional cationically polymerizable compound (W2). Contains at least one of them.

The polyfunctional cationically polymerizable compound (W1) is either one or both of a polyfunctional cationically polymerizable compound (W11) having no siloxane skeleton and a polyfunctional cationically polymerizable compound (W12) having a siloxane skeleton. Can be contained.

The polyfunctional cationically polymerizable compound (W11) does not have a siloxane skeleton and has two or more cationically polymerizable functional groups per molecule. The number of cationically polymerizable functional groups per molecule of the polyfunctional cationically polymerizable compound (W11) is preferably 2 to 4, more preferably 2 to 3.

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

The polyfunctional cationically polymerizable compound (W11) is composed 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. It contains at least one compound among the selected compounds.

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

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

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

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

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

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

Examples of the compound represented by the formula (20) include a tetrahydroinden epoxide represented by the following formula (20a).

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

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

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

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

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

The polyfunctional cationically polymerizable compound (W11) also preferably contains a polyfunctional alicyclic epoxy compound. In this case, the composition (X) can have a particularly high cationic polymerization reactivity.

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

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

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

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

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

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

When the composition (X) contains the polyfunctional cationically polymerizable compound (W11), the ratio of the polyfunctional cationically polymerizable compound (W11) to the total amount of the resin component is preferably 5% by mass or more and 95% by mass or less. .. The resin component refers to a cationically polymerizable compound in the composition (X), and includes a polyfunctional cationically polymerizable compound (W1) and a monofunctional cationically polymerizable compound (W2). When the proportion of the polyfunctional cationically polymerizable compound (W11) is 5% by mass or more, the composition (X) can have particularly excellent reactivity during the photocationic polymerization reaction, whereby the cured product has high strength. Can have (hardness). Further, when the ratio of the polyfunctional cationically polymerizable compound (W11) is 95% by mass or less, when the composition (X) contains the hygroscopic agent (E), the hygroscopic agent (E) is contained in the composition (X). ) Can be easily dispersed evenly. The proportion of the polyfunctional cationically polymerizable compound (W11) is more preferably 12% by mass or more, further preferably 15% by mass or more, further preferably 20% by mass or more, and 25% by mass or more. Is particularly preferable. The proportion of the polyfunctional cationically polymerizable compound (W11) is more preferably 85% by mass or less, and further preferably 60% by mass or less. For example, the proportion of the polyfunctional cationically polymerizable compound (W11) is preferably 20% by mass or more and 60% by mass or less.

When the polyfunctional cationically polymerizable compound (W11) contains a polyfunctional alicyclic epoxy compound, the polyfunctional alicyclic epoxy compound may be a part of the polyfunctional cationically polymerizable compound (W11), and all of them may be. May be. The ratio of the polyfunctional alicyclic epoxy compound to the polyfunctional cationically polymerizable compound (W11) is preferably in the range of 15 to 100% by mass. When this ratio is 15% by mass or more, the polyfunctional alicyclic epoxy compound can particularly contribute to the improvement of the ultraviolet curability of the composition (X).

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, and 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 the heat-resistant discoloration of the cured product and the optical component. The polyfunctional cationically polymerizable compound (W12) can also contribute to lowering the elastic modulus of the cured product and the optical component. When the composition (X) contains a hygroscopic agent, the polyfunctional cationically polymerizable compound (W12) can also contribute to the improvement of the dispersibility of the hygroscopic agent in the composition (X) and the cured product.

The polyfunctional cationically polymerizable compound (W12) is preferably 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, the increase in viscosity of the composition (X) can be suppressed.

The cationically polymerizable functional group contained in 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.

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

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

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

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

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

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

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

The polyfunctional cationically polymerizable compound (W12) preferably has an alicyclic epoxy structure, and it is particularly preferable that the polyfunctional cationically polymerizable compound (W12) contains the compound represented by the formula (10a). The compound represented by the formula (10a) can particularly contribute to the improvement of the cationic polymerization reactivity and the reduction of the viscosity of the composition (X), and particularly to the improvement of the heat-resistant discoloration property and the low elastic modulus of the cured product and the optical component. Can contribute. When the composition (X) contains the hygroscopic agent (E), it can particularly contribute to the improvement of the dispersibility of the hygroscopic agent (E) in the composition (X).

When the composition (X) contains the polyfunctional cationically polymerizable compound (W12), the ratio of the polyfunctional cationically polymerizable compound (W12) to the total amount of the resin component is preferably in the range of 5 to 95% by mass. .. In this case, particularly when the composition (X) contains the hygroscopic agent (E), the dispersibility of the hygroscopic agent (E) in the composition (X) and the cured product is particularly improved, and the composition (X) Can have a particularly high photocationic polymerization reactivity.

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

The viscosity of the monofunctional cationically polymerizable compound (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.

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.

