Curable composition, cured product, optical material, diffractive optical element, and compound

Abstract

Provided are: a curable composition containing a compound represented by general formula (1) or (2); a cured product, an optical material, and a diffractive optical element using the curable composition; and a compound represented by general formula (1) or (2). In the formula, Q1 represents a group represented by formula (q1a) or (q1b), Q2 represents a group represented by formula (q2), and Q3 represents a group represented by formula (q3). In the formula, R1 represents a (meth) acryloyl group, a vinyl group or an allyl group. * represents a bond. # imgabs0 # *-S-CH3 (q2) *-S-R1 (q3).

Description

Technical Field

[0001] The present invention relates to a curable composition, a cured product, an optical material, a diffractive optical element and a compound. Background Art

[0002] In recent years, research on optical resins expected to be used in optical components requiring a high refractive index, such as diffractive optical elements, has been actively conducted, and the development of monomers exhibiting a high refractive index as raw materials for optical resins has also been advanced.

[0003] For example, Patent Document 1 describes a polymerizable compound represented by General Formula (I) having a specific structure in which a sulfur atom is bonded to a condensed ring having a benzene ring and an aromatic ring.

[0004] Previous technical literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2018-104696 Summary of the Invention

[0007] Technical issues to be solved by the invention

[0008] There is known a microfabrication technology called imprint technology, which involves imprinting a mold (die) having a microstructure with various patterns ranging from nanometers to hundreds of micrometers onto a material such as resin, and transferring the pattern onto the surface of the material.

[0009] Imprinting involves applying the material to a substrate, pressing the material in a molded state, fixing the transferred pattern by light or heat curing, and finally demolding. Imprinting materials, like inkjet inks, are temporarily stored in tanks before entering the imprinting process. Therefore, they must not crystallize or become turbid in the storage tank (hereinafter referred to as "temporal stability").

[0010] The present invention aims to provide a curable composition that exhibits excellent temporal stability even in its pre-curing state and can also achieve a high refractive index in the resulting cured product. Furthermore, the present invention aims to provide a cured product obtained from the curable composition, an optical material and a diffractive optical element containing the cured product, and a compound contained in the curable composition.

[0011] Means for solving technical problems

[0012] The above-mentioned problems of the present invention are solved by the following means.

[0013] <1>

[0014] A curable composition comprising a compound represented by the following general formula (1) or (2).

[0015] [Chemical Formula 1]

[0016]

[0017] In the above formula, Q 1 represents a group represented by the following formula (q1a) or (q1b), Q 2 represents a group represented by the following formula (q2), Q 3 It represents a group represented by the following formula (q3).

[0018] [Chemical Formula 2]

[0019]

[0020] *-S-CH3 (q2) *-SR 1 (q3)

[0021] In the above formula, R 1 represents a (meth)acryloyl group, a vinyl group, or an allyl group. * represents a bonding bond.

[0022] <2>

[0023] The curable composition according to <1>, wherein

[0024] The compound represented by the general formula (1) or (2) contains the substituent (Q 1 ,Q 3 ) is substituted at the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring, and the substituent (Q 2 ,Q 3 ) is substituted at the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring, or at least one of the compounds.

[0025] <3>

[0026] The curable composition according to <2>, wherein

[0027] The compound represented by the above-mentioned general formula (1) or (2) includes at least one compound represented by any one of the following general formulas (3) to (6).

[0028] [Chemical Formula 3]

[0029]

[0030] In the above formula, R 1 The meaning is the same as above R1 has the same meaning. 2 represents a hydrogen atom or a methylsulfanyl group.

[0031] <4>

[0032] The curable composition according to any one of <1> to <3>, further comprising a compound represented by the following general formula (7).

[0033] [Chemical Formula 4]

[0034]

[0035] In the above formula, Q 4 and Q 5 represents a group represented by any of the following formulas (q1a), (q1b), (q2) or (q3). 4 and Q 5 When one of them is a group represented by any one of the following formulas (q1a), (q1b) or (q2), and the other is a group represented by the following formula (q3).

[0036] [Chemical Formula 5]

[0037]

[0038] *-S-CH3 (q2) *-SR 1 (q3)

[0039] In the above formula, R 1 represents a (meth)acryloyl group, a vinyl group or an allyl group, and * represents a bonding bond.

[0040] <5>

[0041] The curable composition according to any one of <1> to <4>, which is used for imprinting.

[0042] <6>

[0043] A film obtained from the curable composition according to any one of <1> to <5>.

[0044] <7>

[0045] An optical material comprising the cured product according to <6>.

[0046] <8>

[0047] A diffractive optical element comprising a surface having a diffraction grating shape formed from the cured product according to <6>.

[0048] <9>

[0049] A compound represented by the following general formula (1) or (2).

[0050] [Chemical Formula 6]

[0051]

[0052] In the above formula, Q 1 represents a group represented by the following formula (q1a) or (q1b), Q 2 represents a group represented by the following formula (q2), Q 3 It represents a group represented by the following formula (q3).

[0053] [Chemical Formula 7]

[0054]

[0055] *-S-CH3 (q2) *-SR 1 (q3)

[0056] In the above formula, R 1 represents a (meth)acryloyl group, a vinyl group, or an allyl group. * represents a bonding bond.

[0057] In the present invention, when there are multiple substituents or linking groups (hereinafter referred to as substituents, etc.) represented by specific symbols or formulas, or when multiple substituents, etc. are specified at the same time, unless otherwise specified, the substituents, etc. may be the same as each other or different from each other (regardless of whether there is "independently" expression, each substituent, etc. may be the same as each other or different from each other). The same applies to the number of substituents, etc. Furthermore, when multiple substituents, etc. are close (especially, adjacent), unless otherwise specified, these may be linked to each other to form a ring. Furthermore, unless otherwise specified, rings, such as alicyclic rings, aromatic rings, and heterocyclic rings may be further fused to form a fused ring.

[0058] In the present invention, unless otherwise specified, when a double bond exists in an E-type or a Z-type in a molecule, it may be either one or a mixture thereof.

[0059] Furthermore, in the present invention, unless otherwise specified, when a compound has one or two or more asymmetric carbon atoms, the stereochemistry of the asymmetric carbon atoms can be either (R) or (S) independently. As a result, the compound may be a mixture of stereoisomers such as optical isomers or diastereomers, or may be a racemate.

[0060] Furthermore, in the present invention, the compounds and monomers shown include substances that change a part of the structure within the scope that does not impair the effects of the present invention. In addition, for compounds and monomers that are not clearly described as substituted or unsubstituted in text form, it means that they may have any substituents within the scope that does not impair the effects of the present invention. For example, in the compound represented by the general formula (1) or (2), the substituent having Q 1 and Q 3 The naphthalene ring has Q as a substituent 2 and Q 3 The naphthalene ring and the benzene ring in the group represented by formula (q1a) or (q1b) may be unsubstituted or have any substituent. Examples of the optional substituent include any of a saturated or unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, an alkoxy group, an alkylsulfanyl group, an aryloxy group, an arylsulfanyl group, and a halogen atom. From the perspective of imprinting applications, when the substituent is unsubstituted or has a substituent, the substituent is preferably a halogen atom.

[0061] In the present invention, when a substituent is not explicitly stated as substituted or unsubstituted (the same applies to linking groups and rings), it means that the group may have any substituent as long as the desired effect is not impaired. For example, when referred to as "alkyl", it includes both unsubstituted and substituted alkyl groups.

[0062] In the present invention, when the number of carbon atoms in a group is specified, the number of carbon atoms refers to the number of carbon atoms in the entire group unless otherwise specified in the present invention or this specification. In other words, when the group further has a substituent, the number of carbon atoms refers to the total number of carbon atoms including the substituent.

[0063] In the present invention, a numerical range expressed using "to" means a range including the numerical values described before and after "to" as the lower limit and the upper limit.

[0064] In the curable composition of the present invention, each component may be used alone or in combination of two or more. This also applies to the cured product, optical material, and diffractive optical element obtained from the curable composition of the present invention.

[0065] In the present invention, "(meth)acrylate" refers to either or both acrylate and methacrylate, "(meth)acrylic acid" refers to either or both acrylic acid and methacrylic acid, and "(meth)acryloyl" refers to either or both acryloyl and methacryloyl. Monomers in the present invention are distinguished into oligomers and polymers based on molecular weight, and compounds with a weight-average molecular weight of 1000 or less are referred to as monomers.

[0066] In the present invention, an alkyl group refers to a linear or branched alkyl group.

[0067] The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 7, and particularly preferably 1 to 5.

[0068] Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 3-methylbutyl, hexyl, 1-methylpentyl, 4-methylpentyl, heptyl, 1-methylhexyl, 5-methylhexyl, 2-ethylhexyl, octyl, 1-methylheptyl, nonyl, 1-methyloctyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl. Among these, methyl or ethyl is preferred.

[0069] The same applies to the alkyl group in the group containing an alkyl group (alkoxy group, alkylsulfanyl group, etc.).

[0070] Furthermore, the alkyl group may have a substituent, and examples of the alkyl group having a substituent include a halogenated alkyl group and a hydroxyalkyl group.

[0071] In the present invention, the alkylene group includes a group obtained by removing one hydrogen atom bonded to a carbon atom in the above-mentioned alkyl group, and may be a linear alkylene group or a branched alkylene group. Examples thereof include ethylene, propylene, and butylene.

