Inorganic particles contain constituents

Abstract

The present invention provides a composition that reduces haze while maintaining a high refractive index. [Solution] The composition comprises a compound (A) represented by formula (1) and inorganic particles (B). TIFF2026054174000030.tif40136 [In formula (1), R 1 X represents an organic group containing an aromatic hydrocarbon ring with 10 or more carbon atoms in its structure, an organic group containing an aromatic heterocycle, an organic group containing a structure in which two or more benzene rings are bonded via single bonds, -O-, -S-, -CH2-, -C(CH3)2-, -SO-, or -SO2-, an organic group containing a structure in which three benzene rings are bonded via carbon atoms, or an organic group represented by formula (2). X represents -O-, -S-, or -NH-. Y represents *-CR 2 R 3 -**, *-O-**, *-S-**, *-NH-** or *-(ZA) n -** represents an integer between 1 and 3.

Description

Technical Field

[0001] The present invention relates to an inorganic particle-containing composition and a cured product of the composition.

Background Art

[0002] Compositions containing various inorganic particles can contribute to the improvement of the functionality and performance of various materials, such as optical materials, electronic component materials, magnetic recording materials, catalyst materials, ultraviolet absorption materials, dental materials, etc., according to the functions of the inorganic particles. Particularly in optical materials, high-refractive-index compositions are required for applications such as optical lenses, adhesives for optical films, adhesives for optical films, resin compositions for inkjet, resin compositions for nanoimprint, microlens arrays, antireflection layers used for transparent electrodes, antireflection films and antireflection agents, surface coats of optical lenses, organic EL light extraction layers, various hard coat materials, planarization films for thin film transistors (TFTs), overcoats for color filters, various protective films such as antireflection films, and optical filters, insulating films for touch sensors, insulating films for TFTs, photospacers for color filters, protective films for touch panels, etc.

[0003] For example, Patent Document 1 discloses a composition obtained by dispersing zirconium oxide particles in phenylbenzyl (meth) acrylate, and describes that a composition having a high refractive index can be obtained.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Incidentally, when applying inorganic particle-containing compositions to optical applications, not only is a high refractive index required, but also low haze. However, Patent Document 1 does not address the achievement of both high refractive index and low haze. Therefore, the present invention aims to provide a composition in which haze is reduced while maintaining a high refractive index. [Means for solving the problem]

[0006] As a result of diligent research to solve the aforementioned problems, the present inventors have discovered that by using inorganic particles along with a compound having a specific structure, it is possible to provide a composition in which haze is reduced while maintaining a high refractive index, thus completing the present invention.

[0007] In other words, the invention according to the present invention is as follows: [1] A composition comprising a compound (A) represented by the following general formula (1) and inorganic particles (B). [ka] [In formula (1), R 1 This refers to an organic group containing an aromatic hydrocarbon ring with 10 or more carbon atoms in its structure, an organic group containing an aromatic heterocycle, an organic group containing a structure in which two or more benzene rings are bonded via single bonds, -O-, -S-, -CH2-, -C(CH3)2-, -SO-, or -SO2-, an organic group containing a structure in which three benzene rings are bonded via carbon atoms, or an organic group represented by the following general formula (2). X represents -O-, -S-, or -NH-, whether identical or different. Y is the same or different, *-CR 2 R 3 -**, *-O-**, *-S-**, *-NH-** or *-(ZA) n -** represents (* is R 1 This shows the connection with X, and ** indicates the connection with X. R 2 and R 3represents, identically or differently, a hydrogen atom or a methyl group. Z represents -O-, -S- or -NH-. A represents an alkylene group. n represents an integer of 1 to 20. m represents an integer of 1 to 3. [Chemical formula] [In formula (2), R 21 represents a single bond or an alkylene group. R 22 represents, identically or differently, a halogen atom. a represents an integer of 1 to 3. * indicates a bond with Y. [2] The composition according to [1], wherein the refractive index of the compound (A) at 25°C is 1.55 or more. [3] The composition according to [1] or [2], wherein the inorganic particles (B) contain at least one metal element selected from the group consisting of titanium, aluminum, silicon, zirconium, indium, zinc, tin, lanthanum, yttrium, cerium, magnesium, barium, calcium, niobium, and tantalum. [4] The composition according to any one of [1] to [3], wherein the inorganic particles (B) are inorganic particles coated with a coating agent. [5] The composition according to [4], wherein the coating agent contains at least one selected from the group consisting of carboxylic acid compounds, phosphate esters, and silane coupling agents. [6] The composition according to any one of [1] to [5], wherein the content of the inorganic particles (B) is 60% by mass or more in 100% by mass of the solid content of the composition. [7] The composition according to any one of [1] to [6], wherein the average primary particle diameter of the inorganic particles (B) is 50 nm or less. [8] A cured product of the composition according to any one of [1] to [7]. [Advantages of the Invention]

[0008] According to the present invention, it is possible to provide a composition with a reduced haze while maintaining a high refractive index. [Modes for carrying out the invention]

[0009] 1. Compound (A) The composition of the present invention comprises compound (A) represented by the above general formula (1).

[0010] In the above general formula (1), R 1 This represents one of the following organic groups 1) to 5). 1) An organic group containing an aromatic hydrocarbon ring with 10 or more carbon atoms in its structure. 2) Organic groups containing aromatic heterocycles. 3) Organic groups containing a structure in which two or more benzene rings are bonded via single bonds, -O-, -S-, -CH2-, -C(CH3)2-, -SO-, or -SO2-. 4) An organic group containing a structure in which three benzene rings are bonded via carbon atoms. 5) An organic group represented by the following general formula (2). [ka] [In formula (2), R 21 R represents a single bond or an alkylene group. 22 represents a halogen atom, either identical or different. 'a' represents an integer from 1 to 3. '*' indicates a bond with Y.

[0011] The organic group described in 1) above contains an aromatic hydrocarbon ring having 10 or more carbon atoms in its structure. In this specification, an aromatic hydrocarbon ring means an aromatic hydrocarbon ring such as a benzene ring, a fused ring of a benzene ring, a fused ring of a benzene ring and an aliphatic hydrocarbon ring that exhibits aromaticity, or a fused ring of an aliphatic hydrocarbon ring that exhibits aromaticity.

[0012] Examples of the aliphatic hydrocarbon rings mentioned above include cycloalkane rings such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane rings; cycloalkene rings such as cyclopentene, cyclohexene, cyclopentadiene, and cycloheptatriene rings; polycyclic rings consisting only of saturated alicyclic hydrocarbon rings such as norbornane and adamantane rings; and polycyclic rings including unsaturated alicyclic hydrocarbon rings such as norbornene rings.

[0013] The number of carbon atoms in the aromatic hydrocarbon ring having 10 or more carbon atoms is preferably 10 to 40, and more preferably 10 to 30.

[0014] The number of atoms constituting the above-mentioned aromatic hydrocarbon ring having 10 or more carbon atoms is preferably 10 or more, more preferably 10 to 60, and even more preferably 10 to 50.

[0015] Examples of aromatic hydrocarbon rings having 10 or more carbon atoms include naphthalene rings, anthracene rings, phenanthrene rings, triphenylene rings, pyrene rings, perylene rings, fluorene rings, fluorantene rings, and azulene rings, with naphthalene rings and fluorene rings being preferred.

[0016] The above-mentioned aromatic hydrocarbon ring having 10 or more carbon atoms may have substituents. Examples of such substituents include hydrocarbon groups (e.g., alkyl groups), hydroxyl groups, alkoxy groups, carboxyl groups, substituents containing nitrogen atoms (e.g., amino groups, imino groups, nitro groups, nitroso groups), substituents containing halogen atoms (e.g., halogeno groups such as fluorine, chlorine, bromine, and iodine atoms), and substituents containing sulfur atoms (e.g., thiol groups, alkylthio groups, sulfone groups). Among these, substituents containing alkyl groups and halogen atoms are preferred, and alkyl groups (especially alkyl groups having 1 to 4 carbon atoms) and halogeno groups are more preferred.

[0017] The number of substituents on the above-mentioned aromatic hydrocarbon ring having 10 or more carbon atoms is not particularly limited, but is preferably 0 to 10, more preferably 0 to 8, and even more preferably 0 to 5.

[0018] The organic group in 1) above preferably contains 1 to 3 aromatic hydrocarbon rings having 10 or more carbon atoms, more preferably 1 to 2, and even more preferably 1. When it contains 2 or more aromatic hydrocarbon rings having 10 or more carbon atoms, they are preferably bonded via single bonds, divalent hydrocarbon groups, -S-, -SO-, or -SO2-, and preferably via single bonds, i.e., directly bonded. The divalent hydrocarbon group is the same as the divalent hydrocarbon group described later, including preferred embodiments.

[0019] Examples of the organic group in 1) above include a group consisting only of an aromatic hydrocarbon ring having 10 or more carbon atoms, which may have substituents, or a group consisting of an aromatic hydrocarbon ring having 10 or more carbon atoms, which may have substituents, and at least one selected from the group consisting of a divalent hydrocarbon group, -S-, -SO-, and -SO2- (hereinafter sometimes referred to as linker (1)). Among these, a group consisting only of an aromatic hydrocarbon ring having 10 or more carbon atoms, which may have substituents, is preferred. The above-mentioned divalent hydrocarbon group preferably includes a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by combining a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group. The above-mentioned divalent aliphatic hydrocarbon group preferably includes an alkylene group, and more preferably an alkylene group having 1 to 10 carbon atoms. The above-mentioned divalent aromatic hydrocarbon group preferably includes a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a phenylene group which may have an alkyl group, and even more preferably a phenylene group.

[0020] R 1 However, if the group consists only of an aromatic hydrocarbon ring having 10 or more carbon atoms, which may have substituents, it is preferable that Y is bonded to the aromatic hydrocarbon ring. R 1However, if the group consists of an aromatic hydrocarbon ring having 10 or more carbon atoms, which may have substituents, and a linker (1), it is preferable that the aromatic hydrocarbon ring and Y are bonded via the linker (1).

[0021] The organic group in 1) above is particularly preferably an organic group represented by the general formula (3) described later.

[0022] The organic group described in 2) above includes an aromatic heterocycle. Examples of aromatic heterocycles include those that contain one or more atoms selected from nitrogen, oxygen, and sulfur atoms in their ring structure and possess aromaticity.

[0023] The number of atoms constituting the above aromatic heterocycle is preferably 5 or more, more preferably 5 to 50, and even more preferably 5 to 40.

[0024] Examples of the above aromatic heterocycles include thiophene rings, furan rings, pyrrole rings, thiopyran rings, thiazole rings, imidazole rings, pyrazole rings, triazole rings, tetrazole rings, thiazole rings, thiadiazole rings, oxadiazole rings, oxazole rings, pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, triazine rings, isoindole rings, indole rings, indazole rings, purine rings, isoquinoline rings, quinoline rings, carbazole rings, acridine rings, benzofuran rings, dibenzofuran rings, naphthofuran rings, dinaphthofuran rings, benzothiophene rings, dibenzothiophene rings, naphthothiophene rings, and dinaphthothiophene rings. In particular, from the viewpoint of being able to further increase the refractive index, the above aromatic heterocycles preferably contain a sulfur atom, and thiophene rings, thiazole rings, thiadiazole rings, benzothiophene rings, dibenzothiophene rings, naphthothiophene rings, and dinaphthothiophene rings are more preferred.