The ratio of the monofunctional cationically polymerizable compound (W2) to the total amount of the resin component is preferably in the range of 5 to 50% by mass. When the proportion of the monofunctional cationically polymerizable compound (W2) is 5% by mass or more, the viscosity of the composition (X) can be particularly reduced. Further, when the proportion of the monofunctional cationically polymerizable compound (W2) is 50% by mass or less, the composition (X) can have particularly excellent reactivity during the photocationic polymerization reaction, whereby the cured product can be obtained. Can have high strength (hardness). The ratio of the monofunctional cationically polymerizable compound (W2) is more preferably 10% by mass or more, still more preferably 15% by mass or more. The proportion of the monofunctional cationically polymerizable compound (W2) is more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less. When the proportion of the monofunctional cationically polymerizable compound (W2) is particularly 35% by mass or less, the amount of volatilization of the components in the composition (X) during storage of the composition (X) can be effectively reduced. Therefore, even if the composition (X) is stored for a long period of time, the characteristics of the composition (X) are not easily impaired. Further, it is possible to particularly suppress the occurrence of tack on the cured product. For example, the proportion of the monofunctional cationically polymerizable compound (W2) is preferably in the range of 10 to 35% by mass.

Further, particularly when the composition (X) contains the polyfunctional cationically polymerizable compound (W11) and the polyfunctional cationically polymerizable compound (W12), the polyfunctional cationically polymerizable compound (W11) is used with respect to the total amount of the resin component. The ratio of the polyfunctional cationically polymerizable compound (W12) is in the range of 15 to 30% by mass, and the ratio of the monofunctional cationically polymerizable compound (W2) is 15 to 40% by mass. It is preferably in the range of%. In this case, good storage stability of the composition (X), low viscosity and good cationic polymerization reactivity can be achieved in a well-balanced manner, and further, excellent transparency, excellent hygroscopicity and high refractive index of the cured product are balanced. Can be achieved well.

If the cationically polymerizable compound (A2) contains the compound represented by the formula (3) and the compound represented by the formula (16), a photocured product is produced from the composition (X) by adjusting the ratio of both. It is possible to reduce the viscosity of the composition (X) and improve the storage stability while appropriately adjusting the ease of progress of the curing reaction in the case of the above.

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

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

In formula (30), X is at least one selected from the group consisting of halogen, H, hydrocarbon group and alkylene glucol group, and when there are a plurality of X in one molecule, they are different even if they are the same. You may. 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 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.

When the cationically polymerizable compound (A2) contains the aromatic epoxy compound (f1), the aromatic epoxy compound (f1) has a low viscosity, so that the aromatic epoxy compound (f1) lowers the viscosity of the composition (X). Easy to make. Further, the aromatic epoxy compound (f1) is less likely to volatilize, so that even if the composition (X) is stored, the composition (X) is less likely to change in composition due to the volatilization of the aromatic epoxy compound (f1). .. Therefore, the aromatic epoxy compound (f1) tends to enhance the storage stability of the composition (X). Further, since the aromatic epoxy compound (f1) has high reactivity, unreacted components are less likely to remain in the cured product, and therefore outgas is less likely to be generated from the cured product. Further, the aromatic epoxy compound (f1) tends to increase the glass transition temperature of the cured product, and therefore tends to increase the heat resistance of the cured product.

Further, the aromatic epoxy compound (f1) is less likely to generate defective droplets called satellites when the composition (X) is ejected by an inkjet method.

It is preferable that R in the formula (30) is a single bond or an alkylene group. When n in the formula (30) is 2 or 3, it is preferable that at least one of the plurality of Rs in the 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 rays tends to be high.

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

In particular, the aromatic epoxy compound (f1) may contain at least one component selected from the group consisting of the compounds represented by the formulas (301) to (305), (312), (314) and (318), respectively. preferable. These compounds tend to have high reactivity because at least one epoxy group (oxylan) in the compound and a benze ring are bonded by a single bond or an alkylene group, so that the composition (X) is cured. Easy to enhance sex.

The ratio of the aromatic epoxy compound (f1) to the entire cationically polymerizable compound (A2) is preferably 5% by mass or more. In this case, the above-mentioned action by the aromatic epoxy compound (f1) is particularly easy to obtain. This ratio is also preferably 95% by mass or less. In this case, the storability of the composition (X) tends to be good. This ratio is more preferably 10% by mass or more and 90% by mass or less, and further preferably 20% by mass or more and 85% by mass or less.

It is also preferable that the cationically polymerizable compound (A2) contains a compound (f2) having an oxyalkylene skeleton. The oxyalkylene skeleton is a linear skeleton composed of one or more linear oxyalkylene units.

When the cationically polymerizable compound (A2) contains the compound (f2), the compound (f2) has a low viscosity, so that the compound (f2) tends to lower the viscosity of the composition (X). Further, the compound (f2) is less likely to volatilize, and therefore, even if the composition (X) is stored, the composition (X) is less likely to change in composition due to the volatilization of the aromatic epoxy compound (f1). Therefore, the compound (f2) tends to enhance the storage stability of the composition (X).