[0072] In the present invention, a monovalent aromatic hydrocarbon ring group (aryl group) represents a monovalent group obtained by removing one arbitrary hydrogen atom from an aromatic hydrocarbon ring which may be a monocyclic ring or a condensed ring. As a monovalent aromatic hydrocarbon ring group, an aromatic hydrocarbon ring group having 6 to 14 carbon atoms is preferred, and examples thereof include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, and 9-phenanthrenyl. Among these, phenyl is preferred.

[0073] The same applies to the aryl group in the aryl group-containing group (aryloxy group, arylsulfanyl group, etc.).

[0074] In the present invention, a monovalent aromatic heterocyclic group (heteroaryl group) refers to a monovalent group obtained by removing one arbitrary hydrogen atom from an aromatic heterocycle.

[0075] An aromatic heterocycle is an aromatic ring formed by carbon atoms and heteroatoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms. The aromatic heterocycle may be a monocyclic or condensed ring, and the number of atoms constituting the ring is preferably 5 to 20, more preferably 5 to 14. The number of heteroatoms in the ring is not particularly limited, but is preferably 1 to 3, more preferably 1 to 2.

[0076] Examples of heteroaryl groups include furyl, thienyl, pyrrolyl, imidazolyl, isothiazolyl, isoxazolyl, pyridyl, pyrazinyl, quinolyl, benzofuranyl (preferably 2-benzofuranyl), benzothiazolyl (preferably 2-benzothiazolyl), and benzoxazolyl (preferably 2-benzoxazolyl).

[0077] In the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0078] Effects of the Invention

[0079] The curable composition of the present invention exhibits excellent temporal stability in the state before the curing reaction, and can also achieve a high refractive index in the resulting cured product. The cured product, optical material, and diffractive optical element of the present invention can exhibit a high refractive index. The compound of the present invention can produce the curable composition of the present invention exhibiting the above-mentioned excellent properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] Figure 1 This is a schematic cross-sectional view schematically showing a method for producing the cured product of the present invention by imprint technology using the curable composition of the present invention. DETAILED DESCRIPTION

[0081] [Curable composition]

[0082] The curable composition of the present invention contains a compound represented by the following general formula (1) or (2).

[0083] In the present invention, the curable composition refers to a composition that has curability and can obtain a cured product (resin) through a curing reaction.

[0084] The compound represented by the general formula (1) or (2) described below contained in the curable composition of the present invention is Q 3 As shown, the naphthalene ring has R 1 The specific polymerizable group represented by Q 1 or Q 2 As shown, a polymerizable naphthalene sulfide compound has a substituent of a specific structure via a sulfide bond.

[0085] The compound represented by the general formula (1) or (2), having the above-mentioned specific chemical structure, when prepared as a curable composition, exhibits excellent temporal stability in the state of the curable composition before the curing reaction, thereby enabling the obtained cured product to achieve a high refractive index at a high level.

[0086] Hereinafter, the components contained in the curable composition of the present invention will be described in order.

[0087] <Compound represented by general formula (1) or (2)>

[0088] The curable composition of the present invention contains a compound represented by the following general formula (1) or (2).

[0089] [Chemical Formula 8]

[0090]

[0091] In the above formula, Q 1 represents a group represented by the following formula (q1a) or (q1b), Q 2 represents a group represented by the following formula (q2), Q 3 It represents a group represented by the following formula (q3).

[0092] [Chemical Formula 9]

[0093]

[0094] *-S-CH3 (q2) *-SR 1 (q3)

[0095] In the above formula, R 1 represents a (meth)acryloyl group, a vinyl group, or an allyl group. * represents a bonding bond.

[0096] In the group represented by formula (q1a), the substitution position of the methylsulfanyl group (-SCH3) on the benzene ring is not particularly limited. Regarding the bonding position of *-S-, the methylsulfanyl group can be bonded to any of the ortho, meta, and para positions, and is preferably bonded to the meta position.

[0097] Q 1 From the viewpoint of further increasing the liquid refractive index nD of the curable composition of the present invention and the refractive index nD of the cured product, the group represented by formula (q1a) is preferred, and from the viewpoint of further reducing the viscosity of the composition, the group represented by formula (q1b) is preferred.

[0098] R 1 It is preferably a (meth)acryloyl group, and more preferably an acryloyl group.

[0099] The compound represented by the general formula (1) or (2) is preferably a compound represented by the general formula (1) from the viewpoint of further increasing the liquid refractive index nD of the curable composition of the present invention and the refractive index nD of the cured product, and is preferably a compound represented by the general formula (2) from the viewpoint of further reducing the viscosity of the composition.

[0100] The curable composition of the present invention preferably contains a compound represented by general formula (1) from the viewpoint of further increasing the refractive index nD of the liquid and the refractive index nD of the cured product, and preferably contains a compound represented by general formula (2) from the viewpoint of further reducing the viscosity of the composition.

[0101] The substituent Q on the naphthalene ring in the general formula (1) 1 and Q 3 The substitution position of can be any one of the 1st to 8th positions of the naphthalene ring.

[0102] The substituent Q on the naphthalene ring in the general formula (2) 2 and Q 3 The substitution position of can be any one of the 1st to 8th positions of the naphthalene ring.

[0103] In the present invention, positions 1 to 8 of the naphthalene ring are numbered as follows.

[0104] [Chemical Formula 10]

[0105]

[0106] As a substituent (Q 1 ,Q 3 ) and the substitution position of the substituent (Q 2 ,Q 3 ) can be substituted at positions (1,5), (1,6), (2,6), (2,7), (5,1), (6,1), (6,2) and (7,2), preferably (1,5), (1,6), (2,7), (5,1), (6,1) or (7,2).

[0107] The compound represented by the general formula (1) or (2) preferably contains a substituent (Q 1 ,Q 3 ) is substituted at the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring, and the substituent (Q 2 ,Q 3) is substituted at the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring.

[0108] In the present invention, the substituent (Q 1 ,Q 3 ) is substituted at (1,5) position. 1 The substitution position is 1, and Q 3 The substitution position of the compound is 5-position, the substituent (Q 2 ,Q 3 ) is substituted at (1,5) position. 2 The substitution position is 1, and Q 3 The substitution position of is 5. The same applies to the other positions (1,6), (2,6), (2,7), (5,1), (6,1), (6,2), and (7,2).

[0109] The compound represented by the general formula (1) or (2) more preferably contains at least one compound represented by any one of the following general formulas (3) to (6).

[0110] Here, the compound represented by the general formula (3) and the compound represented by the general formula (5) correspond to the substituent (Q) in the general formula (1). 1 ,Q 3 ) is substituted at the (6,1) position and the substituent (Q 2 ,Q 3 ) is substituted at the (6,1) position. Furthermore, the compound represented by the general formula (4) and the compound represented by the general formula (6) are respectively equivalent to the substituent (Q 1 ,Q 3 ) is substituted at the (1,6) position and the substituent (Q 2 ,Q 3 ) is substituted at the (1,6) position.

[0111] [Chemical Formula 11]

[0112]

[0113] In the above formula, R 1 The meaning is the same as R in the above general formula (q3) 1 has the same meaning. 2 represents a hydrogen atom or a methylsulfanyl group.

[0114] R 2From the viewpoint of further increasing the refractive index nD of the liquid curable composition of the present invention and the refractive index nD of the cured product, a methylsulfanyl group is preferred, and from the viewpoint of further reducing the viscosity of the composition, a hydrogen atom is preferred.

[0115] In the compound represented by the general formula (1) or (2), the substituent (Q 1 ,Q 3 ) is substituted at the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring, and the substituent (Q 2 ,Q 3 The total content of compounds in which the substitution position of ) is the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring is, for example, preferably 20 mass % or more, more preferably 50 mass % or more, further preferably 65 mass % or more, especially preferably 80 mass % or more, and can be 100 mass %.

[0116] Regarding the “total content of the compound represented by any one of the general formulae (3) to (6)” in the compound represented by the general formulae (1) or (2), the above-mentioned “substituent (Q) in the general formula (1)” can also be applied. 1 ,Q 3 ) is substituted at the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring, and the substituent (Q 2 ,Q 3 ) is substituted at the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring”.

[0117] Preferred specific examples of the compound represented by the general formula (1) or (2) are listed below, but the present invention is not limited to these compounds.

[0118] [Chemical Formula 12]

[0119]

[0120] [Chemical Formula 13]

[0121]

[0122] The molecular weight of the compound represented by the above general formula (1) or (2) is preferably 232 to 600, more preferably 232 to 500, and even more preferably 232 to 400.

[0123] The compound represented by the general formula (1) or (2) can be synthesized by conventional methods. For example, the synthesis method described in Org. Lett., 2004, Vol. 6, No. 24, pp. 4587-4590, the synthesis method described in U.S. Patent Application Publication No. 2003 / 0195270, and the synthesis method described in J. Org. Chem., 2009, Vol. 74, No. 10, pp. 4005-4008 can be used for synthesis. In addition, the synthesis can be carried out by appropriately referring to the methods described in the Examples.

[0124] Furthermore, as described above, when the compounds represented by the general formula (1) or (2) are prepared into curable compositions containing these compounds, the resulting cured products can achieve a high refractive index. Furthermore, even when the concentration of the compound represented by the general formula (1) or (2) in the curable composition is high, the composition can exhibit excellent temporal stability.