[0025] The above aromatic heterocycle may have substituents. Examples of substituents include alkyl groups, cycloalkyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, substituents containing nitrogen atoms (e.g., amino groups, imino groups, nitro groups, nitroso groups), substituents containing halogen atoms (e.g., halogeno groups such as fluorine, chlorine, bromine, and iodine atoms), and substituents containing sulfur atoms (e.g., thiol groups, alkylthio groups, sulfone groups). Among these, alkyl groups and substituents containing halogen atoms are preferred, and alkyl groups (especially alkyl groups having 1 to 4 carbon atoms) and halogeno groups are more preferred.

[0026] The number of substituents on the above aromatic heterocycle is not particularly limited, but is preferably 0 to 10, more preferably 0 to 8, and even more preferably 0 to 5.

[0027] Examples of organic groups containing the above-mentioned aromatic heterocycle include groups consisting solely of an aromatic heterocycle which may have the above-mentioned substituents, or groups consisting of an aromatic heterocycle which may have the above-mentioned substituents and a divalent hydrocarbon group. Examples of the divalent hydrocarbon group mentioned above include the groups described as divalent hydrocarbon groups that the organic group in 1) may have, preferably divalent aliphatic hydrocarbon groups, more preferably alkylene groups, and even more preferably alkylene groups having 1 to 10 carbon atoms.

[0028] R 1 However, if the group consists only of an aromatic heterocycle which may have substituents, it is preferable that Y is bonded to the aromatic heterocycle. R 1 However, if the group consists of an aromatic heterocycle which may have substituents and a divalent hydrocarbon group, it is preferable that the aromatic heterocycle and Y are bonded via the divalent hydrocarbon group.

[0029] The organic groups described in 3) above include structures in which two or more benzene rings are bonded via single bonds, -O-, -S-, -CH2-, -C(CH3)2-, -SO-, or -SO2- (hereinafter sometimes collectively referred to as linkers (3)).

[0030] The number of benzene rings in the organic group described in 3) above (in particular, the number of benzene rings bonded via the linker (3)) is preferably 2 to 5, more preferably 2 to 4, even more preferably 2 to 3, and most preferably 2.

[0031] The above-mentioned structure in which two or more benzene rings are bonded via a single bond means a structure in which two or more benzene rings are directly bonded, preferably a structure in which 2 to 5 benzene rings are directly bonded, more preferably a structure in which 2 to 4 benzene rings are directly bonded, even more preferably a biphenyl group or a terphenyl group, and particularly preferably a biphenyl group.

[0032] The linker (3) is preferably a single bond, -O-, -S-, -SO-, or -SO2-, and more preferably a single bond or -O-.

[0033] The benzene ring constituting the organic group in 3) above may have substituents. Examples of substituents include alkyl groups, cycloalkyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, substituents containing nitrogen atoms (e.g., amino groups, imino groups, nitro groups, nitroso groups), substituents containing halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and other halogen groups), and substituents containing sulfur atoms (e.g., thiol groups, alkylthio groups, sulfone groups). Among these, alkyl groups and substituents containing halogen atoms are preferred, and alkyl groups (especially alkyl groups having 1 to 4 carbon atoms) and halogen groups are more preferred.

[0034] Examples of the organic group in 3) above include an organic group consisting only of a structure in which two or more benzene rings, which may have substituents, are linked via a linker (3), or a group consisting of a structure in which two or more benzene rings, which may have substituents, are linked via a linker (3) and a divalent hydrocarbon group. Examples of the divalent hydrocarbon group mentioned above include the groups described as divalent hydrocarbon groups that the organic group in 1) may have, preferably divalent aliphatic hydrocarbon groups, more preferably alkylene groups, and even more preferably alkylene groups having 1 to 10 carbon atoms. The organic group in 3) above is preferably an organic group consisting only of a structure in which two or more benzene rings, which may have substituents, are linked via a linker (3), or a group consisting of a structure in which two or more benzene rings, which may have substituents, are linked via a linker (3) and an alkylene group (particularly an alkylene group having 1 to 10 carbon atoms).

[0035] R 1 However, if the organic group consists only of a structure in which two or more benzene rings, which may have substituents, are linked via a linker (3), it is preferable that Y is bonded to one of the benzene rings. R 1 However, if the group consists of a structure in which two or more benzene rings, which may have substituents, are linked via a linker (3), and a divalent hydrocarbon group, it is preferable that one of the benzene rings is linked to Y via the divalent hydrocarbon group.

[0036] The organic group in 3) above is particularly preferably an organic group represented by the general formula (4) described later.

[0037] The organic group described in 4) above includes a structure in which three benzene rings are bonded via carbon atoms, and specifically includes a triphenylmethyl group.

[0038] The benzene ring constituting the organic group in 4) above may have substituents. Examples of substituents include alkyl groups, cycloalkyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, substituents containing nitrogen atoms (e.g., amino groups, imino groups, nitro groups, nitroso groups), substituents containing halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and other halogen groups), and substituents containing sulfur atoms (e.g., thiol groups, alkylthio groups, sulfone groups). Among these, alkyl groups and substituents containing halogen atoms are preferred, and alkyl groups (especially alkyl groups having 1 to 4 carbon atoms) and halogen groups are more preferred.

[0039] Examples of the organic group in 4) above include an organic group consisting only of a structure in which three benzene rings, which may have substituents, are bonded via carbon atoms (hereinafter referred to as a triphenylmethyl group, which may have substituents), or a group consisting of a triphenylmethyl group, which may have substituents, and a divalent hydrocarbon group. Examples of the divalent hydrocarbon group mentioned above include the groups described as divalent hydrocarbon groups that the organic group in 1) may have, preferably divalent aliphatic hydrocarbon groups, more preferably alkylene groups, and even more preferably alkylene groups having 1 to 10 carbon atoms.

[0040] R 1 However, if the organic group consists only of a triphenylmethyl group which may have substituents, it is preferable that Y is bonded to the carbon atoms to which the three benzene rings are bonded. R 1 However, if the group consists of a triphenylmethyl group which may have substituents and a divalent hydrocarbon group, it is preferable that Y is bonded to either benzene ring via the divalent hydrocarbon group.

[0041] The organic group in 5) above is represented by the general formula (2) above. In the above general formula (2), R 21 This represents a single bond or an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 10, and more preferably 1 to 5.

[0042] In the above general formula (2), R 22 This represents a halogen atom, such as a fluorine atom, chlorine atom, bromine atom, or iodine atom, which may be the same or different. From the viewpoint of being able to further increase the refractive index, the halogen atom is preferably an iodine atom.

[0043] In the general formula (2) above, a represents an integer between 1 and 3. It is preferable that a be an integer greater than or equal to 2, and more preferably 3.

[0044] The molecular weight of the organic groups described in 1) to 5) above is preferably 120 or more, more preferably 120 to 800, even more preferably 120 to 500, and particularly preferably 120 to 200. The molecular weight of the organic group refers to the total atomic weight of the atoms constituting the organic group.

[0045] In the above general formula (1), R 1 If you have multiple R 1 They may be the same or different, but it is preferable that they be the same.

[0046] R 1 Preferably, it is the organic group described in 1) above or the organic group described in 3) above.

[0047] In the above general formula (1), X represents -O-, -S-, or -NH-, either identical or different. In the above general formula (1), if there are multiple X values, the multiple X values ​​may be the same or different, but it is preferable that they be the same. In particular, X is preferably -O- or -S-, and more preferably -O-.

[0048] In the above general formula (1), Y is the same or different, *-CR 2 R 3 -**, *-O-**, *-S-**, *-NH-**, or *-(ZA) n-** represents. Compound (A) has a linker moiety represented by Y, which can lower the viscosity of the monomer.

[0049] R 2 and R 3 These represent, either the same or different, a hydrogen atom or a methyl group, with a hydrogen atom being preferred.

[0050] Z represents -O-, -S-, or -NH-, with -O- or -S- being preferred, and -O- being more preferred.

[0051] A represents an alkylene group, which may be linear or branched, but is preferably linear. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 4, even more preferably 2 to 3, and particularly preferably 2.

[0052] n represents an integer between 1 and 20, preferably between 1 and 15, more preferably between 1 and 10, and even more preferably 1. When n represents an integer of 2 or more, the multiple -ZA- may be the same or different, but it is preferable that they be the same.

[0053] In the above general formula (1), if there are multiple Y values, the multiple Y values ​​may be the same or different, but it is preferable that they be the same.

[0054] In particular, Y is *-CR 2 R 3 -**, or *-(ZA) n -** is preferred, and *-CH2-**, or *-(OA) n -** is more preferable, *-CH2-**, or *-(OCH2CH2) n -** is even more preferable.

[0055] In the above general formula (1), m represents an integer from 1 to 3, and is preferably 1.

[0056] Compound (A) is more preferably a compound represented by the following general formula (1A).

[0057] [ka] [In formula (1A), R 1A This represents an organic group represented by general formula (3) or an organic group represented by general formula (4). Y A is, *-CR 2A R 3A -** to*-(OA 1A ) p -** represents (* is R 1A (This shows a bond with the oxygen atom, and ** indicates a bond with the oxygen atom.) R 2A and R 3A These represent a hydrogen atom or a methyl group, either identical or distinct. A 1A This represents an alkylene group with 2 to 4 carbon atoms. p represents an integer between 1 and 10. [ka] [In general formula (3), R 4A This represents a single bond, an alkylene group with 1 to 10 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 12 carbon atoms. 1A This represents an aromatic hydrocarbon ring having 10 or more carbon atoms, which may have substituents. [ka] [In general formula (4), R 5A R represents a single bond or an alkylene group having 1 to 10 carbon atoms. 6A R represents a single bond, -O-, -S-, -CH2-, -C(CH3)2-, -SO-, or -SO2-. 7A and R 8Aq1 represents an alkyl group, cycloalkyl group, hydroxyl group, alkoxy group, carboxyl group, amino group, imino group, nitro group, nitroso group, halogeno group, thiol group, alkylthio group, or sulfone group, either identical or distinct. q1 represents an integer from 0 to 4, and q2 represents an integer from 0 to 5.

[0058] R in equation (3) 4A The alkylene group having 1 to 10 carbon atoms, represented by , may be linear or branched. R in equation (3) 4A Examples of divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms represented by include phenylene groups which may have alkyl groups (particularly alkyl groups having 1 to 4 carbon atoms), and among these, phenylene groups are preferred. R in equation (3) 4A It is preferably a single bond, an alkylene group having 1 to 5 carbon atoms, or a phenylene group which may have an alkyl group having 1 to 4 carbon atoms, with a single bond being more preferred. T in equation (3) 1A Examples of aromatic hydrocarbon rings having 10 or more carbon atoms that may have substituents represented by the above include the structure described as an aromatic hydrocarbon ring having 10 or more carbon atoms that may have substituents on the organic group of 1) above, and the preferred embodiment is the same.