Further, the compound (f2) is less likely to generate defective droplets called satellites when the composition (X) is ejected by an inkjet method. Further, the compound (f2) can make satellites less likely to occur even if the speed of the droplets ejected by the inkjet method is increased. Therefore, depending on the conditions of inkjet, for example, it is possible to increase the ejection speed of droplets by the inkjet method to 4 m / s or more without causing satellites. If the velocity of the droplet can be increased, the trajectory of the droplet is less likely to be affected by disturbance, so that the dimensional accuracy of the cured product produced from the composition (X) can be improved. Further, since the compound (f2) can enhance the storage stability of the composition (X) as described above, the composition (X) is less likely to generate satellites even if the composition (X) is stored for a long period of time. The characteristics are easily maintained.

The oxyalkylene skeleton preferably contains a structure of "-C-C-O-", that is, an oximethylene unit. In this case, satellites are less likely to be generated, and satellites are less likely to be generated even if the drive frequency at which the composition (X) is ejected by, for example, an inkjet method is changed. In addition, the compound (f2) is less likely to volatilize and tends to have a lower viscosity, and the affinity (wetting property) of the composition (X) with respect to the inorganic material tends to increase.

The number of oxyalkylene units in the oxyalkylene skeleton of compound (f2) is preferably 1 or more and 8 or less. In this case, since the compound (f2) tends to have a lower viscosity, satellites are less likely to occur, and the crosslink density of the cured product tends to increase, so that the glass transition temperature of the cured product tends to increase. The number of the oxyalkylene units is more preferably 1 or more and 6 or less, and further preferably 1 or more and 4 or less.

A substituent other than hydrogen may be bonded to the oxyalkylene unit in the oxyalkylene skeleton of the compound (f2). For example, the oxymethylene unit contained in the oxyalkylene skeleton may have a structure of "-CH (CH ₃ ) -CH ₂ -O-".

The ratio of the compound (f2) is preferably 10% by mass or more with respect to the cationically polymerizable compound (A2). In this case, the ink jet property becomes good and the wettability to the base material becomes good. It is also preferable that this ratio is 70% by weight or less. In this case, the glass transition temperature can be sufficiently increased. This ratio is more preferably 15% by mass or more and 60% by mass or less, and further preferably 20% by mass or more and 50% by mass or less.

The compound (f2) contains, for example, at least one compound among a compound (f21) having an oxyalkylene skeleton and an epoxy group and a compound (f22) having an oxyalkylene group and an oxetane group.

The compound (f21) is, for example, the compound represented by the above formula (1b), the compound represented by the formula (4), the compound represented by the formula (5), the compound represented by the formula (6), the compound represented by the formula (7), and the formula. It contains at least one compound selected from the group consisting of the compound represented by (8), the compound represented by the formula (13), the compound represented by the formula (14) and the like. The components that can be contained in the compound (f21) are not limited to the above.

The compound (f22) is at least one selected from the group consisting of, for example, the compound represented by the above formula (3), the compound represented by the formula (12), the compound represented by the formula (16), and the compound represented by the formula (17). Contains the compound of. The components that can be contained in the compound (f22) are not limited to the above.

The cationically polymerizable compound (A2) also preferably contains an epoxy compound and the above-mentioned compound (f22). The epoxy compound contains, for example, at least one of the compounds having an epoxy group among the compounds that can be contained in the above-mentioned cationically polymerizable compound (A2). When the cationically polymerizable compound (A2) contains the epoxy compound and the compound (f22), the curability of the composition (X) when the composition (X) is irradiated with ultraviolet rays is likely to be enhanced, and the composition at this time is likely to be enhanced. Excessive curing of the substance (X) is less likely to occur, and therefore deterioration of transparency due to cloudiness or the like is less likely to occur in the cured substance. The mechanism that causes this effect is presumed to be as follows. Since the reactivity of the compound (f22) is lower than that of the epoxy compound, when the composition (X) is irradiated with ultraviolet rays, the epoxy compound first reacts. The reaction of this epoxy compound tends to increase the curability of the composition (X). Subsequently, the reaction of the compound (f22) makes it difficult for the epoxy compound and the compound (f22) to react at once. It is considered that this makes it difficult for an excessively rapid reaction to occur. In this case, the ratio of the compound (f22) to the cationically polymerizable compound (A2) is preferably 20% by mass or more. In this case, the compound (f22) tends to make the composition (X) particularly low in viscosity and particularly easy to enhance the storage stability of the composition (X). Further, the compound (f22) tends to particularly enhance the curability of the composition (X). The proportion of compound (f22) is also preferably 90% by mass or less. In this case, the curability of the cured product can be sufficiently enhanced. The ratio of the compound (f22) is more preferably 10% by mass or more and 90% by mass or less, and further preferably 20% by mass or more and 80% by mass or less. Further, the ratio of the epoxy compound in this case is preferably 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 80% by mass or less with respect to the total amount of the cationically polymerizable compound (A2). , 25% by mass or more and 75% by mass or less is more preferable. In these cases, the unreacted groups in the cured product can be sufficiently reduced to sufficiently enhance the curability of the cured product.