[0125] When a curable composition of the present invention containing a compound represented by general formula (1) or (2) at a high concentration is prepared, the content of the compound represented by general formula (1) or (2) can be set to, for example, 99.99% by mass or less, preferably 99.95% by mass or less, more preferably 99.90% by mass or less, and further preferably 99.7% by mass or less. In this case, the lower limit of the content of the compound represented by general formula (1) or (2) can be set to, for example, 97% by mass or more, preferably 98% by mass or more, and more preferably 99.0% by mass or more. That is, the content of the compound represented by general formula (1) or (2) can be set to 97 to 99.99% by mass, preferably 98 to 99.95% by mass, more preferably 99.0 to 99.90% by mass, and further preferably 99.0 to 99.7% by mass. In this case, the curable composition of the present invention further does not contain a compound represented by general formula (7) described later.

[0126] Furthermore, when the curable composition of the present invention, which contains the compound represented by the general formula (1) or (2) at a high concentration, further contains a compound represented by the general formula (7) described later as a compound contributing to a high refractive index, the total content of the compound represented by the general formula (1) or (2) and the compound represented by the general formula (7) can be, for example, 99.99% by mass or less, preferably 99.95% by mass or less, more preferably 99.90% by mass or less, and even more preferably 99.7% by mass or less. In this case, the lower limit of the total content of the compound represented by the general formula (1) or (2) and the compound represented by the general formula (7) can be, for example, 97% by mass or more, preferably 98% by mass or more, and more preferably 99.0% by mass or more. That is, the total content of the compound represented by general formula (1) or (2) and the compound represented by general formula (7) can be set to 97 to 99.99% by mass, preferably 98 to 99.95% by mass, more preferably 99.0 to 99.90% by mass, and even more preferably 99.0 to 99.7% by mass.

[0127] The content of the compound represented by the general formula (1) or (2) in the total of the compound represented by the general formula (1) or (2) and the compound represented by the general formula (7) is not particularly limited, and can be, for example, 10 to 90% by mass, preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and even more preferably 30 to 70% by mass. The content of the compound represented by the general formula (7) in the total of the compound represented by the general formula (1) or (2) and the compound represented by the general formula (7) is not particularly limited, and can be, for example, 10 to 90% by mass, preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and even more preferably 30 to 70% by mass.

[0128] When the curable composition of the present invention contains a diluent monomer such as a difunctional (meth)acrylic acid thioester compound described later, the content of the compound represented by the general formula (1) or (2) in the curable composition of the present invention can be, for example, 60% by mass or more. From the perspective of further improving (further improving) the liquid refractive index nD of the curable composition of the present invention and the refractive index nD of the cured product of the present invention (both at 25°C and at a wavelength of 589 nm), it is preferably 65% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more. In this case, the upper limit of the content of the compound represented by the general formula (1) or (2) is not particularly limited, and can be, for example, 99% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. That is, the content of the compound represented by the general formula (1) or (2) is preferably 65 to 99% by mass, more preferably 70 to 95% by mass, even more preferably 75 to 90% by mass, and particularly preferably 75 to 85% by mass. In this case, the curable composition of the present invention further does not contain a compound represented by the general formula (7) described later.

[0129] Furthermore, when the curable composition of the present invention, which contains a diluent monomer such as a difunctional (meth)acrylic acid thioester compound described later, further contains a compound represented by the general formula (7) described later as a compound contributing to a high refractive index, the total content of the compound represented by the general formula (1) or (2) and the compound represented by the general formula (7) can be, for example, 60% by mass or more. From the viewpoint of further improving (further improving) the liquid refractive index nD of the curable composition of the present invention and the refractive index nD of the cured product of the present invention (both at 25° C. and at a wavelength of 589 nm), it is preferably 65% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more. In this case, the upper limit of the total content of the compound represented by the general formula (1) or (2) and the compound represented by the general formula (7) is not particularly limited, and can be, for example, 99% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. That is, the total content of the compound represented by general formula (1) or (2) and the compound represented by general formula (7) is preferably 65 to 99% by mass, more preferably 70 to 95% by mass, further preferably 75 to 90% by mass, and particularly preferably 75 to 85% by mass.

[0130] The content of the compound represented by the general formula (1) or (2) in the total of the compound represented by the general formula (1) or (2) and the compound represented by the general formula (7) is not particularly limited, and can be, for example, 10 to 90% by mass, preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and even more preferably 30 to 70% by mass. The content of the compound represented by the general formula (7) in the total of the compound represented by the general formula (1) or (2) and the compound represented by the general formula (7) is not particularly limited, and can be, for example, 10 to 90% by mass, preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and even more preferably 30 to 70% by mass.

[0131] In the curable composition of the present invention, the compound represented by the general formula (1) or (2) may contain one or more. That is, in the curable composition of the present invention, at least one of the compounds represented by the general formula (1) or (2) may be contained. In the case where at least one crystalline compound is used as the compound represented by the general formula (1) or (2), it is preferred to contain two or more compounds represented by the general formula (1) or (2) from the viewpoint of easily preparing a curable composition exhibiting excellent stability over time. In the case of containing two or more, the combination is not particularly limited, and only the compound represented by the general formula (1) may be two or more, only the compound represented by the general formula (2) may be two or more, or it may be a combination of one or more compounds represented by the general formula (1) and one or more compounds represented by the general formula (2).

[0132] In the curable composition of the present invention, as an embodiment containing two or more compounds represented by the general formula (1) or (2), for example, a embodiment containing a mixture of compounds represented by the general formula (1) or (2) obtained by synthesis can be mentioned.

[0133] When two or more compounds represented by general formula (1) or (2) are contained, the total content is preferably within the content range of the compounds represented by general formula (1) or (2). When two or more compounds represented by general formula (7) are contained, the total content is preferably within the content range of the compounds represented by general formula (7).

[0134] <Compound represented by general formula (7)>

[0135] The curable composition of the present invention preferably contains a compound represented by the following general formula (7) in addition to the compound represented by the above general formula (1) or (2).

[0136] [Chemical Formula 14]

[0137]

[0138] In the above formula, Q 4 and Q 5 represents a group represented by any one of the above formulas (q1a), (q1b), (q2) or (q3). 4 and Q 5 In the case where one of them is a group represented by any one of the above formula (q1a), (q1b) or (q2), and the other is a group represented by the above formula (q3).

[0139] Regarding the substituent Q 4 and Q 5 The combination of substituents that can be used is not particularly limited. For example, in the synthesis of the compound represented by the above general formula (1) or (2), a compound represented by the general formula (7) can be obtained as a by-product, wherein Q 4 and Q 5 are the same substituents.

[0140] The substituent Q on the naphthalene ring in the general formula (7) 4 and Q 5 The substitution position of can be any one of the 1st to 8th positions of the naphthalene ring.

[0141] Positions 1 to 8 of the naphthalene ring are numbered as described above.

[0142] As a substituent (Q 4 ,Q 5 ) can be substituted at positions (1,5), (1,6), (2,6), (2,7), (5,1), (6,1), (6,2) and (7,2), preferably (1,5), (1,6), (2,7), (5,1), (6,1) or (7,2).

[0143] The compound represented by the general formula (7) preferably contains a substituent (Q 4 ,Q 5 ) is substituted at the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring. More preferably, the compound comprises a substituent (Q 4 ,Q 5 ) is substituted at the (1,6) position or the (6,1) position of the naphthalene ring.

[0144] In the present invention, the substituent (Q 4 ,Q 5 ) is substituted at (1,5) position. 4 The substitution position is 1, and Q 5The substitution position of is 5. The same applies to the other positions (1,6), (2,6), (2,7), (5,1), (6,1), (6,2), and (7,2).

[0145] In the compound represented by the general formula (7), the substituent (Q 4 ,Q 5 The total content of compounds in which the substitution position of ) is the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring is, for example, preferably 20 mass % or more, more preferably 50 mass % or more, further preferably 65 mass % or more, especially preferably 80 mass % or more, and can be 100 mass %.

[0146] Regarding the "substituent (Q)" in the compound represented by the general formula (7) 4 ,Q 5 ) is substituted at the (1,6) position or the (6,1) position of the naphthalene ring”, and the above “substituent (Q in the general formula (7)” can also be applied. 4 ,Q 5 ) is substituted at the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring”.

[0147] Preferred specific examples of the compound represented by general formula (7) are listed below, but the present invention is not limited to these compounds.

[0148] [Chemical Formula 15]

[0149]

[0150] The molecular weight of the compound represented by the general formula (7) is preferably 220 to 600, more preferably 220 to 550, and even more preferably 220 to 500.

[0151] Regarding the method for synthesizing the compound represented by the general formula (7), the description regarding the method for synthesizing the compound represented by the general formula (1) or (2) can be appropriately cited and used.

[0152] The total content of the compound represented by the above-mentioned general formula (1) or (2) and the compound represented by the above-mentioned general formula (7) in the curable composition of the present invention, and the content of the compound represented by the above-mentioned general formula (7) in the total content of the compound represented by the above-mentioned general formula (1) or (2) and the compound represented by the above-mentioned general formula (7) are as described above.

[0153] When the curable composition of the present invention further contains a compound represented by the general formula (7) in addition to the compound represented by the general formula (1) or (2), the compound represented by the general formula (1) or (2) contained may be one or more, or two or more, and the compound represented by the general formula (7) may be one or more, or two or more.