[0059] R in equation (4) 5A The alkylene group having 1 to 10 carbon atoms, represented by , may be in a linear or branched chain configuration. R in equation (4) 5A It is preferably a single bond or an alkylene group having 1 to 5 carbon atoms, with a single bond being more preferable. R in equation (4) 6A The bond is preferably a single bond, -O-, -S-, -SO-, or -SO2-, and more preferably a single bond or -O-. R in equation (4) 7A and R 8A Each of these is independently preferably an alkyl group or a halogen group, and more preferably an alkyl group or halogen group having 1 to 4 carbon atoms. In equation (4), q1 is preferably an integer between 0 and 3, and more preferably 0. In equation (4), q2 is preferably an integer between 0 and 3, and more preferably 0.

[0060] R 2A and R 3A These represent, either the same or different, a hydrogen atom or a methyl group, with a hydrogen atom being preferred.

[0061] A 1A This represents an alkylene group having 2 to 4 carbon atoms, with an alkylene group having 2 to 3 carbon atoms being preferred, and an ethylene group being more preferred.

[0062] p represents an integer between 1 and 10, preferably between 1 and 5, and more preferably 1.

[0063] The refractive index of compound (A) at 25°C is preferably 1.54 or higher, more preferably 1.55 or higher, even more preferably 1.56 or higher, and even more preferably 1.57 or higher. The upper limit of this refractive index is not particularly limited, but it may be, for example, 1.7 or lower. The refractive index of compound (A) can be determined by the method described in the examples below.

[0064] The viscosity of compound (A) is preferably 5000 mPa·s or less, more preferably 2000 mPa·s or less, even more preferably 1000 mPa·s or less, even more preferably 500 mPa·s or less, and particularly preferably 100 mPa·s or less. The lower limit of the viscosity is not particularly limited, but may be 5 mPa·s or more. The viscosity is a value obtained by measuring it using a cone-plate viscometer at 25°C, and can be specifically determined by the method described in the examples below.

[0065] Specific examples of the above compound (A) include the compounds shown below.

[0066] R 1 As an example, compound (A) having the organic group described in 1) above: [ka] [ka]

[0067] R 1 As an example, compound (A) having the organic group described in 2) above: [ka]

[0068] R 1 As an example, compound (A) having the organic group described in 3) above: [ka] [ka]

[0069] R 1 As an example, compound (A) having the organic group described in 4) above: [ka]

[0070] R 1 As an example, compound (A) having the organic group described in 5) above: [ka]

[0071] The method for producing the above compound (A) is not particularly limited. For example, the compound in formula (1) where X is -O- can be produced via an α-halomethylacrylate alkyl ester, a 2,2'-[oxybis(methylene)]bisacrylate alkyl ester, or a transesterification reaction between an α-allyloxymethylacrylate ester and the corresponding alcohol. Furthermore, compounds in formula (1) where X is -S- can be produced, for example, by reacting α-allyloxymethylacrylic acid with the corresponding thiol. Furthermore, compounds in formula (1) where X is -NH- can be produced, for example, by condensing α-allyloxymethylacrylic acid with the corresponding amine.

[0072] 2. Inorganic particles (B) The composition of the present invention contains inorganic particles (B). By including inorganic particles (B), it becomes easier to control various physical properties of the composition of the present invention, such as refractive index, relative permittivity, and hardness.

[0073] The inorganic particles (B) are preferably at least one selected from the group consisting of metal particles, metal oxide particles, and metal hydroxides, and more preferably metal oxide particles. Examples of metals that constitute the inorganic particles (B) include Ti, Al, Si, Zr, In, Zn, Sn, La, Y, Ce, Mg, Ba, Ca, Nb, Ta, etc.

[0074] Examples of the aforementioned metal oxides include single metal oxides composed of one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, indium oxide, zinc oxide, tin oxide, lanthanum oxide, yttrium oxide, cerium oxide, magnesium oxide, niobium oxide, and tantalum oxide; and oxides composed of two or more metal elements such as indium tin oxide, tin antimony oxide, barium titanate, strontium titanate, titanite, and spinel. Examples of the aforementioned metal hydroxides include aluminum hydroxide and magnesium hydroxide. The inorganic particles (B) may be composed of one of these materials or of two or more materials.

[0075] The inorganic particles (B) are preferably metal oxides, more preferably single metal oxides, and even more preferably at least one selected from aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, and zinc oxide. Among these, zirconium dioxide particles (ZrO2 particles) and / or silicon dioxide particles (SiO2 particles) are preferred in that they can provide compositions with high refractive index and high dielectric constant or high hardness.

[0076] From the viewpoint of further increasing the refractive index of the resulting composition, the refractive index of the inorganic particles (B) is, for example, 1.60 to 2.72, preferably 1.65 to 2.50, and more preferably 1.70 to 2.20.

[0077] The crystalline structure of the inorganic particles (B) can be determined by X-ray diffraction, and is preferably cubic, tetragonal, monoclinic, etc., and multiple crystalline structures may be present. However, it is difficult to distinguish between cubic and tetragonal inorganic particles in X-ray diffraction measurements, and even if cubic particles are present, their proportion is counted as the proportion of tetragonal particles. From the viewpoint of further increasing the refractive index, it is preferable that 50% or more of the total crystalline structure be tetragonal and / or cubic. In addition, the ratio of the total tetragonal and cubic crystals to monoclinic crystals ((tetragonal + cubic) / monoclinic) is preferably 1.0 to 30, more preferably 1.1 to 20.

[0078] The crystallite size of the inorganic particles (B) is preferably 20 nm or less, more preferably 15 nm or less, and even more preferably 10 nm or less, and is usually 1 nm or more. The smaller the crystallite size, the higher the light transmittance of the composition can be. The crystallite size can be determined by X-ray diffraction.

[0079] The inorganic particles (B) may be inorganic particles coated with a coating agent. Using inorganic particles coated with a coating agent improves their dispersibility in the composition containing compound (A).

[0080] The amount of coating agent is preferably 0.5 to 25% by mass, more preferably 3 to 25% by mass, even more preferably 5 to 20% by mass, and even more preferably 10 to 20% by mass, based on 100% by mass of inorganic particles coated with the coating agent.

[0081] Examples of the coating agent include carboxylic acid compounds, phosphate esters, silane coupling agents, surfactants, titanium coupling agents, aluminate-based coupling agents, and the like.

[0082] The carboxylic acid compound is a compound having a carboxyl group (-COOH group). Specifically, the carboxylic acid compound is: Linear saturated aliphatic monocarboxylic acids such as propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, palmitic acid, and stearic acid, as well as isovaleric acid, 3,3-dimethylbutyric acid, 3,3-diethylbutyric acid, 3-methylvaleric acid, isononanoic acid, 4-methylvaleric acid, 4-methyloctanoic acid, isobutyric acid, 2-methylbutyric acid, 2-ethylbutyric acid, 2-ethylhexanoic acid, 2-methylvaleric acid, and 2-methylhexane Saturated aliphatic carboxylic acids, including branched-chain saturated aliphatic monocarboxylic acids such as acids, 2-methylheptanoic acid, 2-propylbutyric acid, 2-hexylvaleric acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-methylhexadecanoic acid, pivalic acid, 2,2-dimethylbutyric acid, 2,2-dimethylvaleric acid, 2,2-diethylbutyric acid, 2,2-dimethylhexanoic acid, and neodecanoic acid, as well as saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid; Alicyclic hydrocarbon group-containing carboxylic acids, including monocarboxylic acids containing alicyclic hydrocarbon groups such as naphthenic acid, and dicarboxylic acids containing alicyclic hydrocarbon groups such as cyclohexanedicarboxylic acid; Unsaturated carboxylic acids including unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, oleic acid, linoleic acid, linolenic acid, cinnamic acid, and 2-hexenoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and unsaturated carboxylic acids containing (meth)acryloyl groups such as 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, and 2-(meth)acryloyloxyethyl phthalic acid; Ether-containing carboxylic acids such as methoxyacetic acid, ethoxyacetic acid, 3-ethoxypropionic acid, 2-methoxyethoxyacetic acid, and 2-methoxyethoxyethoxyacetic acid; Hydroxy group-containing carboxylic acids, including lactic acid, hydroxystearic acid, glycolic acid, DL-lactic acid, 2-hydroxyisobutyric acid, dimethylolpropionic acid, hydroxypivalic acid, 3-hydroxypropionic acid, DL-2-hydroxybutyric acid, DL-3-hydroxybutyric acid, 2-hydroxy-2-methylbutyric acid, β-hydroxyisovaleric acid, 2,2-bis(hydroxymethyl)butyric acid, 4-hydroxycyclohexanecarboxylic acid, (o-,m-,p-)hydroxybenzoic acid, and hydroxy group-containing polycarboxylic acids such as malic acid and citric acid; Carbonyl group-containing carboxylic acids such as pyruvate, levulinic acid, 2-oxovaleric acid, β-methyllevulinic acid, and α-methyllevulinic acid; Aromatic carboxylic acids, including aromatic monocarboxylic acids such as benzoic acid, and aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, and trimellitic acid; Sulfide bond-containing carboxylic acids such as phenylthioacetic acid; Amino group-containing carboxylic acids, including amino group-containing monocarboxylic acids such as glycine, alanine, 2-methylalanine, cysteine, serine, threonine, valine, leucine, isoleucine, methionine, and lysine, and amino group-containing dicarboxylic acids such as aspartic acid and glutamic acid; Cyano group-containing carboxylic acids such as cyanoacetic acid; Examples include heterocyclic compounds substituted with carboxyl groups such as proline; and so on.

[0083] The carboxylic acid compound preferably contains at least a secondary carboxylic acid. Inorganic particles coated with a secondary carboxylic acid have good affinity for compound (A) and can exhibit better dispersibility even when the concentration of inorganic particles in the composition is high.

[0084] The term "secondary carboxylic acid" refers to a carboxylic acid in which the carbon bonded to the carboxyl group (-COOH group) is a secondary carbon. The secondary carboxylic acid is preferably a monocarboxylic acid, more preferably a saturated or unsaturated aliphatic monocarboxylic acid, and even more preferably a saturated aliphatic monocarboxylic acid.

[0085] The secondary carboxylic acid preferably has 4 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 7 to 16.

[0086] Examples of secondary carboxylic acids include isobutyric acid, 2-methylbutyric acid, 2-ethylbutyric acid, 2-ethylhexanoic acid, 2-methylvaleric acid, 2-methylhexanoic acid, 2-methylheptanoic acid, 2-propylbutyric acid, 2-hexylvaleric acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, and 2-methylhexadecanoic acid. 2-ethylhexanoic acid, 2-methylvaleric acid, 2-methylhexanoic acid, 2-methylheptanoic acid, 2-propylbutyric acid, 2-hexylvaleric acid, and 2-hexyldecanoic acid are preferred, 2-ethylhexanoic acid and 2-hexyldecanoic acid are more preferred, and 2-ethylhexanoic acid is even more preferred.

[0087] Furthermore, the carboxylic acid compound may preferably include an unsaturated carboxylic acid, and it is even more preferable to use a secondary carboxylic acid and an unsaturated carboxylic acid in combination.

[0088] Among the unsaturated carboxylic acids mentioned above, unsaturated monocarboxylic acids and carboxylic acids containing a (meth)acryloyl group are preferred, and α,β-unsaturated carboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and 2-hexenoic acid, and carboxylic acids containing a (meth)acryloyl group are more preferred.