The epoxy compound preferably contains a compound having at least one oxylan ring that does not form a glycidyl ether group. In this case, the epoxy compound tends to particularly increase the curability of the composition (X). It is more preferable that the epoxy compound contains a compound having two or more oxylane rings that do not form a glycidyl ether group. It is also preferable that the epoxy compound contains a compound having no glycidyl ether group. It is particularly preferable that the epoxy compound contains a compound having two or more oxylane rings that do not form a glycidyl ether group and that does not have a glycidyl ether group.

It is particularly preferable that the cationically polymerizable compound (A2) contains the compound (f2) and the epoxy compound, and the epoxy compound further contains the above-mentioned aromatic epoxy compound (f1). In this case, the composition (X) tends to have particularly excellent storage stability, and when the composition (X) is ejected by an inkjet method, it is particularly difficult to generate defective droplets called satellites. Further, even if the speed of the droplets ejected by the inkjet method is increased, satellites can be made particularly difficult to occur. Further, even if the composition (X) is stored for a long period of time, the characteristic of the composition (X) that satellites are unlikely to be generated is particularly easy to be maintained. In this case, it is particularly preferable that the compound (f2) contains the compound (f22).

The total ratio of the aromatic epoxy compound (f1) and the compound (f22) to the cationically polymerizable compound (A2) is preferably 55% by mass or more. In this case, the action of the combination of the aromatic epoxy compound (f1) and the compound (f22) is particularly remarkable. This ratio is more preferably 60% by mass or more, and further preferably 70% by mass or more. It is particularly preferable that the cationically polymerizable compound (A2) contains only the aromatic epoxy compound (f1) and the compound (f22).

The cationically polymerizable compound (A2) is preferably an alicyclic epoxy from the viewpoint of reactivity. Specifically, the cationically polymerizable compound (A2) is, for example, a compound represented by the formula (20a) (for example, product number THI-DE manufactured by JX Energy Co., Ltd.) and a compound represented by the formula (1a) (for example, a product name manufactured by Daicel Corporation). It contains at least one selected from the group consisting of celoxide 8010), a compound represented by the formula (1b) (for example, product name celoxide 2021P manufactured by Daicel), and limonene dioxide (for example, LDO manufactured by Arkema). The percentage of the cationically polymerizable compound (A2) to the entire cationically polymerizable compound (A) is preferably 40% by mass or more.

The photocationic polymerization initiator (B2) is not particularly limited as long as it is a catalyst that generates protonic acid or Lewis acid by being irradiated with light. The photocationic polymerization initiator (B2) can contain at least one of an ionic photoacid generation type cation curing catalyst and a nonionic photoacid generation type cation curing catalyst.

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

The nonionic photoacid generation type cationic curing catalyst is at least one selected from the group consisting of, for example, nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, and N-hydroxyimide phosphonate. Can contain the components of. The components that can be contained in the nonionic photoacid generation type cationic curing catalyst are not limited to the above.

More specific examples of compounds that can be contained in the photocationic polymerization initiator (B2) are DPI series (105, 106, 109, 201, etc.), BI-105, MPI series (103, 105, 106, etc.) manufactured by Midori Kagaku. 109, etc.), BBI series (101, 102, 103, 105, 106, 109, 110, 200, 210, 300, 301, etc.), TSP series (102, 103, 105, 106, 109, 200, 300, 1000, etc.) ), HDS-109, MDS series (103, 105, 109, 203, 205, 209, etc.), BDS-109, MNPS-109, DTS series (102, 103, 105, 200, etc.), NDS series (103, 105, etc.) , 155, 165, etc.), DAM series (101, 102, 103, 105, 201, etc.), SI series (105, 106, etc.), PI-106, NDI series (105, 106, 109, 1001, 1004, etc.), PAI series (01, 101, 106, 1001, 1002, 1003, 1004, etc.), MBZ-101, PYR-100, NB series (101, 201, etc.), NAI series (100, 1002, 1003, 1004, 101, 105, etc.) , 106, 109, etc.), TAZ series (100, 101, 102, 103, 104, 107, 108, 109, 110, 113, 114, 118, 122, 123, 203, 204, etc.), NBC-101, ANC- 101, TPS-Actate, DTS-Actate, Di-Boc Bisphinol A, tert-Butyl lithocholate, tert-Butyl deoxycholate, tert-Butty holate, BX, BC-2, MPI-103, BDS-105, TP -103, BMS-105, and TMS-105;
Union Carbide, USA Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, and Cyracure UVI-950;
BASF's Irgacure 250, Irgacure 261 and Irgacure 264;
CG-24-61 manufactured by Ciba Geigy Co., Ltd .;
ADEKA CORPORATION ADEKA CORPORATION SP-150, ADEKA CORPORATION SP-151, ADEKA CORPORATION SP-170 and ADEKA CORPORATION SP-171;
DAICAT II manufactured by Daicel Corporation;
UVAC1590 and UVAC1591 manufactured by Daicel Cytec Co., Ltd .;
CI-2064, CI-2369, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758, and CIT-1682; manufactured by Nippon Soda Corporation;
PI-2074, a tetrakis (pentafluorophenyl) borate toluyl cumyliodonium salt manufactured by Rhodia;
3M FFC509;
CD-1010, CD-1011 and CD-1012 manufactured by Sartomer, USA;
Includes CPI-100P, CPI-101A, CPI-110P, CPI-110A and CPI-210S from Sun Appro Co., Ltd .; and UVI-6992 and UVI-6976 from Dow Chemical. The photocationic polymerization initiator (B2) can contain at least one compound selected from the group consisting of these compounds.