[0154] When containing two or more compounds represented by general formula (1) or (2), the combination is not particularly limited. The compounds represented by general formula (1) alone may be two or more, the compounds represented by general formula (2) alone may be two or more, or the combination may be one or more compounds represented by general formula (1) and one or more compounds represented by general formula (2).

[0155] Furthermore, the compounds represented by the general formula (1) or (2) include both liquid (amorphous) compounds and crystalline compounds.

[0156] When the compound represented by the general formula (1) or (2) is a crystalline compound, from the viewpoint of being able to suppress the crystallization precipitation of the compound, it is preferred to prepare a mixture of two or more compounds represented by the general formula (1) or (2), or a mixture of two or more compounds represented by one or more compounds represented by the general formula (1) or (2) and one or more compounds represented by the general formula (7). From the viewpoint of being able to suppress the crystallization precipitation of the compound, it is more preferred to prepare a mixture of three or more compounds represented by the general formula (1) or (2), or a mixture of three or more compounds represented by one or more compounds represented by the general formula (1) or (2) and one or more compounds represented by the general formula (7).

[0157] The form containing three or more of the above compounds is not particularly limited, and examples thereof include a form containing a mixture of a compound represented by the general formula (1), a compound represented by the general formula (2), and a compound represented by the general formula (7) obtained by synthesis.

[0158] In this way, when the compound represented by general formula (1) or (2) is a liquid compound, it can be used directly. When it is a crystalline compound, it can be used as a mixture of the above two or more compounds (preferably a mixture of the above three or more compounds). As a result, it can be treated as a compound that suppresses crystallization, and the workability during the preparation of the curable composition is excellent, and crystallization of the prepared curable composition can also be suppressed.

[0159] Furthermore, the compounds represented by the general formula (1) or (2) include compounds having little coloration and compounds having slight coloration.

[0160] When the compound represented by general formula (1) or (2) is a slightly colored compound, it can be used as a mixture of two or more of the above compounds (preferably a mixture of three or more of the above compounds), thereby suppressing crystallization and allowing it to be treated as a compound with almost no coloring.

[0161] The coloration of the compound represented by general formula (1) or (2) can be evaluated by the transmittance at a wavelength of 450 nm. Therefore, the above-mentioned "slightly colored" means that the transmittance at a wavelength of 450 nm is less than 91% and less than 96%. "Almost no coloration" means that the transmittance at a wavelength of 450 nm is 96% or more.

[0162] In addition, the above-mentioned "transmittance of the compound represented by general formula (1) or (2) at a wavelength of 450 nm" is a value measured by spreading a melted sample to a thickness of 150 μm and using an ultraviolet-visible spectrophotometer (for example, UV-2600 (trade name), manufactured by Shimadzu Corporation), and the measurement conditions are as described in the examples described later.

[0163] <Other ingredients>

[0164] The curable composition of the present invention may further contain other components in addition to the compound represented by general formula (1) or (2) and the compound represented by general formula (7) that may be contained. Examples of such other components include a difunctional (meth)acrylic acid thioester compound and a photoradical polymerization initiator.

[0165] (Difunctional (meth)acrylic acid thioester compound)

[0166] The curable composition of the present invention preferably contains a difunctional (meth)acrylic acid thioester compound as a diluting monomer in addition to the compound represented by the above general formula (1) or (2) and optionally the compound represented by the general formula (7).

[0167] The difunctional (meth)thioacrylic acid ester compound is a compound having two (meth)acryloylthio groups.

[0168] There are no particular restrictions on the group linking two (meth)acryloylthio groups (hereinafter referred to as "linking group LL"), but it is not preferably a group having a branched structure. For example, it is more preferably a group in which a -CH2- that is not adjacent to the S atom in a linear alkylene group or one or two or more non-adjacent -CH2- in a linear alkylene group is replaced by -S-.

[0169] The linear alkylene group that can be used as the linking group LL preferably has 1 to 9 carbon atoms, more preferably 3 to 7 carbon atoms, and even more preferably 3 to 5 carbon atoms.

[0170] In the present invention, "a group in which one or two or more non-adjacent -CH2- groups in a linear alkylene group are substituted with -S-" means a group having an -S- bond in a linear alkylene group and not having a structure in which two or more S atoms are linked (for example, a disulfide structure or a polysulfide structure in which three or more S atoms are linked), and the bond to the (meth)acryloylthio group is -CH2-.

[0171] In a group in which one or two or more non-adjacent -CH2- in a straight-chain alkylene group is replaced by -S-, the description of the straight-chain alkylene group that can be adopted as the above-mentioned linking group LL can be preferably applied as the straight-chain alkylene group before -CH2- is replaced by -S-.

[0172] The molecular weight of the difunctional (meth)acrylic acid thioester compound is preferably 150 to 400, more preferably 200 to 350.

[0173] Preferred specific examples of the difunctional (meth)acrylic acid thioester compound are listed below, but the present invention is not limited to these compounds.

[0174] [Chemical Formula 16]

[0175]

[0176] Among these, the difunctional (meth)acrylic acid thioester compound is preferably the above-mentioned exemplified compound M-1 or M-2.

[0177] There is no particular limitation on the method for obtaining the difunctional (meth)acrylic acid thioester compound. The difunctional (meth)acrylic acid thioester compound can be commercially obtained or synthesized by conventional methods.

[0178] When the curable composition of the present invention contains a difunctional (meth) thioacrylate compound, the content of the difunctional (meth) thioacrylate compound in the curable composition of the present invention can be, for example, 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. The lower limit of the content of the difunctional (meth) thioacrylate compound is not particularly limited, and for example, it can be 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. That is, the content of the difunctional (meth) thioacrylate compound can be 1 to 40% by mass, preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and even more preferably 15 to 25% by mass.

[0179] The function of alleviating stress during thermal changes in the cured product can be adjusted by controlling the amount of the difunctional (meth)acrylic acid thioester compound in the curable composition.

[0180] When the curable composition of the present invention contains a difunctional (meth)acrylate thioester compound, the curable composition of the present invention may contain two or more difunctional (meth)acrylate thioester compounds. When containing two or more difunctional (meth)acrylate thioester compounds, the total content is preferably within the above range.

[0181] (Photoradical polymerization initiator)

[0182] The curable composition of the present invention preferably contains a photoradical polymerization initiator. The curable composition of the present invention can obtain a cured product exhibiting a high refractive index through photopolymerization based on the action of the photoradical polymerization initiator. As the photoradical polymerization initiator, compounds commonly used as photoradical polymerization initiators can be appropriately used according to the conditions of the photopolymerization (photocuring) step described below. Specifically, the following compounds can be used.

[0183] For example, α-acylphosphine oxide compounds such as 1,2-diphenylethanedione and methyl phenylglyoxylate; bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,4,4-trimethylpentylphosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and ethylphenyl(2,4,6-trimethylbenzoyl)phosphinate (also known as (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide); 1-phenyl-2-hydroxy-2-nitropropane; α-Hydroxyketone compounds such as α-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methylpropane-1-one; benzyl ketal compounds such as 2,2-dimethoxy-1,2-diphenylethane-1-one; α-aminoketone compounds such as 2-methyl-1-(4-methylphenylthio)-2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone; 1-[4-(phenylthio)phenyl]octane-1,2-dione = 2-(O-benzoyl oxime) (available from BASF Japan Ltd.), oxime ester compounds such as Irgacure OXE01 (product name) (available from BASF Japan Ltd.), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone=O-acetoxime (Irgacure OXE02 (product name) available from BASF Japan Ltd.), Irgacure OXE03 and Irgacure OXE04 (all product names, available from BASF Japan Ltd.), and ADEKA ARKLS N-1919T, ADEKA ARKLS NCI-831E, ADEKA ARKLS NCI-930, and ADEKA ARKLS NCI-730 (all product names, available from ADEKA CORPORATION).

[0184] Among them, in the present invention, as the photoradical polymerization initiator, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 (product name) available from BASF Japan Ltd.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Irgacure 819 (product name) available from BASF Japan Ltd.), (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (Irgacure TPO (product name) available from BASF Japan Ltd.), 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651 (product name)), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropane-1-one, 2-methyl-1-(4-methylphenylthio)-2-morpholinopropane-1-one, ethylphenyl(2,4,6-trimethylbenzoyl)phosphonate (Irgacure TPO-L (product name) available from BASF Japan Ltd.) or ADEKA ARKLS NCI-831E (product name, available from ADEKA CORPORATION).

[0185] The photoradical polymerization initiator may be contained alone or in combination of two or more.

[0186] When a photoradical polymerization initiator is contained, the content of the photoradical polymerization initiator in the curable composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 1.0% by mass, and even more preferably 0.05 to 0.5% by mass.

[0187] The curable composition of the present invention containing the compound represented by general formula (1) or (2) may contain polymers or monomers other than the above-mentioned components, dispersants, plasticizers, heat stabilizers, release agents, solvents, etc., as long as it does not deviate from the gist of the present invention.

[0188] When used as an imprint material, the content of inorganic particles in the curable composition is preferably suppressed to 30% by mass or less, and more preferably no inorganic particles are contained.