[0089] Examples of the phosphate esters include (meth)acryloyl group-containing phosphate esters such as 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxypropyl acid phosphate, 3-(meth)acryloyloxypropyl acid phosphate, and 2-(meth)acryloyloxyethylphenyl acid phosphate; (poly)alkylene glycol monoalkyl ether phosphate esters such as triethylene glycol monomethyl ether phosphate and dipropylene glycol monomethyl ether phosphate; alkyl phosphate esters such as methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, n-octyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, and oleyl acid phosphate; and the like. In addition, commercially available phosphate esters can be used as appropriate, such as DISPERBYK-110, 111, 180 (manufactured by Bic Chemie Japan), Prysurf A125C, A212C, A208B, A208F, A208N, A219B, and AL (manufactured by Daiichi Kogyo Seiyaku). Among these, (meth)acryloyl group-containing phosphate esters and (poly)alkylene glycol monoalkyl ether phosphate esters are preferred as phosphate esters.

[0090] Examples of the aforementioned surfactants include ionic surfactants such as anionic surfactants, cationic surfactants, and amphoteric surfactants, as well as nonionic surfactants.

[0091] Examples of the anionic surfactants include fatty acid-based surfactants such as sodium oleate, sodium stearate, sodium laurate, potassium fatty acid, and sodium fatty acid ester sulfonate; phosphoric acid-based surfactants such as alkyl phosphate and alkyl phosphate ester salts such as sodium alkyl phosphate; olefin-based surfactants such as sodium alpha-olefin sulfonate; alcohol-based surfactants such as sodium alkyl sulfate; alkylbenzene-based surfactants; and the like.

[0092] Examples of the cationic surfactants mentioned above include alkylmethylammonium chloride, alkyldimethylammonium chloride, alkyltrimethylammonium chloride, and alkyldimethylbenzylammonium chloride.

[0093] Examples of the aforementioned amphoteric surfactants include carboxylic acid-based surfactants such as alkylaminocarboxylates and phosphate ester-based surfactants such as phosphobetaines.

[0094] Examples of the nonionic surfactants include fatty acid-based surfactants such as polyoxyethylene lanolin fatty acid esters and polyoxyethylene sorbitan fatty acid esters; polyoxyethylene alkylphenyl ethers; fatty acid alkanolamides; and phosphoric acid-based surfactants such as organic phosphate esters, alkyl phosphate esters, phosphate polyesters, and polyoxyalkylene alkyl ether phosphate esters.

[0095] In this specification, carboxylic acid compounds and phosphate esters that can be used as surfactants are treated as carboxylic acid compounds and phosphate esters, rather than as surfactants.

[0096] Examples of the silane coupling agent include (meth)acryloxy group-containing silane coupling agents such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, and 3-(meth)acryloxypropylmethyldiethoxysilane.

[0097] Examples of the titanium coupling agent include isopropyltriisostearoyl titanate, isopropyldimethacrylateisostearoyl titanate, isopropyltri(dodecyl)benzenesulfonyl titanate, neopentyl(diallyl)oxytri(dioctyl)phosphate titanate, and neopentyl(diallyl)oxytrineododecanoyl titanate.

[0098] Examples of the aluminate-based coupling agent include acetalkoxyaluminum diisopropylate.

[0099] These coating agents can be used individually or in combination of two or more.

[0100] The coating agent preferably contains at least one selected from the group consisting of carboxylic acid compounds, phosphate esters, and silane coupling agents, and more preferably contains at least one selected from the group consisting of secondary carboxylic acids, unsaturated carboxylic acids, phosphate esters, and silane coupling agents. In particular, the coating agent preferably contains at least a secondary carboxylic acid, and more preferably a secondary carboxylic acid in combination with at least one selected from the group consisting of an unsaturated carboxylic acid, a phosphate ester, and a silane coupling agent. A combination of a secondary carboxylic acid, an unsaturated carboxylic acid, and a phosphate ester, a combination of a secondary carboxylic acid and a phosphate ester, or a combination of a secondary carboxylic acid, a silane coupling agent, and an unsaturated carboxylic acid is even more preferred.

[0101] The total proportion of carboxylic acid compounds (particularly secondary carboxylic acids and unsaturated carboxylic acids), phosphate esters, and silane coupling agents in 100 mol% of the coating agent is preferably 30 mol% or more, more preferably 50 mol% or more, even more preferably 80 mol% or more, particularly preferably 90 mol% or more, and may also be 100 mol%.

[0102] The proportion of carboxylic acid compounds in 100 mol% of the coating agent (preferably the total proportion of secondary carboxylic acids and unsaturated carboxylic acids) is preferably 5 to 100 mol%, more preferably 10 to 90 mol%, and even more preferably 15 to 85 mol%.

[0103] The proportion of secondary carboxylic acid in 100 mol% of the coating agent is preferably 5 to 100 mol%, more preferably 10 to 40 mol%, and even more preferably 15 to 30 mol%. Furthermore, the total amount of unsaturated carboxylic acid, phosphate ester, and silane coupling agent relative to the amount of secondary carboxylic acid is preferably 0.5 to 10.0 in molar ratio, more preferably 1.5 to 6.0, and even more preferably 2.5 to 4.0.

[0104] The proportion of unsaturated carboxylic acid in 100 mol% of the coating agent is, for example, 0 to 90 mol%, preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 30 to 65 mol%. Furthermore, the amount of unsaturated carboxylic acid relative to the amount of secondary carboxylic acid is, for example, 0 to 4.0 in molar ratio, preferably 0.5 to 4.0, more preferably 1.0 to 3.5, and even more preferably 1.2 to 3.0.

[0105] The proportion of phosphate ester in 100 mol% of the coating agent is, for example, 0 to 95 mol%, preferably 10 to 90 mol%, and more preferably 20 to 85 mol%. Furthermore, the amount of phosphate ester relative to the amount of secondary carboxylic acid is, for example, 0 to 8.0 in molar ratio, preferably 0.5 to 6.0, and more preferably 1.0 to 4.0.

[0106] The proportion of the silane coupling agent in 100 mol% of the coating agent is, for example, 0 to 80 mol%, preferably 10 to 60 mol%, more preferably 20 to 50 mol%, and even more preferably 25 to 45 mol%. Furthermore, the amount of silane coupling agent relative to the amount of secondary carboxylic acid is, for example, 0 to 5.0 in molar ratio, preferably 0.5 to 3.0, and more preferably 0.8 to 1.5.

[0107] The average primary particle diameter of the inorganic particles (B) is preferably 1 to 50 nm, more preferably 5 to 30 nm, and even more preferably 5 to 20 nm. If the inorganic particles are coated with a coating agent, the average primary particle diameter of the coated inorganic particles is indicated. When the average primary particle diameter of the inorganic particles (B) is within the above range, the transparency of the composition is further enhanced. The average primary particle diameter can be determined by observing the inorganic particles (B) under magnification using an electron microscope such as a transmission electron microscope (TEM), field emission transmission electron microscope (FE-TEM), or field emission scanning electron microscope (FE-SEM), randomly selecting 100 particles, measuring their lengths along their long axes, and calculating their arithmetic mean.

[0108] 3. Composition The composition of the present invention comprises the above compound (A) and the above inorganic particles (B). This makes it possible to provide a composition with reduced haze while maintaining a high refractive index. Specifically, compound (A) can function as a dispersion medium for the inorganic particles (B). Compound (A) has a skeleton represented by the following formula (hereinafter referred to as the α-(allyloxymethyl)acryloyl skeleton), which improves the dispersibility of the inorganic particles (B), and R 1 This method provides a composition with reduced haze while maintaining a high refractive index due to its structure. [ka] Furthermore, since compound (A) has good compatibility with inorganic particles (B), it is possible to reduce the viscosity of the composition. Moreover, the composition of the present invention is preferable in that it has good curability and yields a cured product with good residual film properties and flexibility.

[0109] The content of compound (A) in 100% by mass of solid components in the composition is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass. In this specification, solid components refer to components excluding the solvent.

[0110] The content of inorganic particles (B) in 100% by mass of solid components in the composition is, for example, 30 to 97% by mass, preferably 60 to 95% by mass, more preferably 70 to 90% by mass, and even more preferably 80 to 90% by mass.

[0111] Furthermore, the content of inorganic particles (B) is preferably 1.2 to 15 parts by mass, more preferably 2 to 10 parts by mass, and even more preferably 4 to 8 parts by mass, per 1 part by mass of compound (A).

[0112] The total content of compound (A) and inorganic particles (B) in 100% by mass of solid components in the composition is preferably 60% by mass or more, more preferably 75% by mass or more, even more preferably 85% by mass or more, and even more preferably 90% by mass or more, and may be 95% by mass or more or 100% by mass.

[0113] Because the composition of the present invention contains the above-mentioned compound (A) and inorganic particles (B), it exhibits a high refractive index while also having good transparency. The refractive index of the composition of the present invention is preferably 1.680 or higher, more preferably 1.700 or higher, and even more preferably 1.710 or higher. There is no particular upper limit, but it may be, for example, 1.800 or lower. The total light transmittance of the composition of the present invention is preferably 90.5% or higher, and there is no particular upper limit, but it may be, for example, 98% or lower. The haze of the composition of the present invention is preferably 0.75 or less, and may also be 0.70 or less or 0.65 or less. The lower limit of the haze of the composition is not particularly limited, but may be, for example, 0.50 or more.

[0114] The composition of the present invention is also preferable in that it has low viscosity. The viscosity of the composition of the present invention at 40°C is preferably 15,000 mPa·s or less, more preferably 8,000 mPa·s or less, and even more preferably 5,000 mPa·s or less, and the lower limit is not particularly limited but may be 500 mPa·s or more.

[0115] The refractive index, total light transmittance, haze, and viscosity of the composition can be measured according to the methods described in the examples below.

[0116] Furthermore, the composition of the present invention may also contain polymerizable monomers other than compound (A) (hereinafter sometimes referred to as "other polymerizable monomers"), polymerization initiators, solvents, polymers (resins), or other additives.

[0117] 3-1. Other polymerizable monomers Other polymerizable monomers include monofunctional monomers having one polymerizable double bond or crosslinkable monomers having two or more polymerizable double bonds, and one or more of these can be used in combination.

[0118] As monofunctional monomers, Alkyl methacrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate; cycloalkyl methacrylates such as cyclohexyl (meth)acrylate; 2,4-dibromo-6-sec-butylphenyl (meth)acrylate, 2,4-dibromo-6-isopropylphenyl (meth)acrylate (meth)acrylate aryl esters such as acrylate, phenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, pentabromophenyl (meth)acrylate; (meth)acrylate aralkyl esters such as benzyl (meth)acrylate, pentabromobenzyl (meth)acrylate; phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, (Meth)acrylic acid esters having aryloxy units such as 2-bromophenoxyethyl (meth)acrylate, 1-naphthyloxyethyl (meth)acrylate, 2-naphthyloxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, and 3-phenoxy-2-hydroxypropyl (meth)acrylate; arylthioethyl (meth)acrylate such as phenylthioethyl (meth)acrylate, 1-naphthylthioethyl (meth)acrylate, and 2-naphthylthioethyl (meth)acrylate; (Meth)acrylic acid esters represented by: (meth)acrylic acid esters having an oxy group; alkylene glycol mono(meth)acrylates such as methoxypolyethylene glycol (meth)acrylate and phenoxypolyethylene glycol (meth)acrylate; (meth)acrylic acid esters having a glycidyl group such as glycidyl (meth)acrylate; (meth)acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; Styrene monomers such as styrene, 4-tert-butylstyrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-chlorostyrene, and p-chloromethylstyrene; Examples include carboxyl group-containing monomers such as (meth)acrylic acid; and so on.