The ratio of the photocationic 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 a particularly good cationic polymerization reactivity. Further, when this ratio is 4% by mass or less, the composition (X) can have good storage stability, and the production cost is reduced by not containing an excess photocationic polymerization initiator (B2). Is possible.

The composition (X) may contain a sensitizer (C). In this case, since the sensitizer (C) can accelerate the reaction of the photopolymerization initiator (B), the difference between the first curing shrinkage rate and the second curing shrinkage rate of the composition (X) is small. It's easy to do.

The sensitizer (C) is, 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, which can contain at least one compound selected from the group. The components that the sensitizer (C) can contain are not limited to the above.

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

The sensitizer (C) preferably contains an anthracene-based compound. In this case, since the transparency of the composition (X) is less likely to be impaired, the coating film of the composition (X) tends to be uniformly cured from the surface layer to the deep part, and therefore unevenness is less likely to occur in the cured product.

The percentage of the sensitizer (C) to the composition (X) is preferably 0.05% by mass or more. In this case, the reactivity of the composition (X) tends to be particularly high, and therefore the difference between the first curing shrinkage rate and the second curing shrinkage rate tends to be particularly small. This percentage is more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more. The percentage of the sensitizer (C) is preferably 2.0% by mass or less. In this case, the coating film of the composition (X) tends to be uniformly cured from the surface layer to the deep part, and therefore unevenness is less likely to occur in the cured product. This percentage is more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less.

The composition (X) may contain a leveling agent (D). The leveling agent (D) tends to smooth the surface of the coating film of the composition (X). Therefore, when the coating film is irradiated with ultraviolet rays, the coating film tends to be cured uniformly, and therefore, unevenness is less likely to occur on the cured product.

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 the inorganic material such as silicon nitride is enhanced, the smoothness of the coating film and the cured film is particularly likely to be enhanced. The silane compound (D11) preferably contains a silane compound (D12) having an azacyclopentane skeleton (pyrrolidin skeleton). In this case, the smoothness of the coating film and the cured film tends to be particularly improved. The silane compound (D12) has, for example, a structure in which 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.

The silane compound (D12) preferably contains a azasila cyclopentane-type silane. The azasila cyclopentane type silane has, for example, a structure represented by the following formula (4).

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

The carbon number of each of R ¹ and R ² is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and further preferably 1 or more and 2 or less.

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 number of carbon atoms of the hydrocarbon group is preferably 3 or more and 20 or less, more preferably 4 or more and 17 or less, and further preferably 6 or more and 14 or less. 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, an octyl group / a tetradecyl group; an isopropyl group, a tertiary butyl group or an isobutyl. A branched chain alkyl group such as a group; a cyclic alkyl group such as a cyclohexyl group; an aryl group such as a phenyl group, a trill group or a xylyl group; an aralkyl group such as a phenethyl group or a diphenylmethyl group.

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

The compound that can be contained in the silane compound (D1) is not limited to the above-mentioned silane compound (D11). The silane compound (D1) can contain an appropriate organic alkoxysilane, for example, the silane compound (D1) is derived from N-phenyl-3-aminopropyltrimethoxysilane, phenyltrimethoxysilane, hexyltrimethoxysilane and the like. Can contain at least one compound selected from the group.

Further, the compound that can be contained in the leveling agent (D) is not limited to the silane compound (D1). For example, the leveling agent (D) can contain at least one compound selected from the group consisting of a fluorine compound, an acrylic copolymer, and an alcohol alkoxylate compound.

The percentage of the leveling agent (D) to the composition (X) is preferably 0.1% by mass or more. In this case, unevenness is less likely to occur on the cured product. This percentage is more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more. Further, 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 inkjet ejection property from being deteriorated due to an excessive decrease in surface tension. This percentage is more preferably 2.5% by mass or less, and even more preferably 2.0% by mass or less.

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

The hygroscopic agent (E) is preferably an inorganic particle having hygroscopicity, and contains at least one component selected from the group consisting of, for example, zeolite particles, silica gel particles, calcium chloride particles, and titanium oxide nanotube particles. Is preferable. It is particularly preferable that the hygroscopic agent (E) contains zeolite particles.

Zeolite particles having an average particle size of 200 nm or less can be produced, for example, by pulverizing a general industrial zeolite. In producing the zeolite particles, the zeolite may be crushed and then crystallized by hydrothermal synthesis or the like. In this case, the zeolite particles can have particularly high hygroscopicity. Examples of such a method for producing zeolite particles are disclosed in JP-A-2016-69266A, JP-A-2013-049602, and the like.