[0189] The viscosity of the curable composition of the present invention at 60°C is preferably less than 50 mPa·s, more preferably less than 35 mPa·s, even more preferably less than 30 mPa·s, and particularly preferably less than 25 mPa·s, from the perspective of improving workability during formation of the cured product, particularly improving mold followability during imprinting, and thus forming a higher quality cured product. The lower limit is not particularly limited, but is practically 1 mPa·s or greater.

[0190] The viscosity of the curable composition is measured using a rheometer (for example, trade name: HAAKE Rheostress 6000, manufactured by Thermo Scientific) by the method described in the Examples below. 1 mPa·s is 1 cP.

[0191] The liquid refractive index of the curable composition of the present invention can be evaluated using the refractive index (nD) at 25° C. and a wavelength of 589 nm (also referred to simply as “liquid refractive index nD of the curable composition” in the present invention).

[0192] The liquid refractive index nD of the curable composition of the present invention can be 1.650 or higher, preferably 1.660 or higher, and more preferably 1.670 or higher. The upper limit of the liquid refractive index nD of the curable composition of the present invention is not particularly limited, but is practically 1.750 or lower.

[0193] The liquid refractive index nD of the curable composition is a value measured using an Abbe refractometer (e.g., multi-wavelength Abbe refractometer DR-M2 or DR-M4, manufactured by ATAGO CO., LTD.). Specifically, the measurement can be performed by preparing a sample (curable composition) for measurement as described in the Examples below. Furthermore, reference can be made to JIS (Japanese Industrial Standards) B 7090:1999 Optics and optical instruments - Standard wavelengths (ISO (International Organization for Standardization) 7944:1998 Optics and optical instruments - Reference wavelengths), as appropriate.

[0194] The curable composition of the present invention can be used for production of a cured product requiring a high refractive index.

[0195] Among them, the curable composition of the present invention is excellent in stability over time and therefore can be used as a material for imprinting such as nanoimprinting, and can be preferably used in the production of a cured product exhibiting a high refractive index.

[0196] 〔Cured product〕

[0197] The cured product of the present invention is a cured product obtained from the curable composition of the present invention, and is a cured product obtained by curing the curable composition containing the compound represented by the above-mentioned general formula (1) or (2).

[0198] The cured product of the present invention is obtained by polymerizing a monomer containing a compound represented by the general formula (1) or (2) and curing the resulting product. The cured product of the present invention may contain unreacted monomers (e.g., a compound represented by the general formula (1) or (2), a compound represented by the general formula (7), a difunctional (meth)acrylic acid thioester compound, etc.).

[0199] As described above, the cured product of the present invention can express a high refractive index.

[0200] The refractive index of the cured product of the present invention can be evaluated using the refractive index (nD) at 25° C. and a wavelength of 589 nm (also referred to simply as “refractive index nD of the cured product” in the present invention).

[0201] The refractive index nD of the cured product of the present invention can be 1.670 or more, preferably 1.680 or more, more preferably 1.690 or more, and even more preferably 1.700 or more. In the region where the refractive index nD of the cured product is 1.670 or more, according to 10 -3 The difference in grades results in different high refractive index performance when used in optical components.

[0202] The upper limit of the refractive index nD of the cured product of the present invention is not particularly limited, but is practically 1.800 or less.

[0203] The refractive index nD of the cured product is a value measured using an Abbe refractometer (e.g., multi-wavelength Abbe refractometer DR-M2 or DR-M4, manufactured by ATAGO CO., LTD.). Specifically, a sample for measurement (cured product) can be prepared and measured according to the description in the Examples described below. Furthermore, when forming the cured product, a heating step may be used instead of the ultraviolet irradiation step described in the Examples described below, or both a heating step and an ultraviolet irradiation step may be used. Furthermore, reference may be made to JIS B 7090:1999 Optics and optical instruments - Reference wavelengths (ISO 7944:1998 Optics and optical instruments - Reference wavelengths), as appropriate.

[0204] The transmittance of the cured product of the present invention is preferably 85% or greater, more preferably 90% or greater, and even more preferably 95% or greater, over the entire visible light wavelength range of 360 to 830 nm. The upper limit of the transmittance of the cured product of the present invention is not particularly limited, but is practically 99% or less.

[0205] The transmittance of the cured product is a value of external transmittance including surface reflection measured for a cured product having a thickness of 150 μm using an ultraviolet-visible spectrophotometer (eg, UV-2600 (product name), manufactured by Shimadzu Corporation).

[0206] [Method for producing cured product]

[0207] The cured product of the present invention can be produced by a method comprising the step of photocuring the above-mentioned curable composition. When photocuring is performed, it is preferred that the curable composition contain the above-mentioned photoradical polymerization initiator.

[0208] Regarding the conditions for photocuring, the description of light irradiation in a diffractive optical element described later can be preferably applied.

[0209] In the method for producing a cured product of the present invention, it is preferred that the curable composition of the present invention is pressed against a casting mold (die) and photocured to obtain a cured product to which the pattern of the casting mold (die) is transferred.

[0210] From the perspective of releasability, the casting mold (die) is preferably one that has been surface-treated with chromium nitride. For example, the description of the chromium nitride treatment in paragraph

[0108] of International Publication No. 2019 / 044863 can be directly applied, except that "mold" is read as "casting mold (die)".

[0211] Figure 1 This is a schematic cross-sectional view schematically illustrating a method for producing a cured product of the present invention using the curable composition of the present invention by an imprint technique. Furthermore, the size, shape, and thickness of the substrate 3, the size, shape, transfer pattern, and thickness of the mold (die) 5, and the amount of curable composition 1 used can be appropriately adjusted to obtain a cured product 7 having the desired size, shape, transferred pattern, and thickness.

[0212] like Figure 1 As shown, (a) a curable composition 1 is first clamped between a casting mold (die) 5 and a substrate 3, (b) the curable composition 1 is pressed while being engraved on the casting mold (die) 5, and the curable composition 1 is photocured by ultraviolet irradiation (UV irradiation), thereby producing a cured product 7 having a pattern transferred to the casting mold (die) 5, and (c) the cured product 7 can be produced by demolding (peeling off) the obtained cured product 7 and the substrate 3 from the casting mold (die) 5.

[0213] Furthermore, there is no particular limitation on ultraviolet irradiation as long as the curable composition 1 is cured, and irradiation may be performed from either the mold 5 or the substrate 3. Preferably, the substrate 3 is transparent and irradiation is performed from the substrate 3 side.

[0214] The obtained cured product 7 may be used in a form integrated with the substrate 3 or in a form consisting of the cured product 7 after the substrate 3 is separated.

[0215] Regarding the substrate 3 , the description of the transparent substrate in the diffractive optical element described later can be preferably applied.

[0216] [Applications of Cured Products]

[0217] The cured product of the present invention can be used in various applications. Due to its high refractive index, it is preferably used as an optical material, particularly a diffractive optical element. The diffractive optical element of the present invention can be used, for example, as a diffractive optical element for waveguides in augmented reality glasses (AR glasses).

[0218] Diffractive optical element

[0219] The diffractive optical element of the present invention includes a surface having a diffraction grating shape formed from the cured product of the present invention, and is formed by curing the curable composition of the present invention.

[0220] The maximum thickness of the diffraction optical element of the present invention is preferably 0.05 μm to 100 μm. The maximum thickness is more preferably 0.1 μm to 50 μm, and further preferably 0.2 μm to 30 μm. Furthermore, the step difference (grating thickness) of the diffraction grating shape (periodic structure) possessed by the diffraction optical element is preferably 0.05 μm to 100 μm, more preferably 0.05 μm to 50 μm, and further preferably 0.1 μm to 30 μm. In addition, the pitch of the diffraction grating shape possessed by the diffraction optical element can be between 0.05 μm and 1 mm, and is also preferably set to 0.05 μm to 100 μm, and is preferably changed within the same diffraction optical element according to the required optical aberration.

[0221] The diffractive optical element can be manufactured through the following steps, for example.

[0222] The curable composition is clamped between the surface of a mold, such as a casting mold, having a surface processed into a diffraction grating shape, and a transparent substrate. Thereafter, the curable composition may be pressurized and stretched to a desired range. While clamped, light is irradiated from the transparent substrate side to cure the curable composition. The cured product is then demolded from the mold, such as a casting mold. After demolding, ultraviolet irradiation may be further performed from the side opposite to the transparent substrate side.

[0223] Examples of the transparent substrate include flat glass such as BK glass and flat transparent resins (such as (meth)acrylic resin, polycarbonate resin, and polyethylene terephthalate). The surface of the transparent substrate may be subjected to a surface treatment such as ozone treatment.

[0224] The transparent substrate used in the above-mentioned production may be directly contained in the diffractive optical element or may be peeled off.

[0225] The light used in the light irradiation for curing the curable composition is preferably ultraviolet light or visible light, more preferably ultraviolet light. For example, a metal halide lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a germicidal lamp, a xenon lamp, an LED (Light Emitting Diode) light source lamp, etc. can be preferably used. The illuminance of the ultraviolet light used in the light irradiation for curing the curable composition is preferably 1 to 100 mW / cm 2 , more preferably 1 to 75 mW / cm 2 , more preferably 5 to 50 mW / cm 2 The UV light exposure may be multiple times with different intensities. The UV light exposure is preferably 0.4 to 10 J / cm 2 , more preferably 0.5 to 5 J / cm 2 , more preferably 1 to 3 J / cm 2 The atmosphere during light irradiation is preferably air or an inert gas-substituted atmosphere, and more preferably an atmosphere in which air is substituted with nitrogen until the oxygen concentration becomes 1% or less.