[0119] Other examples of monofunctional monomers include compounds containing two or more monocyclic aromatic rings and having one polymerizable double bond in one molecule (hereinafter referred to as monofunctional monomers containing multiple aromatic rings). The monocyclic aromatic rings may be monocyclic aromatic hydrocarbon rings or monocyclic aromatic heterocyclic rings, but monocyclic aromatic hydrocarbon rings are preferred, and benzene rings are preferred. Note that "containing two or more monocyclic aromatic rings in one molecule" may include structures in which monocyclic aromatic rings are linked by linking groups (e.g., single bonds, alkylene groups, ether groups, etc.), or may include structures in which two or more monocyclic aromatic rings are fused together, such as naphthalene rings. In particular, compounds having a structure in which two monocyclic aromatic rings are linked by a single bond, a structure in which two monocyclic aromatic rings are linked by an ether group, or a structure containing a naphthalene ring are preferred.

[0120] Examples of monofunctional monomers containing multiple aromatic rings include biphenylmethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate, 1-naphthylmethyl (meth)acrylate, 9-fluorenylmethyl (meth)acrylate, ethoxylated phenylphenol (meth)acrylate, ethoxylated cumylphenol (meth)acrylate, 2-(1-naphthyloxy)ethyl (meth)acrylate, 2-(2-naphthyloxy)ethyl (meth)acrylate, naphthyloxypolyethylene glycol (meth)acrylate, and N-vinylcarbazole.

[0121] Examples of crosslinkable monomers include alkylene glycosides such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and tetramethylene glycol di(meth)acrylate. Examples include crosslinkable (meth)acrylic acid esters, such as poly(meth)acrylate; polyfunctional styrene monomers such as divinylbenzene; polyfunctional allyl ester monomers such as diallyl phthalate, diallyl isophthalate, triallyl cyanurate, and triallyl isocyanurate; 2-(2-vinyloxyethoxy)ethyl (meth)acrylate; urethane acrylate oligomers (for example, the Shiko® series (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), the CN series (manufactured by Sartomer Co., Ltd.), the Unidick® series (manufactured by DIC Corporation), the Kayarad® UX series (manufactured by Nippon Kayaku Co., Ltd.), etc.).

[0122] The content of other polymerizable monomers in 100% by mass of the solid components in the composition is preferably 30% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0123] 3-2. Polymerization Initiators As polymerization initiators, known radical polymerization initiators can be used, and it is particularly preferable to use photoradical polymerization initiators. Examples of photoradical polymerization initiators include alkylphenones such as acetophenone, 3-methylacetophenone, benzyldimethylketal, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-hydroxycyclohexylphenyl ketone; benzophenones including benzophenone, 4-chlorobenzophenone, and 4,4'-diaminobenzophenone; benzoin ethers such as benzoin propyl ether and benzoin ethyl ether; thioxanthones such as 4-isopropylthioxanthone; xanthones, fluorenone, camphorquinone, benzaldehyde, and anthraquinone. Polymerization initiators can be used individually or in combination of two or more.

[0124] The content of the polymerization initiator is not particularly limited, but is preferably 1 to 10 parts by mass, and more preferably 2 to 5 parts by mass, per 100 parts by mass of compound (A).

[0125] The total content of compound (A), inorganic particles (B), other polymerizable monomers, and polymerization initiators in 100% by mass of the solid components in the composition is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 97% by mass or more, and may be 100% by mass.

[0126] 3-3. Solvent Examples of solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 1-methoxy-2-propanol, and ethylene glycol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate and propyl acetate; ethers such as ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether; modified ethers such as propylene glycol monomethyl ether acetate (especially ether-modified and / or ester-modified alkylene glycols); hydrocarbons such as benzene, toluene, xylene, ethylbenzene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, and mineral spirits; halogenated hydrocarbons such as dichloromethane and chloroform; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; water; and oils such as mineral oil, vegetable oil, wax oil, and silicone oil. These can be used individually or in combination of two or more. From a handling standpoint, solvents with a boiling point of approximately 40°C or higher and 250°C or lower at atmospheric pressure (1013 hPa) are preferred.

[0127] 3-4. Polymers (resins) As polymers (resins), one or more types can be used, and examples include polyamides such as 6-nylon, 66-nylon, and 12-nylon; polyimides; polyurethanes; polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyvinyl chlorides; polyvinylidene chlorides; polyvinyl acetates; polystyrenes; (meth)acrylic resin polymers; ABS resins; fluororesins; phenol-formaldehyde resins; phenolic resins such as cresol-formaldehyde resins; epoxy resins; urea resins; melamine resins; amino resins such as guanamine resins; polyvinyl butyral resins; polyurethane resins; ethylene-vinyl acetate copolymer resins; ethylene-(meth)acrylic acid ester copolymer resins, and other soft and hard resins.

[0128] 3-5. Other additives Other additives include surfactants, curing agents, curing accelerators, colorants, internal release agents, coupling agents, reactive diluents, plasticizers, stabilizers, flame retardant aids, crosslinking agents, low shrinkage agents, polymerization inhibitors, antioxidants, UV absorbers, defoaming agents, leveling agents, thixotropes, and thickeners.

[0129] 4. Hardened material The present invention also includes cured products of the above-described compositions. Articles made from these cured products are suitably used in optical applications, ink applications, and the like. The compositions of the present invention have good curability, meaning they can be cured with low irradiation energy, and the resulting cured products also have excellent thermal stability. The shape of the cured product is not particularly limited, nor is its thickness, but examples include plate-like, sheet-like, film-like, and fibrous forms. In particular, the thickness of the cured product when it is plate-like, sheet-like, or film-like, and the diameter when it is fibrous, is preferably 0.01 μm to 5 mm, more preferably 0.1 μm to 500 μm, and more preferably 1 μm to 100 μm.

[0130] When the composition of the present invention is coated to a thickness of approximately 0.05 μm to 0.2 μm, the radiation level is 3500 mJ / cm². 2 The composition can be cured with the following ultraviolet irradiation dose. The ultraviolet irradiation dose is more preferably 2000 mJ / cm². 2 The following, and more preferably 1500 mJ / cm² 2 The lower limit is not particularly limited, but for example, 500 mJ / cm². 2 It is to that extent.

[0131] The refractive index of the cured product can be, for example, 1.760 or higher, more preferably 1.770 or higher, and even more preferably 1.780 or higher. There is no particular upper limit, but for example, 1.850. The aforementioned refractive index values ​​are preferably those for when the thickness or fiber diameter of the cured product is 10 μm to 1 mm (preferably 50 to 500 μm).

[0132] Because the composition of the present invention has excellent refractive index and transparency, it can be applied to various applications such as resist applications, optical applications, ink applications, coating applications, and adhesive applications. Specifically, it is suitably used in optical lenses, adhesives for optical films, adhesives for optical films, resin compositions for inkjet applications, resin compositions for nanoimprint applications, microlens arrays, anti-reflective layers used in transparent electrodes, anti-reflective films and anti-reflective agents, surface coatings for optical lenses, organic EL light extraction layers, various hard coating materials, planarization films for TFTs, overcoats for color filters, various protective films such as anti-reflective films, and optical materials such as optical filters, insulating films for touch sensors, insulating films for TFTs, photospacers for color filters, and protective films for touch panels. [Examples]

[0133] The present invention will be described in more detail below with reference to examples. The present invention is not limited by the following examples, and it is certainly possible to implement it with appropriate modifications within the scope that is consistent with the spirit described below, and all such modifications are included within the technical scope of the present invention.

[0134] The physical properties and characteristics disclosed in the examples and comparative examples were measured by the following methods.

[0135] (1) Analysis of the crystal structure The crystal structure of the particles was analyzed using an X-ray diffractometer (Rigaku Corporation, RINT-TTRIII). The measurement conditions were as follows: X-ray source: CuKα (0.154nm) X-ray output settings: 50kV, 300mA Sampling width: 0.0200° Scan speed: 10.0000° / min Measurement range: 10~75° Measurement temperature: 25℃

[0136] (2) Determination of the proportion of tetragonal and monoclinic crystals Based on values ​​calculated using an X-ray diffractometer (Rigaku Corporation, RINT-TTRIII), the values ​​were quantified using the reference intensity ratio method (RIP method) with calculation software (Rigaku Corporation, PDXL) (peak assignment was also done according to the specifications of the calculation software). In this measurement, it was difficult to distinguish between tetragonal and cubic crystals, so even if cubic crystals were present, their proportion was counted as the proportion of tetragonal crystals.

[0137] (3) Calculation of crystallite size by X-ray diffraction analysis The crystallite size of the particles was calculated using calculation software (PDXL, Rigaku Corporation) based on the full width at half maximum of the 30° peak, which was analyzed and calculated using an X-ray diffractometer (RINT-TTRIII, Rigaku Corporation).

[0138] (4) Measurement of average primary particle size using an electron microscope The average primary particle diameter was measured by observation using an ultra-high-resolution electrolytic emission scanning electron microscope (Hitachi High-Technologies Corporation, S-4800). Particles were observed at a magnification of 150,000x, and the length along the long axis of each particle was measured for any 100 particles. The average value of these measurements was defined as the average primary particle diameter.

[0139] (5) Measurement of organic content Using a TG-DTA (thermogravimetric-indicative thermal analysis) apparatus, particles were heated from room temperature to 800°C at a rate of 10°C / min in an air atmosphere, and the weight (mass) loss rate of the particles was measured. This weight (mass) loss rate was defined as the organic content of the particles.

[0140] (6) Measurement of the refractive index of compounds The refractive index of the compounds was measured using an ATAGO DR-M4 multi-wavelength Abbe refractometer (measurement temperature 25°C, interference filter wavelength 589 (D) nm).

[0141] (7) Viscosity measurement of compounds The viscosity of the compound was measured at a temperature of 25°C using a cone-plate viscometer (Brookfield, DV1MRVCJ0).

[0142] (8) Measurement of viscosity of the composition The viscosity of the composition was measured using a viscometer (TV-100EH viscometer, manufactured by Toki Sangyo Co., Ltd.). Set temperature: 40℃ Sample volume: 0.2 mL Preheat time: 5 minutes Measurement time: 5 minutes Cone rotor: 3° × R9.7

[0143] (9) Measurement of the refractive index of the composition The refractive index of the composition was measured using an ATAGO DR-M4 multi-wavelength Abbe refractometer (measurement temperature 20°C, interference filter wavelength 589(D)nm).

[0144] (10) Measurement of haze and total light transmittance The haze and total light transmittance of the composition were measured using a turbidimeter (NDH7000, manufactured by Nippon Denshoku Industries Co., Ltd.). For sample preparation, 100 μm thick spacers were placed at both ends of a large microscope slide (Matsunami Glass Industry Co., Ltd., part number: S9112), and 0.5 g of the composition to be measured was weighed and placed in the center. Another large microscope slide was then placed on top, ensuring no air bubbles were introduced, to serve as the sample.