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

The pH of the zeolite particles is preferably 7 or more and 10 or less. When the pH of the zeolite particles is 7 or more, the crystals of the zeolite particles are less likely to be destroyed, so that the encapsulant made from the composition (X) containing the zeolite particles can have particularly high hygroscopicity. Further, when the pH of the zeolite particles is 10 or less, the zeolite particles are less likely to inhibit the curing when the composition (X) is cured. The pH of the zeolite particles is determined by heating a dispersion obtained by adding 0.05 g of zeolite particles to 99.95 g of ion-exchanged water at 90 ° C. for 24 hours, and then measuring the pH of the supernatant of the dispersion with a pH meter. It is a value obtained by measuring with. As the pH measuring device, for example, a compact pH meter <LAQUAtwin> B-711 manufactured by HORIBA, Ltd. can be used.

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

The average particle size of the hygroscopic agent (E) is more preferably 150 nm or less, further preferably 100 nm or less, and particularly preferably 70 nm or less. Further, the average particle size of the hygroscopic agent (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 hygroscopicity.

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

When the composition (X) contains the hygroscopic agent (E), the ratio of the hygroscopic agent (E) to the total amount of the composition (X) is preferably 1% by mass or more and 20% by mass or less. When the ratio of the hygroscopic agent (E) is 1% by mass or more, the cured product can have particularly high hygroscopicity. Further, if the proportion of the hygroscopic agent (E) is 20% by mass or less, the viscosity of the composition (X) can be particularly reduced, and the composition (X) has a sufficiently low viscosity that can be applied by an inkjet method. You can also. The proportion of the hygroscopic agent (E) is more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The proportion of the hygroscopic agent (E) is more preferably 15% by mass or less, and particularly preferably 13% by mass or less.

The composition (X) may further contain an inorganic filler other than the hygroscopic agent (E). In particular, the composition (X) preferably contains nano-sized high-refractive index particles. Examples of high refractive index particles include zirconia particles. When the composition (X) contains high refractive index particles, the cured product can have a high refractive index while maintaining good transparency of the cured product. Therefore, when the cured product is applied to the sealing material 5 in the light emitting device 1, it is possible to improve the efficiency of taking out the light transmitted through the sealing material 5 and emitted to the outside. The average particle size of the high-refractive index particles is preferably in the range of 5 to 30 nm, and more preferably in the range of 10 to 20 nm.

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

When the composition (X) contains the hygroscopic agent (E), it is preferable that the composition (X) further contains the dispersant (F). In this case, the dispersant (F) can improve the dispersibility of the hygroscopic agent (E) in the composition (X). Therefore, in the composition (X), the increase in viscosity and the decrease in storage stability due to the hygroscopic agent (E) are unlikely to occur.

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

When the composition (X) contains the hygroscopic agent (E), the amount of the dispersant (F) with respect to 100 parts by mass of the hygroscopic agent (E) is preferably 5 parts by mass or more and 60 parts by mass or less. When the amount of the dispersant (F) is 5 parts by mass or more, the function of the dispersant (F) can be effectively exhibited, and when the amount is 60 parts by mass or less, the dispersant (F) in the encapsulant 5 is used. It is possible to prevent the free molecules of the material from inhibiting the adhesion between the sealing material 5 and the member made of the inorganic material. Further, the amount of the dispersant (F) is more preferably 15 parts by mass or more, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. preferable.

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

The light emitting element 4 includes, for example, a light emitting diode. The light emitting diode includes, for example, at least one of an organic EL element (organic light emitting diode) and a micro light emitting diode. When the light emitting element 4 includes an organic light emitting diode, the light emitting device 1 provided with the light emitting element 4 is, for example, an organic EL display. When the light emitting element 4 includes a micro light emitting diode, the light emitting device 1 provided with the light emitting element 4 is, for example, a micro LED display. In addition, EL is an abbreviation for electroluminescence.

An example of the structure of the light emitting device 1 will be described with reference to FIG. This light emitting device 1 is a top emission type. The light emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 at intervals, a light emitting element 4 on a surface of the support substrate 2 facing the transparent substrate 3, and a passion layer covering the light emitting element 4. 6 and a sealing material 5 are provided.

The support substrate 2 is made of, for example, a resin material, but is not limited thereto. The transparent substrate 3 is made of a translucent material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate. The light emitting element 4 includes, for example, a pair of electrodes 41 and 43 and an organic light emitting layer 42 between the electrodes 41 and 43. The organic light emitting layer 42 includes, for example, a hole injection layer 421, a hole transport layer 422, an organic light emitting layer 423, and an electron transport layer 424, and these layers are laminated in the above order.

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

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

Further, a second encapsulant 52 is filled between the second passivation layer 62 and the transparent substrate 3. The second encapsulant 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 encapsulant 52 may be the same as or different from that of the encapsulant 5.