[0226] The curable composition of the present invention is used as an imprint material. A mold (die) having a desired pattern ranging in size from nanometers to hundreds of micrometers is pressed onto the material. The mold is then photocured to produce a cured product of the present invention having the pattern transferred from the mold. The diffraction grating shape can then be produced by demolding.

[0227] Regarding the photocuring conditions, the description in the method for producing a cured product and the description in the production of a diffractive optical element can be applied.

[0228] Regarding the above-mentioned aspects, descriptions of commonly used imprinting can be adopted without particular limitation. For example, reference can be made to Handbook of Nanoimprint Technology (edited by the Society of Applied Physics and Nanoimprint Technology Research Group, published by Ohmsha, Ltd., December 1, 2019).

[0229] Example

[0230] The present invention will be described in further detail below with reference to the examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the purpose of the present invention. Thus, the scope of the present invention is not to be interpreted as limited by the specific examples shown below. In addition, in the following, room temperature refers to 25°C unless otherwise specified.

[0231] In addition, all steps from the preparation of the curable composition to the production of the cured product and the evaluation test were performed under an environment illuminated by a yellow light.

[0232] [Synthesis example]

[0233] The compound represented by the general formula (1) or (2) and the compound represented by the general formula (7) were synthesized as follows.

[0234] [Synthesis Example 1: Synthesis of Compounds (A-4) and (A-5)]

[0235] [Chemical Formula 17]

[0236]

[0237] <Synthesis of Compounds (A-4A) and (A-5A)>

[0238] 12.8 g (66.8 mmol) of 1,6-naphthalenedithiol, 12.9 g (63.6 mmol) of 3-bromothioanisole, 95 mL of N,N-dimethylacetamide (DMAc), and 18.0 g (130.4 mmol) of potassium carbonate were mixed and the atmosphere was purged with nitrogen. Then, 2.91 g (3.18 mmol) of tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) and 3.68 g (6.36 mmol) of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) were added and heated to an internal temperature (liquid temperature) of 120°C. After stirring for 5 hours, 800 mL of ethyl acetate and 800 mL of 1N hydrochloric acid were added, the insoluble matter was filtered, and the mixture was washed and separated. Next, 800 mL of water was added, the mixture was stirred, and the mixture was washed and separated. After dehydration with magnesium sulfate, filtration, and concentration, an oily composition was obtained, which was then purified by column chromatography to obtain 5.2 g of a mixture of compound (A-4A) and compound (A-5A), with a yield of 26%.

[0239] <Synthesis of Compounds (A-4) and (A-5)>

[0240] A mixture of 3.0 g (9.5 mmol) of compound (A-4A) and compound (A-5A) and 5 mL of N,N-dimethylacetamide (DMAc) were mixed and cooled to an internal temperature (liquid temperature) of 0°C. 1.33 g (10.5 mmol) of 3-chloropropionyl chloride (3CPC) was added dropwise to adjust the liquid temperature to 7°C or lower, and then heated to an internal temperature (liquid temperature) of 25°C. After stirring for 1 hour, the mixture was cooled to 0°C, 2.31 g (22.9 mmol) of triethylamine (TEA) was added dropwise to adjust the liquid temperature to 7°C or lower, and then heated to an internal temperature (liquid temperature) of 25°C. After stirring for 1 hour, 20 mL of ethyl acetate and 20 mL of 1N hydrochloric acid were added, the insoluble matter was filtered out, and then washed and separated. Next, 20 mL of a 5% aqueous sodium bicarbonate solution was added, stirred, washed, and separated. After dehydration, filtration, and concentration using magnesium sulfate, an oily composition was obtained, which was then purified by column chromatography to obtain 1.83 g of a mixture of compound (A-4) and compound (A-5). The yield was 52%. Analysis by high-performance liquid chromatography (HPLC) and calculation of the concentration of each compound based on the area at a wavelength of 254 nm for compound (A-4) and compound (A-5) revealed a composition ratio of compound (A-4):compound (A-5) = 45% by mass:55% by mass.

[0241] Compound (A-4) 1 H-NMR (300MHz, CDCl3): δ (ppm) 2.45 (s, 3H), 5.8-5.9 (m, 1H), 6.4-6.6 (m, 2H), 7.1-7.5 (m, 8H), 7.9-8.1 (m, 2H)

[0242] Compound (A-5) 1 H-NMR (300MHz, CDCl3): δ (ppm) 2.45 (s, 3H), 5.8-5.9 (m, 1H), 6.4-6.6 (m, 2H), 7.1-7.5 (m, 8H), 7.9-8.1 (m, 1H), 8.2-8.3 (m, 1H)

[0243] [Synthesis Example 2: Synthesis of Compounds (A-21) and (A-22)]

[0244] A mixture of compound (A-21) and compound (A-22) described later was synthesized in the same manner as in Synthesis Example 1, except that 3-bromothioanisole was replaced with bromobenzene (yield 28%). The concentrations of each compound were calculated based on the area at a wavelength of 254 nm for compound (A-21) and compound (A-22), and the composition ratio calculated based on these results was compound (A-21):compound (A-22) = 45% by mass:55% by mass.

[0245] Compound (A-21) 1 H-NMR (300MHz, CDCl3): δ (ppm) 5.8-5.9 (m, 1H), 6.4-6.6 (m, 2H), 7.1-7.7 (m, 9H), 7.9-8.1 (m, 2H)

[0246] Compound (A-22) 1 H-NMR (300MHz, CDCl3): δ (ppm) 5.8-5.9 (m, 1H), 6.4-6.6 (m, 2H), 7.1-7.7 (m, 9H), 7.9-8.1 (m, 1H), 8.2-8.3 (m, 1H)

[0247] [Synthesis Example 3: Synthesis of Compounds (B-4) and (B-5)]

[0248] [Chemical Formula 18]

[0249]

[0250] <Synthesis of Compounds (B-4A) and (B-5A)>

[0251] While mixing 18.6 g (96.9 mmol) of 1,6-naphthalenedithiol, 13.7 g (96.9 mmol) of iodomethane, and 240 mL of N,N-dimethylacetamide (DMAc), the mixture was cooled until the internal temperature (liquid temperature) reached 0°C. After adding 13.2 g (101.8 mmol) of N,N-diisopropylethylamine (DIPEA) dropwise so that the liquid temperature did not exceed 7°C, the mixture was heated until the internal temperature (liquid temperature) reached 25°C. After stirring for 1 hour, 800 mL of ethyl acetate and 800 mL of 1N hydrochloric acid were added, washed, and separated. Subsequently, 800 mL of water was added, stirred, washed, and separated. After dehydration, filtration, and concentration based on magnesium sulfate, an oily composition was obtained, which was then purified by column chromatography to obtain 6.8 g of a mixture of compound (B-4A) and compound (B-5A). The yield was 34%.

[0252] <Synthesis of Compounds (B-4) and (B-5)>

[0253] A mixture of 5.0 g (24.2 mmol) of compound (B-4A) and compound (B-5A) and 12 mL of N,N-dimethylacetamide (DMAc) were mixed and cooled to an internal temperature (liquid temperature) of 0°C. 3.38 g (26.7 mmol) of 3-chloropropionyl chloride (3CPC) was added dropwise to adjust the liquid temperature to 7°C or lower, and then heated to an internal temperature (liquid temperature) of 25°C. After stirring for 1 hour, the mixture was cooled to 0°C, 5.89 g (58.1 mmol) of triethylamine (TEA) was added dropwise to adjust the liquid temperature to 7°C or lower, and then heated to an internal temperature (liquid temperature) of 25°C. After stirring for 1 hour, 40 mL of ethyl acetate and 40 mL of 1N hydrochloric acid were added, the insoluble matter was filtered out, and then the mixture was washed and separated. Next, 40 mL of a 5% aqueous sodium bicarbonate solution was added and stirred, and then the mixture was washed and separated. After dehydration, filtration and concentration based on magnesium sulfate, an oily composition was obtained, which was then purified by column chromatography to obtain a mixture of 3.2 g of compound (B-4) and compound (B-5). Yield 51%. By high performance liquid chromatography (HPLC) analysis, the concentration of each compound was calculated based on the area under a wavelength of 254 nm for compound (B-4) and compound (B-5). The composition ratio calculated based on these results was compound (B-4): compound (B-5) = 43% by mass: 57% by mass. Furthermore, a portion of the mixture was purified again by column chromatography (eluent: a mixed solution of toluene and hexane) to separate compound (B-4) and compound (B-5).