[0145] (11) Evaluation of residual film properties A 0.1g sample of the composition to be measured was placed in the center of a large microscope slide (manufactured by Toshin Riko Co., Ltd., size: 5cm x 5cm). The film was then deposited using a spin coater (1000rpm, 10 seconds), and the residual film percentage (%) after deposition was calculated using the following formula. A residual film percentage of 98% or more was marked with ○, 95% or more but less than 98% was marked with △, and less than 95% was marked with ×. Residual film percentage (%) = 100 × {(Weight after film deposition) / (Weight before film deposition)}

[0146] (12) Evaluation of curability A curable composition was obtained by mixing 3.0 g of the composition obtained in the following examples or comparative examples with 0.036 g of a photoradical polymerization initiator (Omnirad184, manufactured by IGM Resins). The obtained curable composition was coated onto a large glass slide (manufactured by Matsunami Glass Industry Co., Ltd., product number: S9112) to a thickness of 0.1 μm using an applicator #01, and cured with a high-pressure mercury lamp at 700 mJ / cm². 2 The coating was irradiated with ultraviolet light. The number of irradiations was increased, and the point at which fingerprints no longer appeared on the coating film was considered to be cured, and the number of irradiations required for curing was confirmed.

[0147] (13) Evaluation of flexural resistance 10 g of the composition obtained in the following examples or comparative examples was mixed with 0.045 g of a photoradical polymerization initiator (Omnirad 184, IGM Resins) to obtain a curable composition. The obtained curable composition was diluted with propylene glycol monomethyl ether to a solid content of 75% by mass to obtain a coating solution. The coating solution was applied to a 100 μm easy-adhesion PET film (Cosmoshine A4360, Toyobo Co., Ltd.) using a bar coater #24, dried at 80°C for 5 minutes, and then UV cured in air (3000 mJ / cm²). 2 By doing so, an evaluation sample (thickness 40 μm) was obtained in which a cured layer was laminated on a PET film. The flexibility of the cured layer was confirmed by mandrel testing in accordance with JIS K5600-5-1 (Paints - General test methods - Part 5: Mechanical properties of coatings). Specifically, the laminate was wrapped around a mandrel so that the cured layer was on the mandrel side, and the condition of the cured layer was observed visually. The evaluation was carried out while decreasing the diameter of the mandrel as follows, and the minimum diameter of the mandrel in which no cracks occurred in the cured layer was determined. The smaller the minimum diameter, the better the flexibility. Mandrel diameters: 32mm, 25mm, 16mm, 12mm, 10mm, 8mm, 6mm, 5mm, 4mm, 3mm, 2mm.

[0148] [Production Example 1-1: Synthesis of 2-(allyloxymethyl)acrylate-1-naphthylmethyl] A stirrer bar, 75.00 g of 1-naphthalene methanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 106.58 g of α-allyloxymethyl methyl acrylate (AOMA), 107 mg of polymerization inhibitor (6-t-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industry Co., Ltd.), 107 mg of polymerization inhibitor (Polystop 7300P, manufactured by Hakuto Co., Ltd.), and 37.7 g of heptane were weighed into a 300 mL separable flask. 5.7 g of heptane was placed in a holder, and the system was heated and stirred at 90-100°C for 1 hour under reduced pressure of 300 Torr. The water and heptane accumulated in the holder were collected, and the water in the system was removed. Then, heptane was placed in the holder, and a titanium solution, a mixture of 2.56 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 2.56 g of heptane, was added to the separable flask to carry out the transesterification reaction. While periodically removing the lower phase accumulated in the holder, heating was continued by gas chromatography analysis until the area ratio of the target substance, 2-(allyloxymethyl)acrylate-1-naphthylmethyl, exceeded 96%. The internal temperature was adjusted to 70°C, 43.5g of a 7% oxalic acid aqueous solution was added, and the mixture was heated and stirred for 30 minutes. After standing for 30 minutes, the aqueous phase was removed. Next, 43.5g of water was used, and the above washing procedure was repeated a total of two times. This washing procedure removed the titanium tetraisopropoxide used as a catalyst. The pressure inside the system was reduced to 300 Torr, and the internal temperature was raised to 110°C to remove heptane and water. Then, while maintaining the internal temperature at 100-105°C, the pressure inside the system was reduced to 50 Torr. Once it reached 50 Torr, the internal temperature was raised to 110°C to remove any remaining trace amounts of heptane. The internal temperature was then lowered to around 50°C, and once it reached 50°C, the pressure inside the system was reduced to 2-5 Torr. After reaching 2-5 Torr, the internal temperature was raised to 110°C, and AOMA was distilled off to complete the removal of light boiling components. The obtained solution was filtered through a 0.8 μm PTFE membrane filter to obtain 2-(allyloxymethyl)acrylate-1-naphthylmethyl (hereafter, FX-AO-MA-NM-T) represented by the following formula (A1). The obtained target product contained 3.4% by mass of AOMA. Furthermore, the refractive index of FX-AO-MA-NM-T measured according to "(6) Measurement of the refractive index of the compound" was 1.57, and the viscosity of FX-AO-MA-NM-T measured according to "(7) Measurement of the viscosity of the compound" was 37 mPa·s.

[0149] [ka]

[0150] [Production Example 1-2: Synthesis of 2-(allyloxymethyl)acrylate-3-phenoxybenzyl] A stirrer bar, 70.00 g of 3-phenoxybenzyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.), 80.24 g of α-allyloxymethylacrylate (AOMA), 80 mg of polymerization inhibitor (6-t-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industry Co., Ltd.), 80 mg of polymerization inhibitor (Polystop 7300P, manufactured by Hakuto Co., Ltd.), and 31.2 g of heptane were weighed into a 300 mL separable flask. 6.1 g of heptane was placed in a holder, and the system was heated and stirred at 90-100°C for 1 hour under reduced pressure of 300 Torr. The water and heptane accumulated in the holder were collected, and the water in the system was removed. Then, heptane was placed in the holder, and a titanium solution, a mixture of 1.93 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1.93 g of heptane, was added to the separable flask to carry out the transesterification reaction. While periodically removing the lower phase accumulated in the holder, heating was continued until the area ratio of the target product, 2-(allyloxymethyl)acrylate-3-phenoxybenzyl, exceeded 95% by gas chromatography analysis. The internal temperature was adjusted to 70°C, 35.9g of a 7% oxalic acid aqueous solution was added, and the mixture was heated and stirred for 30 minutes. After standing for 30 minutes, the aqueous phase was removed. Next, 35.9g of water was used, and the above washing procedure was repeated a total of two times. This washing procedure removed the titanium tetraisopropoxide used as a catalyst. The pressure inside the system was reduced to 300 Torr, and the internal temperature was raised to 110°C to remove heptane and water. Then, while maintaining the internal temperature at 100-105°C, the pressure inside the system was reduced to 50 Torr. Once it reached 50 Torr, the internal temperature was raised to 110°C to remove any remaining trace amounts of heptane. The internal temperature was then lowered to around 50°C, and once it reached 50°C, the pressure inside the system was reduced to 3-5 Torr. After reaching 3-5 Torr, the internal temperature was raised to 110°C, and AOMA was distilled off to complete the removal of light boiling components. The obtained solution was filtered through a 0.8 μm PTFE membrane filter to obtain 2-(allyloxymethyl)acrylate-3-phenoxybenzyl (hereafter, FX-AO-MA-PO-B), represented by the following formula (A2). The obtained product contained 3.4% by mass of AOMA. The refractive index of FX-AO-MA-PO-B was 1.55, and its viscosity was 23 mPa·s.

[0151] [ka]

[0152] [Production Example 1-3: Synthesis of 2-(2-phenylphenoxy)ethyl 2-(allyloxymethyl)acrylate] A stirrer bar, 80.00 g of 2-(2-biphenylyloxy)ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 85.70 g of α-allyloxymethylacrylate (AOMA), 86 mg of polymerization inhibitor (6-t-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industry Co., Ltd.), 86 mg of polymerization inhibitor (Polystop 7300P, manufactured by Hakuto Co., Ltd.), and 34.4 g of heptane were weighed into a 300 mL separable flask. 5.7 g of heptane was placed in the holder, and the system was heated and stirred at 90-100°C for 1 hour under reduced pressure of 300 Torr. The water and heptane accumulated in the holder were collected, and the water in the system was removed. Then, heptane was placed in the holder, and a titanium solution, a mixture of 2.06 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 2.06 g of heptane, was added to the separable flask to carry out the transesterification reaction. While periodically removing the lower phase accumulated in the holder, heating was continued by gas chromatography analysis until the area ratio of the target product, 2-(allyloxymethyl)acrylate-2-(2-phenylphenoxy)ethyl, exceeded 94%. The internal temperature was adjusted to 70°C, 39.5g of a 7% oxalic acid aqueous solution was added, and the mixture was heated and stirred for 30 minutes. After standing for 30 minutes, the aqueous phase was removed. Next, 39.5g of water was used, and the above washing procedure was repeated a total of two times. This washing procedure removed the titanium tetraisopropoxide used as a catalyst. The pressure inside the system was reduced to 300 Torr, and the internal temperature was raised to 110°C to remove heptane and water. Then, while maintaining the internal temperature at 100-105°C, the pressure inside the system was reduced to 50 Torr. Once it reached 50 Torr, the internal temperature was raised to 110°C to remove any remaining trace amounts of heptane. The internal temperature was then lowered to around 50°C, and once it reached 50°C, the pressure inside the system was reduced to 3-5 Torr. After reaching 3-5 Torr, the internal temperature was raised to 110°C, and AOMA was distilled off to complete the removal of light boiling components. The obtained solution was filtered through a 0.8 μm PTFE membrane filter to obtain 2-(allyloxymethyl)acrylate-2-(2-phenylphenoxy)ethyl (hereafter, FX-AO-MA-HR-D) represented by the following formula (A3). The obtained product contained 3.2% by mass of AOMA. The refractive index of FX-AO-MA-HR-D was 1.56, and its viscosity was 73 mPa·s.