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

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

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

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

More specifically, for example, first, the support substrate 2 is prepared. A partition wall 7 is formed on one surface of the support substrate 2 by a photolithography method using, for example, a photosensitive resin material. Subsequently, a plurality of light emitting elements 4 are provided on one surface of the support substrate 2. The light emitting element 4 can be manufactured by an appropriate method such as a vapor deposition method or a coating method. In particular, it is preferable to manufacture the light emitting element 4 by a coating method such as an inkjet method. As a result, the element array 9 is manufactured on the support substrate 2.

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

Next, the composition (X) is molded on the first passivation layer 61 by, for example, an inkjet method to prepare a coating film. If the inkjet method is applied to both the formation of the light emitting element 4 and the coating of the composition (X), the 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 prepare a sealing material 5. The thickness of the sealing material 5 is, for example, 5 μm or more and 50 μm or less.

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

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

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

Next, ultraviolet rays are irradiated from the outside toward the transparent substrate 3. Ultraviolet rays pass through the transparent substrate 3 and reach the ultraviolet curable resin material. As a result, the ultraviolet curable resin material is cured, and the second encapsulant 52 is produced.

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

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

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

The application of the composition (X) according to the present embodiment is not limited to the production of the sealing material 5 for the light emitting element 4. The composition (X) can be used to make various optical components that transmit light emitted by a light source. For example, the optical component may be a color resist. That is, for example, the composition (X) may contain a phosphor to prepare a color resist in a color filter from the composition (X). This color filter can be provided in a display device such as an organic EL display or a micro LED display which is a light emitting device.

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

The details of the components shown in the table are as follows. The viscosities of the following components are measured using a rheometer (manufactured by Anton Paar Japan Co., Ltd., model number DHR-2) under the conditions of a temperature of 25 ° C. and a shear rate of 1000 s ^-1 .
-Acryloyl morpholine, viscosity 12 mPa · s.
-Morpholine acrylate-4-yl: Viscosity 16 mPa · s.
-Polyethylene glycol 200 dimethacrylate: manufactured by Shin Nakamura Chemical Industry Co., Ltd., viscosity 14 mPa · s.
-Tripropylene glycol diacrylate: Viscosity 15 mPa · s.
-Pentaerythritol tetraacrylate: viscosity 350 mPa · s.
-Irgacure TPO: Made by BASF, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, absorption coefficient of light with a wavelength of 405 nm 165 ml / g · cm, with photobleaching property.
-Irgacure819: Made by BASF, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, extinction coefficient of light with a wavelength of 405 nm 900 ml / g · cm, photobleaching property.
-Irgacure 907: Made by BASF, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, extinction coefficient of light with a wavelength of 405 nm 0 ml / g · cm, no photobleaching property.
-Irgacure 184: manufactured by BASF, 1-hydroxy-cyclohexyl-phenyl-ketone, extinction coefficient of light with a wavelength of 405 nm 0 ml / g · cm, no photobleaching property.
-Sensitizer 1: Anthracene-based sensitizer, manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name Anthracene (registered trademark) UVS-581.
-Sensitizer 2: Thioxanthone-based sensitizer, 2,4-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd., product name KAYACURE DETX-S.
-Leveling agent 1: 2,2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane.
-Leveling agent 2: 2,2-dimethoxy-1-tetradecyl-1-aza-2-silacyclopentane.
-Leveling agent 3: Phenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-103.
-Leveling agent 4: Hexyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-3063.

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

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

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

(3) Transmittance A coating film having a thickness of 10 μm is prepared by applying the composition, and an LED-UV irradiator (model number E075IIHD, peak wavelength 395 nm) manufactured by Ushio Co., Ltd. is used for this coating film in the atmosphere. A film was prepared by irradiating with ultraviolet rays at an irradiation intensity of 3 W / cm ² for 5.3 seconds and then heating at 100 ° C. for 5 minutes. The total light transmittance of this film according to JIS K7361-1 was measured.

(4) Reaction rate The composition was measured with an infrared spectrophotometer (manufactured by Agilent Technologies, model number Agent Carry 610 FTIR microscope system) to obtain an IR spectrum.

The composition is applied to prepare a coating film having a thickness of 10 μm, and the coating film is irradiated with ultraviolet rays having a peak wavelength of 395 nm using a UV irradiator (manufactured by CCS, model number CKL-200) with an irradiation intensity of 3 W / cm ² and an integrated light intensity. Irradiation was performed under the condition of 0.9 J / cm ² . Subsequently, the composition (cured product) after irradiation with ultraviolet rays was measured with the above-mentioned infrared spectrophotometer to obtain an IR spectrum.

In each of the two IR spectra, the peak intensity of acryloyl group absorption appearing at 810 cm ^-1 was measured. From the peak intensity I ₀ for the coating film and the peak intensity I ₁ for the cured product, the formula {1- (I ₀ −I ₁ ) / I ₀ } × 100 (%) is used before and after irradiation with ultraviolet rays. The reduction rate of the reactive functional group ((meth) acryloyl group) in the composition in the above was calculated. The result was taken as the reaction rate.