[0254] Compound (B-4) 1 H-NMR (300MHz, CDCl3): δ (ppm) 2.58 (s, 3H), 5.8-5.9 (m, 1H), 6.4-6.6 (m, 2H), 7.3-7.5 (m, 2H), 7.6-7.7 (m, 2H), 7.8-7.9 (m, 1H), 8.0-8.1 (m, 1H)

[0255] Compound (B-5) 1 H-NMR (300MHz, CDCl3): δ (ppm) 2.58 (s, 3H), 5.8-5.9 (m, 1H), 6.4-6.6 (m, 2H), 7.4-7.5 (m, 3H), 7.6-7.7 (m, 1H), 7.9-8.0 (m, 1H), 8.34 (d, 1H)

[0256] [Synthesis Example 4: Synthesis of a mixture of compounds (B-4), (B-5), (C-1) and (C-2)]

[0257] [Chemical Formula 19]

[0258]

[0259] <Synthesis of Compounds (B-4A), (B-5A), (C-1), and 1,6-Naphthalenedithiol Mixture>

[0260] While mixing 18.6 g (96.9 mmol) of 1,6-naphthalenedithiol, 13.7 g (96.9 mmol) of iodomethane, and 240 mL of N,N-dimethylacetamide (DMAc), the mixture was cooled until the internal temperature (liquid temperature) reached 0°C. After adding 13.2 g (101.8 mmol) of N,N-diisopropylethylamine (DIPEA) dropwise so that the liquid temperature did not exceed 7°C, the mixture was heated until the internal temperature (liquid temperature) reached 25°C. After stirring for 1 hour, 800 mL of ethyl acetate and 800 mL of 1N hydrochloric acid were added, followed by washing and liquid separation. Subsequently, 800 mL of water was added, stirred, washed, and liquid separated. By dehydration with magnesium sulfate, filtration, and concentration, 19.5 g of a mixture of compound (B-4A), compound (B-5A), compound (C-1), and 1,6-naphthalenedithiol was obtained as an oily composition. The yield was 98%.

[0261] <Synthesis of a mixture of compounds (B-4), (B-5), (C-1), and (C-2)>

[0262] A mixture of 5.0 g (24.2 mmol) of compound (B-4A), compound (B-5A), compound (C-1), and 1,6-naphthalenedithiol and 12 mL of N,N-dimethylacetamide (DMAc) was mixed and cooled to an internal temperature (liquid temperature) of 0°C. 3.38 g (26.7 mmol) of 3-chloropropionyl chloride (3CPC) was added dropwise to keep the liquid temperature below 7°C, and then heated to an internal temperature (liquid temperature) of 25°C. After stirring for 1 hour, the mixture was cooled to 0°C, 5.89 g (58.1 mmol) of triethylamine (TEA) was added dropwise to keep the liquid temperature below 7°C, and then heated to an internal temperature (liquid temperature) of 25°C. After stirring for 1 hour, 40 mL of ethyl acetate and 40 mL of 1N hydrochloric acid were added, the insoluble matter was filtered, and then washed and separated. Next, 40 mL of a 5% aqueous sodium bicarbonate solution was added, stirred, and then washed and separated. After dehydration, filtration and concentration based on magnesium sulfate, an oily composition was obtained, which was then purified by column chromatography to obtain 5.4 g of a mixture of compound (B-4), compound (B-5), compound (C-1) and compound (C-2). The yield was 85%. By high performance liquid chromatography (HPLC) analysis, the concentration of each compound was calculated based on the area under a wavelength of 254 nm for compound (B-4), compound (B-5), compound (C-1) and compound (C-2). The composition ratio calculated based on these results was compound (B-4): compound (B-5): compound (C-1): compound (C-2) = 20 mass %: 25 mass %: 25 mass %: 30 mass %.

[0263] [Synthesis Example 5: Synthesis of a mixture of compounds (B-4), (B-5) and (C-2)]

[0264] Compound (C-1) was removed during purification by column chromatography in Synthesis Example 4, and Compound (B-4), Compound (B-5), and Compound (C-2) were separated (yield 63%). Analysis by high-performance liquid chromatography (HPLC) calculated the concentration of each compound based on the area at a wavelength of 254 nm for Compound (B-4), Compound (B-5), and Compound (C-2). The composition ratio calculated from these results was Compound (B-4): Compound (B-5): Compound (C-2) = 28% by mass: 34% by mass: 38% by mass.

[0265] [Synthesis Example 6: Synthesis of Compound (C-1)]

[0266] While mixing 5.0 g (26.0 mmol) of 1,6-naphthalenedithiol, 7.4 g (52.0 mmol) of iodomethane, and 65 mL of N,N-dimethylacetamide (DMAc), the mixture was cooled until the internal temperature (liquid temperature) reached 0°C. After adding 7.1 g (54.6 mmol) of N,N-diisopropylethylamine (DIPEA) dropwise so that the liquid temperature did not exceed 7°C, the mixture was heated until the internal temperature (liquid temperature) reached 25°C. After stirring for 1 hour, 50 mL of ethyl acetate and 50 mL of 1N hydrochloric acid were added, washed, and separated. Then, 50 mL of water was added and stirred, followed by washing and separation. After dehydration, filtration, and concentration based on magnesium sulfate, the mixture was purified by column chromatography to obtain 5.4 g of compound (C-1). The yield was 95%.

[0267] 1 H-NMR (300MHz, CDCl3): δ (ppm) 2.56 (s, 3H), 2.59 (s, 3H), 7.3-7.4 (m, 1H), 7.4-7.5 (m, 2H), 7.5-7.6 (m, 2H), 8.2 (d, 1H)

[0268] [Synthesis Example 7: Synthesis of Compound (C-2)]

[0269] 5.0 g (26.0 mmol) of 1,6-naphthalenedithiol and 12.5 mL of N,N-dimethylacetamide (DMAc) were mixed and cooled to an internal temperature (liquid temperature) of 0°C. 7.3 g (57.2 mmol) of 3-chloropropionyl chloride (3CPC) was added dropwise to keep the liquid temperature below 7°C, and then heated to an internal temperature (liquid temperature) of 25°C. After stirring for 8 hours, the mixture was cooled to 0°C, 11.6 g (114 mmol) of triethylamine (TEA) was added dropwise to keep the liquid temperature below 7°C, and then heated to an internal temperature (liquid temperature) of 25°C. After stirring for 1 hour, 50 mL of ethyl acetate and 50 mL of 1N hydrochloric acid were added, insoluble matter was filtered, and the mixture was washed and separated. Next, 50 mL of a 5% aqueous sodium bicarbonate solution was added, stirred, and then washed and separated. The oily composition was obtained by dehydration with magnesium sulfate, filtration, and concentration, and then purified by column chromatography to obtain 6.6 g of compound (C-2). The yield was 85%.

[0270] 1 H-NMR (300MHz, CDCl3): δ (ppm) 5.8-5.9 (m, 2H), 6.4-6.6 (m, 4H), 7.5-7.6 (m, 2H), 7.7-7.8 (m, 1H), 7.9-8.0 (m, 1H), 8.05 (s, 1H), 8.23 (d, 1H)

[0271] [Example 1: Preparation of curable composition]

[0272] The compound represented by general formula (1) or (2), the compound represented by general formula (7) or the comparative compound, and the diluent monomer, namely the difunctional (meth)acrylic acid thioester compound M, were mixed to the composition shown in Table 1 below. The mixture was dissolved in ethyl acetate and then concentrated at 60°C and 40 hPa under reduced pressure until the ethyl acetate disappeared. A photoradical polymerization initiator (referred to as "photopolymerization initiator" in Table 1) was added to the obtained concentrate, and the mixture was stirred while heating to 60°C to obtain a uniform mixture, thereby preparing a curable composition.

[0273] Curable compositions No. 101 to 107 are compositions containing the compound represented by the general formula (1) or (2) of the present invention, and curable composition No. c11 is a composition containing a comparative compound for comparison instead of the compound represented by the general formula (1) or (2) of the present invention.

[0274] [Example 2: Preparation of Cured Material]

[0275] The curable composition prepared above was sandwiched between hydrophobized glass plates so that the film thickness of the cured product became 150 μm. A UV irradiation apparatus (EXECURE 3000 (product name), manufactured by HOYA CANDEO OPTRONICS) was used in an atmosphere substituted with nitrogen (N2) with an oxygen concentration of 1% or less, and the integrated light intensity was 1.2 J / cm 2 , illumination 5mW / cm 2 After UV (ultraviolet) irradiation under conditions of , the film was peeled off from the glass plate to produce a cured product.

[0276] Furthermore, the transmittance values of the 150 μm-thick cured products of curable compositions Nos. 101 to 107 prepared above, as measured by the above-mentioned measurement method, were all 85% or higher over the entire visible light wavelength range of 360 to 830 nm.

[0277] [Evaluation 1] Refractive index

[0278] The refractive index (nD) of the measurement sample at a wavelength of 589 nm was measured at 25°C using a multi-wavelength Abbe refractometer DR-M2 or DR-M4 (product name, manufactured by ATAGO CO., LTD.). The measurement sample used the curable composition prepared above for the liquid refractive index nD of the composition, and the cured product prepared above with a film thickness of 150 μm for the refractive index nD. The refractive index nD of the cured product was evaluated according to the following criteria.

[0279] The results are summarized in Table 1. In addition, regarding the refractive index nD of the cured product, specific values are shown in parentheses in the table together with the evaluation results.

[0280] -Evaluation criteria for the refractive index nD of cured products-

[0281] A:1.700≤nD

[0282] B: 1.690≤nD<1.700

[0283] C: 1.680≤nD<1.690

[0284] D: 1.670≤nD<1.680

[0285] E:nD<1.670

[0286] [Evaluation 2] Viscosity measurement

[0287] The shear rate of the curable composition prepared above was measured using a rheometer (product name: HAAKE Rheostress 6000, manufactured by Thermo Scientific). -1 , and viscosity η at 60°C, and were evaluated according to the following criteria. 1 cP is 1 mPa·s.

[0288] The results are summarized in Table 1. Specific values are shown in parentheses along with the evaluation results. However, the viscosity values in the table are described with the unit "cP" omitted.