[0153] [ka]

[0154] [Production Example 1-4: Synthesis of 2-(allyloxymethyl)acrylate-4-phenylbenzyl] A stirrer bar, 70.00 g of 4-hydroxymethylbiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.), 89.01 g of α-allyloxymethylacrylate (AOMA), 89 mg of polymerization inhibitor (6-t-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industry Co., Ltd.), 89 mg of polymerization inhibitor (Polystop 7300P, manufactured by Hakuto Co., Ltd.), and 33.1 g of heptane were weighed into a 300 mL separable flask. 5.5 g of heptane was placed in a holder, and the system was heated and stirred at 90-100°C for 1 hour under reduced pressure of 300 Torr. The water and heptane accumulated in the holder were collected, and the water in the system was removed. Then, heptane was placed in the holder, and a titanium solution, a mixture of 2.14 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 2.14 g of heptane, was added to the separable flask to carry out the transesterification reaction. While periodically removing the lower phase accumulated in the holder, heating was continued by gas chromatography analysis until the area ratio of the target product, 2-(allyloxymethyl)acrylate-4-phenylbenzyl, exceeded 96%. The internal temperature was adjusted to 70°C, 34.7g of a 7% oxalic acid aqueous solution was added, and the mixture was heated and stirred for 30 minutes. After standing for 30 minutes, the aqueous phase was removed. Next, 34.7g of water was used, and the above washing procedure was repeated a total of two times. This washing procedure removed the titanium tetraisopropoxide used as a catalyst. The pressure inside the system was reduced to 300 Torr, and the internal temperature was raised to 110°C to remove heptane and water. Then, while maintaining the internal temperature at 100-105°C, the pressure inside the system was reduced to 50 Torr. Once it reached 50 Torr, the internal temperature was raised to 110°C to remove any remaining trace amounts of heptane. The internal temperature was then lowered to around 50°C, and once it reached 50°C, the pressure inside the system was reduced to 4-5 Torr. After reaching 4-5 Torr, the internal temperature was raised to 110°C, and AOMA was distilled off to complete the removal of light boiling components. The obtained solution was filtered through a 0.8 μm PTFE membrane filter to obtain 2-(allyloxymethyl)acrylate-4-phenylbenzyl (hereafter, FX-AO-MA-BP-ML) represented by the following formula (A4). The obtained product contained 4.7% by mass of AOMA. The refractive index of FX-AO-MA-BP-ML was 1.56, and its viscosity was 25 mPa·s.

[0155] [ka]

[0156] [Production Example 1-5: Synthesis of 2-(allyloxymethyl)acrylate-9-fluorenylmethyl] A stirrer bar, 50.00 g of 9-fluorenyl methanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 118.17 g of α-allyloxymethyl methyl acrylate (AOMA), 118 mg of polymerization inhibitor (6-t-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industry Co., Ltd.), 118 mg of polymerization inhibitor (Polystop 7300P, manufactured by Hakuto Co., Ltd.), and 35.0 g of heptane were weighed into a 300 mL separable flask. 5.8 g of heptane was placed in the holder, and the system was heated and stirred at 90-100°C for 1 hour under reduced pressure of 300 Torr. The water and heptane accumulated in the holder were collected, and the water in the system was removed. Then, heptane was placed in the holder, and a titanium solution, a mixture of 1.42 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1.42 g of heptane, was added to the separable flask to carry out the transesterification reaction. While periodically removing the lower phase accumulated in the holder, heating was continued by gas chromatography analysis until the area ratio of the target product, 2-(allyloxymethyl)acrylate-9-fluorenylmethyl, exceeded 97%. The internal temperature was adjusted to 70°C, 41.0 g of a 7% oxalic acid aqueous solution was added, and the mixture was heated and stirred for 30 minutes. After standing for 30 minutes, the aqueous phase was removed. Next, 41.0 g of water was used, and the above washing procedure was repeated a total of two times. This washing procedure removed the titanium tetraisopropoxide used as a catalyst. The pressure inside the system was reduced to 300 Torr, and the internal temperature was raised to 110°C to remove heptane and water. Then, while maintaining the internal temperature at 100-105°C, the pressure inside the system was reduced to 50 Torr. Once it reached 50 Torr, the internal temperature was raised to 110°C to remove any remaining trace amounts of heptane. The internal temperature was then lowered to around 50°C, and once it reached 50°C, the pressure inside the system was reduced to 4-5 Torr. After reaching 3-5 Torr, the internal temperature was raised to 110°C, and AOMA was distilled off to complete the removal of light boiling components. The obtained solution was filtered through a 0.8 μm PTFE membrane filter to obtain 2-(allyloxymethyl)acrylate-9-fluorenylmethyl (hereafter, FX-AO-MA-FM) represented by the following formula (A5). The obtained product contained 3.7% by mass of AOMA. The refractive index of FX-AO-MA-FM was 1.58, and its viscosity was 220 mPa·s.

[0157] [ka]

[0158] [Production Example 2-1: Production of coated zirconium oxide nanoparticles coated with 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid (coated ZrO2 particles 1)] In a separable flask equipped with a stirrer, thermometer, and condenser, 50 parts by mass of basic zirconium carbonate (SZBC, manufactured by Saint-Gobain ZirPro (Handan) Co., Ltd; ZrO2 content 41.1% by mass, moisture content 40.2% by mass), 74 parts by mass of mineral spirits as solvents, and 2.5 parts by mass of 2-ethylhexanoic acid were added and stirred at room temperature for 5 to 10 minutes (Step (1)). Then, the flask was immersed in an oil bath and stirred while the internal temperature was raised to 85°C. After that, the internal temperature was maintained at 85°C to 90°C and stirring was continued for 3 hours (Step (2)). Subsequently, 24 parts by mass of 2-ethylhexanoic acid were added and the oil bath temperature was adjusted to maintain the internal temperature at 100 to 130°C for 4 hours to react the basic zirconium carbonate with 2-ethylhexanoic acid (Step (3)). The reaction product was a white slurry at the start of the reaction, but at the end of the reaction it had become a translucent, cloudy liquid. When the reaction solution was cooled to room temperature, it separated into two layers, with the upper layer being the mineral spirit layer. The upper layer was filtered, and a small amount of mineral spirit was added to adjust the Zr concentration to approximately 12% by mass (step (4)).

[0159] 42.4 parts by mass of the zirconium 2-ethylhexanoate-mineral spirit solution obtained in step (4) were mixed with 7.3 parts by mass of pure water and charged into an autoclave equipped with a thermometer and stirrer, and the atmosphere in the reactor was replaced with nitrogen gas. Then, the internal temperature was heated to 190°C and the reaction was carried out for 9 hours, and then the internal temperature was raised to 195°C and the reaction was carried out for 8 hours to synthesize zirconium oxide nanoparticles. The pressure in the container when the reaction was carried out at 190°C was 1.2 MPa, and the pressure in the container when the reaction was carried out at 195°C was 1.40 MPa. The solution after the reaction was removed, the resulting precipitate was filtered and washed with acetone, and then dried under reduced pressure to obtain zirconium oxide nanoparticles (coated ZrO2 particles 1).

[0160] The crystal structure of the obtained coated ZrO2 particles 1 was confirmed according to the above-described "(1) Analysis of Crystal Structure" and "(2) Determination of the Ratio of Tetragonal and Monoclinic Crystals." Diffraction lines attributed to tetragonal and monoclinic crystals were detected. From the intensity of the diffraction lines, the ratio of tetragonal to monoclinic crystals was determined to be 92 / 8, and the crystallite size calculated by "(3) Calculation of Crystallite Size by X-ray Diffraction Analysis" was 5 nm. Furthermore, the average particle size (number-mean primary particle size) of the coated ZrO2 particles 1, measured by "(4) Measurement of Average Primary Particle Size by Electron Microscopy," was 18 nm. In addition, analysis of the obtained coated ZrO2 particles 1 by infrared absorption spectroscopy revealed absorption originating from CH and absorption originating from COOH. These absorptions are thought to be due to 2-ethylhexanoic acid and / or carboxylates derived from 2-ethylhexanoic acid coating the coated ZrO2 particles 1.

[0161] The organic content of coated ZrO2 particles 1, measured according to "(5) Measurement of Organic Content" described above, was 12% by mass. Therefore, it was found that 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid coating coated ZrO2 particles 1 constituted 12% by mass of the entire coated ZrO2 particles 1.

[0162] [Production Example 2-2: Production of zirconium oxide nanoparticles coated with carboxylate derived from 2-ethylhexanoic acid and / or 2-ethylhexanoic acid, crotonic acid, and 2-methacryloyloxyethyl acid phosphate (coated ZrO2 particles 2)] The coated ZrO2 particles 1 (10 parts by mass) obtained in the above production example 2-1, crotonic acid (1.5 parts by mass), and 2-methacryloyloxyethyl acid phosphate (0.5 parts by mass) were stirred and mixed in toluene (12 parts by mass) until uniformly dispersed. Next, n-hexane (36 parts by mass) was added to agglomerate the dispersed particles and make the solution cloudy, and the agglomerated particles were separated from the cloudy liquid using filter paper. Subsequently, the separated agglomerated particles were added to n-hexane (36 parts by mass), stirred for 10 minutes, and the agglomerated particles were separated using filter paper. The resulting particles were vacuum-dried at room temperature to prepare zirconium oxide nanoparticles (coated ZrO2 particles 2) surface-treated with 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid, crotonic acid, and 2-methacryloyloxyethyl acid phosphate.

[0163] The obtained coated ZrO2 particles 2 were dispersed in deuterated chloroform to prepare the measurement sample. 1 Analysis was performed using 1H-NMR. The results showed that the molar ratio of carboxylate derived from 2-ethylhexanoic acid and / or 2-ethylhexanoic acid, crotonic acid, and 2-methacryloyloxyethyl acid phosphate was 21:57:22.

[0164] The organic content of coated ZrO2 particles 2, measured according to "(5) Measurement of Organic Content" above, was 14% by mass. Therefore, it was found that 2-ethylhexanoic acid and / or carboxylate, crotonic acid, and 2-methacryloyloxyethyl acid phosphate, which coat coated ZrO2 particles 2, account for 14% by mass of the total coated ZrO2 particles 2.

[0165] [Production Example 2-3: Production of zirconium oxide nanoparticles coated with carboxylate derived from 2-ethylhexanoic acid and / or 2-ethylhexanoic acid, triethylene glycol monomethyl ether phosphate, and 2-methacryloyloxyethyl acid phosphate (coated ZrO2 particles 3)] The coated ZrO2 particles 1 (10 parts by mass) obtained in the above production example 2-1, triethylene glycol monomethyl ether phosphate (1.5 parts by mass), and 2-methacryloyloxyethyl acid phosphate (0.5 parts by mass) were stirred and mixed in toluene (12 parts by mass) until uniformly dispersed. Next, n-hexane (36 parts by mass) was added to agglomerate the dispersed particles and make the solution cloudy, and the agglomerated particles were separated from the cloudy liquid using filter paper. Subsequently, the separated agglomerated particles were added to n-hexane (36 parts by mass), stirred for 10 minutes, and the agglomerated particles were separated using filter paper. The resulting particles were vacuum-dried at room temperature to prepare zirconium oxide nanoparticles (coated ZrO2 particles 3) surface-treated with 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid, triethylene glycol monomethyl ether phosphate, and 2-methacryloyloxyethyl acid phosphate.

[0166] The obtained coated ZrO2 particles 3 were dispersed in deuterated chloroform to prepare the sample for measurement. 1 Analysis was performed using 1H-NMR. The results showed that the molar ratio of carboxylate derived from 2-ethylhexanoic acid and / or 2-ethylhexanoic acid, triethylene glycol monomethyl ether phosphate, and 2-methacryloyloxyethyl acid phosphate was 21:51:28.

[0167] The organic content of coated ZrO2 particles 3, measured according to "(5) Measurement of Organic Content" above, was 14% by mass. Therefore, it was found that 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid, triethylene glycol monomethyl ether phosphate, and 2-methacryloyloxyethyl acid phosphate, which coat coated ZrO2 particles 3, account for 14% by mass of the total coated ZrO2 particles 3.