(5) Shrinkage rate difference To JIS K6941 under the conditions of composition thickness 10 μm, UV irradiator (manufactured by CCS, model number CKL-200), peak wavelength 395 nm, irradiation intensity 7 W / cm ² and integrated light intensity 2.1 J / cm ² . The curing shrinkage rate of the ultraviolet curable resin based on the above was measured, and the curing shrinkage rate of the composition was calculated.

The curing shrinkage of the composition was calculated in the same manner except that the irradiation conditions of ultraviolet rays were changed to an irradiation intensity of 3 W / cm ² and an integrated light intensity of 0.9 J / cm ² .

The absolute value of the difference between the two curing shrinkage rates obtained above was calculated.

(6) Streak unevenness The composition was applied onto a quartz glass piece (dimensions 50 mm × 25 mm × 1 mm) having a silicon oxynitride film (SiON film) formed on the surface by a plasma CVD method to prepare a coating film having a thickness of 10 μm. .. This coating film is cured by irradiating this coating film with ultraviolet rays using a model number Unijet E075IIHD (peak wavelength 395 nm) manufactured by Ushio, Inc. under an atmospheric atmosphere under the conditions of an irradiation intensity of 5 W / cm ² and an integrated light intensity of 3000 mJ / cm ² . , A cured film was obtained.

By visually observing the surface of the cured film, "A" is when the cured film has no streaky irregularities, and "B" is when less than 10% of the surface of the cured film has streaky irregularities. The case where streaky unevenness was observed in the region of 10% or more of the surface of the cured film was evaluated as "C".

Claims (15)

An ultraviolet curable resin composition containing a photopolymerizable compound (A) and a photopolymerization initiator (B).
A coating film having a thickness of 10 μm is prepared from the ultraviolet curable resin composition, and ultraviolet rays having a peak wavelength of 385 nm to 405 nm are applied to the coating film with an irradiation intensity of 7 W / cm ² and an integrated light intensity. The absolute value of the difference between the curing shrinkage rate when irradiated under the condition of 2.1 J / cm ² and the curing shrinkage rate when irradiated under the condition of irradiation intensity 3 W / cm ² and integrated light intensity 0.9 J / cm ² is 2, less than 2 percentage points,
UV curable resin composition. A coating film having a thickness of 10 μm is prepared from the ultraviolet curable resin composition, and the coating film is irradiated with ultraviolet rays having a peak wavelength of 395 nm under the conditions of an irradiation intensity of 3 W / cm ² and an integrated light amount of 0.9 J / cm ² . The reaction rate of the photopolymerizable compound (A) is 80% or more.
The ultraviolet curable resin composition according to claim 1. The photopolymerizable compound (A) contains a radically polymerizable compound (A1).
The ultraviolet curable resin composition according to claim 1 or 2. The radically polymerizable compound (A1) contains an acrylic compound (Y).
The ultraviolet curable resin composition according to claim 3. The photopolymerization initiator (B) contains a photopolymerization initiator (B3) having photobleaching properties, and the ratio of the photopolymerization initiator (B3) to the photopolymerization initiator (B) is 50% by mass. That's it,
The ultraviolet curable resin composition according to any one of claims 1 to 4. The photopolymerization initiator (B) contains a photopolymerization initiator (B4) having an absorption coefficient of light having a wavelength of 405 nm of 5 ml / g · cm or more, and the photopolymerization initiation with respect to the photopolymerization initiator (B). The percentage of the agent (B4) is 50% by mass or more.
The ultraviolet curable resin composition according to any one of claims 1 to 5. The sensitizer (C) is further contained, and the percentage of the sensitizer (C) to the ultraviolet curable resin composition is 0.05% by mass or more.
The ultraviolet curable resin composition according to any one of claims 1 to 6. The leveling agent (D) is further contained, and the percentage of the leveling agent (D) to the ultraviolet curable resin composition is 0.1% by mass or more.
The ultraviolet curable resin composition according to any one of claims 1 to 7. For making optical components that transmit the light emitted by a light source,
The ultraviolet curable resin composition according to any one of claims 1 to 8. Molded by inkjet method,
The ultraviolet curable resin composition according to any one of claims 1 to 9. At least one of the viscosity at 25 ° C. and the viscosity at 40 ° C. is 30 mPa · s or less.
The ultraviolet curable resin composition according to any one of claims 1 to 10. A cured product of the ultraviolet curable resin composition according to any one of claims 1 to 11.
Optical parts. An optical component comprising molding the ultraviolet curable resin composition according to any one of claims 1 to 11 by an ultraviolet method and then irradiating the ultraviolet curable resin composition with ultraviolet rays to cure the composition. Production method. The optical component comprises a light source and an optical component that transmits light emitted by the light source, and the optical component includes a cured product of the ultraviolet curable resin composition according to any one of claims 1 to 11.
Light emitting device. It is a method of manufacturing a light emitting device including a light source and an optical component that transmits light emitted by the light source.
The optical component is manufactured by the method according to claim 13.
Manufacturing method of light emitting device.

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