[0168] [Production Example 2-4: Production of zirconium oxide nanoparticles coated with carboxylate derived from 2-ethylhexanoic acid and / or 2-ethylhexanoic acid, 2-acryloyloxyethyl succinate, and 3-methacryloxypropyltrimethoxysilane (coated ZrO2 particles 4)] A cloudy slurry was prepared by dispersing coated ZrO2 particles 1 (10 parts by mass) obtained in the above production example 2-1 in methyl isobutyl ketone (40 parts by mass). 3-methacryloxypropyltrimethoxysilane (1.6 parts by mass, Shin-Etsu Chemical Co., Ltd., KBM-503) and water (0.9 parts by mass) were added to this solution as surface treatment agents, and the mixture was heated under reflux at 80°C for 1 hour to obtain a clear dispersion solution. The mixture was then cooled to 50°C, and then 2-acryloyloxyethyl succinate (1.4 parts by mass) was added and stirred for 30 minutes to obtain a zirconium oxide dispersion.

[0169] Next, n-hexane was added to agglomerate the dispersed particles and make the solution cloudy. After separating the agglomerated particles from the cloudy liquid using filter paper, the solution was heated and dried at room temperature to prepare zirconium oxide nanoparticles (coated ZrO2 particles 4) coated with 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid, 2-acryloyloxyethyl succinate, and 3-methacryloxypropyltrimethoxysilane.

[0170] The obtained coated ZrO2 particles 4 were dispersed in deuterated chloroform to prepare the sample for measurement. 1 Analysis was performed using 1H-NMR. The results showed that the molar ratio of carboxylate derived from 2-ethylhexanoic acid and / or 2-ethylhexanoic acid, 3-methacryloxypropyltrimethoxysilane, and 2-acryloyloxyethyl succinate was 27:35:38.

[0171] The mass loss rate of coated ZrO2 particles 4, measured according to "(5) Measurement of Organic Content" above, was 14% by mass. Therefore, it was found that 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid, 3-methacryloxypropyltrimethoxysilane, and 2-acryloyloxyethyl succinate, which coat the coated ZrO2 particles 4, account for 14% by mass of the entire coated ZrO2 particles 4.

[0172] [Example 1: Preparation of Composition A1] Composition A1 with a particle content of 85% by mass was obtained by blending coated ZrO2 particles 2 (17 parts by mass) obtained in Production Example 2-2 and FX-AO-MA-NM-T (3.0 parts by mass) obtained in Production Example 1-1 and uniformly stirring.

[0173] [Example 2: Preparation of Composition A2] Composition A2 with a particle content of 85% by mass was obtained in the same manner as in Example 1, except that FX-AO-MA-PO-B obtained in Production Example 1-2 was used instead of FX-AO-MA-NM-T.

[0174] [Example 3: Preparation of Composition A3] Composition A3 with a particle content of 85% by mass was obtained in the same manner as in Example 1, except that FX-AO-MA-HR-D obtained in Production Example 1-3 was used instead of FX-AO-MA-NM-T.

[0175] [Example 4: Preparation of Composition A4] Composition A4 with a particle content of 85% by mass was obtained in the same manner as in Example 1, except that FX-AO-MA-BP-ML obtained in Production Example 1-4 was used instead of FX-AO-MA-NM-T.

[0176] [Example 5: Preparation of Composition A5] Composition A5 with a particle content of 85% by mass was obtained in the same manner as in Example 1, except that FX-AO-MA-FM obtained in Production Example 1-5 was used instead of FX-AO-MA-NM-T.

[0177] [Example 6: Preparation of Composition A6] A composition A6 with a particle content of 85% by mass was obtained in the same manner as in Example 1, except that coated ZrO2 particles 3 were used instead of coated ZrO2 particles 2.

[0178] [Example 7: Preparation of Composition A7] A composition A7 with a particle content of 85% by mass was obtained in the same manner as in Example 1, except that coated ZrO2 particles 4 were used instead of coated ZrO2 particles 2.

[0179] [Comparative Example 1: Preparation of Composition C1] A composition (C1) with a particle content of 85% by mass was obtained in the same manner as in Example 1, except that the compound represented by the following formula (C1) (hereinafter, FX-AO-MA) was used instead of FX-AO-MA-NM-T.

[0180] [Chemical formula]

[0181] [Comparative Example 2: Preparation of Composition C2] A composition C2 with a particle content of 85% by mass was obtained in the same manner as in Example 1, except that Light Acrylate NMT-A (manufactured by Kyoeisha Chemical Co., Ltd., the compound represented by the following formula (C2), hereinafter NMT-A) was used instead of FX-AO-MA-NM-T.

[0182] [Chemical formula]

[0183] [Comparative Example 3: Preparation of Composition C3] A composition C3 with a particle content of 85% by mass was obtained in the same manner as in Example 1, except that Light Acrylate POB-A (manufactured by Kyoeisha Chemical Co., Ltd., the compound represented by the following formula (C3), hereinafter POB-A) was used instead of FX-AO-MA-NM-T.

[0184] [Chemical formula]

[0185] [Comparative Example 4: Preparation of Composition C4] Composition C4 with a particle content of 85% by mass was obtained in the same manner as in Example 1, except that light ester POB-MA (manufactured by Kyoeisha Chemical Co., Ltd., a compound represented by the following formula (C4), hereafter POB-MA) was used instead of FX-AO-MA-NM-T.

[0186] [ka]

[0187] [Comparative Example 5: Preparation of Composition C5] Composition C5 with a particle content of 85% by mass was obtained in the same manner as in Example 1, except that HRD-01 (manufactured by Nisshoku Techno Fine Chemicals Co., Ltd., represented by the following formula (C5), hereafter HRD-01) was used instead of FX-AO-MA-NM-T.

[0188] [ka]

[0189] The viscosity, refractive index, haze, and total light transmittance of each composition obtained in Examples 1-7 and Comparative Examples 1-5 were evaluated according to "(8) Measurement of viscosity of composition", "(9) Measurement of refractive index of composition", and "(10) Measurement of haze and total light transmittance". The results are shown in Table 1.

[0190] [Table 1]

[0191] A comparison of Examples 1-7 and Comparative Example 1 shows that compositions with high refractive indices can be obtained in the examples. The cured products obtained by curing the compositions obtained in the examples reflect the refractive index of the compositions and can therefore be cured products with high refractive indices. Furthermore, a comparison of Examples 1-7 and Comparative Examples 2-5 shows that the examples yield particle-containing compositions with low haze (especially low haze and high total light transmittance) while maintaining a high refractive index comparable to that obtained when using conventional high-refractive-index monomers. This effect is even clearer when comparing monomers having similar partial skeletons. Specifically, as can be seen from the comparison between the compositions containing monomers with a naphthylmethyl skeleton in Example 1 and Comparative Example 2, the comparison between the compositions containing monomers with a phenoxybenzyl skeleton in Example 2 and Comparative Examples 3-4, and the comparison between the compositions containing monomers with a (2-phenylphenoxy)ethyl skeleton in Example 3 and Comparative Example 5, in all cases, the compositions obtained in the examples can be prepared as particle-containing compositions with low haze (especially low haze and high total light transmittance) while maintaining a high refractive index, demonstrating their superiority as transparent materials. Furthermore, in the above comparison, the refractive index and viscosity of the compositions were equivalent, demonstrating the superiority of compositions using monomers having an α-(allyloxymethyl)acryloyl skeleton as dispersion media for compositions containing inorganic particles. That is, as shown in Table 2, when comparing the monomers individually, monomers having an α-(allyloxymethyl)acryloyl skeleton have a lower refractive index and higher viscosity compared to their corresponding (meth)acrylate compounds. However, when used as dispersion media for compositions containing inorganic particles, this difference disappears. This is thought to be due to the good compatibility of monomers having an α-(allyloxymethyl)acryloyl skeleton with inorganic particles, resulting in a decrease in viscosity and an improvement in refractive index.

[0192] [Table 2]

[0193] Table 2 above shows the refractive index and viscosity of each compound, measured according to "(6) Measurement of the refractive index of the compound" and "(7) Measurement of the viscosity of the compound".

[0194] Next, for the compositions obtained in Examples 1 and 2 and Comparative Examples 1 to 4, "(11) Evaluation of residual film properties", "(12) Evaluation of curability", and "(13) Evaluation of flex resistance" were carried out to evaluate the residual film properties, curability, and flex resistance. The results are shown in Table 3.

[0195]

Table 3

[0196] From the comparison between Examples 1 and 2 and Comparative Example 1, it can be seen that the examples are superior in terms of residual film properties. Residual film properties are very important properties, such as in the design of thin films and preventing quality fluctuations during the production of cured products. Also, from the comparison between Examples 1 to 2 and Comparative Examples 2 to 3, it has been shown that the compositions of the examples have a rapid curability equivalent to that of compositions using conventional acrylate-based compounds. Furthermore, it has been shown that the example compositions have flex resistance imparted. That is, by applying the compositions of the examples and the cured products formed from the compositions, it is possible to achieve both high transparency, good residual film properties, good curability, and good flex resistance, which are important properties for use in various optical applications while showing a high refractive index.

Claims

1. A composition comprising a compound (A) represented by the following general formula (1) and inorganic particles (B). 【Chemistry 1】 [In formula (1), R 1 This includes organic groups containing aromatic hydrocarbon rings with 10 or more carbon atoms in their structure, organic groups containing aromatic heterocycles, and groups with two or more benzene rings bonded together by single bonds, -O-, -S-, and -CH. 2 -, -C(CH 3 ) 2 -, -SO- or -SO 2 This represents an organic group containing a structure bonded via a -, an organic group containing a structure in which three benzene rings are bonded via carbon atoms, or an organic group represented by the following general formula (2). X represents either the same or different -O-, -S-, or -NH-. Y is the same or different and is *-CR 2 R 3 -**, *-O-**, *-S-**, *-NH-** or *-(Z-A) n -** (where * represents a bond with R 1 and ** represents a bond with X). R 2 and R 3 These represent a hydrogen atom or a methyl group, either identical or distinct. Z represents -O-, -S-, or -NH-. A represents an alkylene group. n represents an integer between 1 and 20. m represents an integer between 1 and 3. 【Chemistry 2】 [In formula (2), R 21 R represents a single bond or an alkylene group. 22 represents a halogen atom, either identical or different. 'a' represents an integer from 1 to 3. * indicates a bond with Y.

2. The composition according to claim 1, wherein the refractive index of compound (A) at 25°C is 1.55 or higher.

3. The composition according to claim 1, characterized in that the inorganic particles (B) include at least one metallic element selected from the group consisting of titanium, aluminum, silicon, zirconium, indium, zinc, tin, lanthanum, yttrium, cerium, magnesium, barium, calcium, niobium, and tantalum.

4. The composition according to claim 1, wherein the inorganic particles (B) are inorganic particles coated with a coating agent.

5. The composition according to claim 4, wherein the coating agent comprises at least one selected from the group consisting of carboxylic acid compounds, phosphate esters, and silane coupling agents.

6. The composition according to claim 1, wherein the content of the inorganic particles (B) is 60% by mass or more of 100% by mass of the solid components of the composition.

7. The composition according to claim 1, wherein the average primary particle diameter of the inorganic particles (B) is 50 nm or less.

8. A cured product of the composition according to any one of claims 1 to 7.

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