[0289] -Evaluation criteria for viscosity-

[0290] A:η<25cP

[0291] B: 25cP≤η<30cP

[0292] C: 30cP≤η<35cP

[0293] D: 35cP≤η<50cP

[0294] [Evaluation 3] Temporal stability of liquid

[0295] The curable composition prepared above was stored at 25°C for one week. The presence of crystallization and / or turbidity over time was visually observed, and the temporal stability of the liquid was evaluated according to the following criteria. Storage was performed under yellow light.

[0296] -Evaluation criteria for temporal stability of liquids-

[0297] A: Neither crystal precipitation nor turbidity occurred, and the solution remained transparent.

[0298] B: At least one of turbidity and crystal precipitation slightly occurred.

[0299] C: At least one of turbidity and crystal precipitation occurred, and a significant change occurred.

[0300]

[0301] Notes

[0302] The blending amount (wt%) of each component described in the column of each component refers to mass %.

[0303] The ratio of each component described in the column of "Main Monomer" refers to the content ratio of each compound constituting the main monomer, and wt% refers to mass%. When the main monomer is a mixture of two or more types of compounds, the content ratio of each compound is described in the order of the compounds described in the "Type" column.

[0304] The main monomers in curable compositions Nos. 101 to 103 refer to mixtures of compounds represented by formula (1) or (2) obtained in Synthesis Examples 1 to 3, respectively, and the blending amounts refer to the blending amounts of the mixture.

[0305] Furthermore, the main monomers in curable compositions No. 106 and 107 refer to mixtures of the compounds represented by general formula (1) or (2) and the compound represented by general formula (7) obtained by the above-mentioned Synthesis Examples 4 and 5, respectively, and the blending amounts refer to the blending amounts as a mixture.

[0306] The components in the table are as follows.

[0307] Main monomer: represents a compound represented by the following general formula (1) or (2), a compound represented by the general formula (7), or a comparative compound.

[0308] (Compound represented by general formula (1) or (2))

[0309] [Chemical Formula 20]

[0310]

[0311] (Compound represented by general formula (7))

[0312] [Chemical Formula 21]

[0313]

[0314] (Comparative Compound)

[0315] [Chemical Formula 22]

[0316]

[0317] Comparative compound Z-1 is the polymerizable compound (A-1) described in paragraph

[0129] used in the examples of JP-A-2018-104696.

[0318] Diluting monomer: represents the following difunctional (meth)acrylic acid thioester compound M.

[0319] (Difunctional (meth)acrylic acid thioester compound M)

[0320] [Chemical Formula 23]

[0321]

[0322] (Photopolymerization initiator)

[0323] IrgTPO: Irgacure TPO (product name, manufactured by BASF Japan Ltd., available as Omnirad TPOH (product name, manufactured by IGM Resins BV)), diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide

[0324] The following can be seen from the results in Table 1.

[0325] Comparative compound Z-1 has an acryloyloxy group as a functional group, and the acryloyloxy group and the naphthalene ring are connected by -S-phenylene-CH2-. 1 or Q 2 From the perspective of the specific substituents represented by the compound, it is not a compound represented by the general formula (1) or (2) of the present invention. In the curable composition No. c11 containing the comparative compound Z-1, the temporal stability of the composition (liquid) was poor, and the refractive index nD of the obtained cured product was low, not reaching a sufficient level, and was poor.

[0326] In contrast, the compositions (liquids) of curable compositions No. 101 to 107 containing compounds represented by general formula (1) or (2) of the present invention exhibited excellent temporal stability, and the refractive index nD of the resulting cured products was high, exceeding 1.701. Furthermore, as shown in Table 2 below, curable composition No. 105 exhibited slight crystallization over time due to the presence of compound (B-5), a crystalline compound. However, curable composition No. 102, which was combined with compound (B-4), exhibited no crystallization or turbidity over time, demonstrating even more excellent temporal stability of the composition (liquid). Furthermore, curable compositions No. 106 and 107, each composed of a mixture of three or more compounds as a main monomer and a diluent monomer, also exhibited a high refractive index nD and even more excellent temporal stability of the composition (liquid).

[0327] [Example 3: Evaluation of Compounds]

[0328] Samples No. 201 to 211, r21, and r22, which were the main monomer compounds synthesized above or their mixtures, were evaluated for crystallization and coloration. The results are summarized in Tables 2-1 and 2-2 (hereinafter referred to as "Table 2").

[0329] [Evaluation 4] Crystallization

[0330] Approximately 200 mg of a sample was placed in a 1.5 mL vial and heated at 70°C to completely melt. The sample was then cooled at a rate of 10°C / min until the sample temperature reached 25°C. The sample temperature was then maintained at 25°C and observed over time. The time it took for the entire melted liquid to crystallize was measured, and the crystallization properties were evaluated according to the following evaluation criteria.

[0331] -Evaluation criteria for crystallization-

[0332] A: No precipitation of crystals was observed even after 96 hours.

[0333] B: Crystals were entirely precipitated over a period of more than 48 hours to 96 hours.

[0334] C: Crystals were entirely precipitated over a period of more than 24 hours to 48 hours.

[0335] D: Crystals were entirely precipitated over a period of more than 12 hours to 24 hours.

[0336] E: Crystals were entirely precipitated within 12 hours.

[0337] [Rating 5] Coloring

[0338] Approximately 30 mg of a sample was placed on a glass slide and heated to 70°C to completely melt it. Another glass slide was then placed over the sample to sandwich it and spread to a thickness of 150 μm. The transmittance (T%) at a wavelength of 450 nm was then measured using a UV-visible spectrophotometer (Shimadzu Corporation, trade name: UV2600) with one of the slides used as a reference. Coloration was evaluated according to the following evaluation criteria.

[0339] -Evaluation criteria for coloring-

[0340] A: T% ≥ 96%

[0341] B: 96%>T%≥95%

[0342] C: 95%>T%≥93%

[0343] D: 93%>T%≥91%

[0344] E:T%<91%

[0345]

[0346] Notes

[0347] The compounds in the table are as shown in the description of the main monomers in the notes of Table 1.

[0348] The amounts listed in the "Compound" column refer to the ratio of each compound constituting the sample, and wt% refers to mass%. When the sample is a mixture of two or more compounds, the ratio of each compound is listed in the order of the compounds listed in the "Type" column.

[0349] From the results in Table 2, the following can be seen.

[0350] Among the individual compounds, although the transmittance of compounds (B-5), (C-1) and (C-2) at a wavelength of 450nm is above 96% and almost no coloring is observed, they are crystalline compounds. Although compound (B-4) is a liquid, since the absorption is on the long wavelength side, the transmittance at a wavelength of 450nm is above 91% and less than 93%, and slight coloring is observed (reference samples No. 201, 202, r21 and r22).

[0351] On the other hand, when a mixture of the two compounds is prepared, crystallization can be suppressed compared to the individual compounds, and the stability over time is improved (for Samples No. 201, r21, and r22, refer to Samples No. 203 and 204; for Samples No. 202, r21, and r22, refer to Samples No. 205 to 207). In particular, the stability over time is higher and more excellent than that of the two mixtures containing Compound (B-4), namely Samples No. 205 to 207, and the two mixtures not containing Compound (B-4), namely Samples No. 203 and 204.

[0352] Furthermore, the results of studies on mixtures of three or more compounds revealed that crystallization can be further suppressed compared to mixtures of two compounds (for samples No. 203 to 207, refer to samples No. 208 to 211). Furthermore, by preparing a mixture of three or more compounds, the amount of compound (B-4) incorporated can be reduced, and coloration can also be suppressed.

[0353] Each sample listed in Table 2 was blended at a ratio of 99.7% by mass to 0.3% by mass of Irgacure TPO (product name, manufactured by BASF Japan Ltd., also available as Omnirad TPO H (product name, manufactured by IGM Resins BV)) as a photoradical polymerization initiator. The mixture was mixed at 60°C and then cooled to 25°C to obtain a curable composition. The curable composition obtained in this manner was evaluated for crystallization properties by the method described in Evaluation 4. As a result, the amount of crystal precipitation was suppressed to a level comparable to or lower than that of each sample listed in Table 2.

[0354] Among these curable compositions, the crystallization properties were evaluated as C or higher. Approximately 30 mg of the curable compositions obtained using Samples No. 202 to 211, in which crystallization was suppressed, were placed on a glass slide, sandwiched between two glass slides, and spread to a thickness of 150 μm. UV curing was then performed under the conditions described in Example 2. This confirmed that a cured film suitable for use in optical components could be obtained.

[0355] That is, the refractive index (nD) of the produced cured film (cured product) at a wavelength of 589 nm was measured by the method described in Evaluation 1 of Example 2. The refractive index nD of the cured product was 1.71 or greater even when any of Samples No. 202 to 211 was used, indicating that a cured film suitable for use in optical components was obtained.

[0356] The type of photoradical polymerization initiator was also varied. The samples listed in Table 2 were blended at 99.0-99.8% by mass, and the photoradical polymerization initiator was blended at 0.2-1.0% by mass, with the total amount being 100% by mass. The mixture was mixed at 60°C and then cooled to 25°C to obtain a curable composition.

[0357] In addition, three forms were implemented as photoradical polymerization initiators: a case where Irgacure TPO-L (product name, manufactured by BASF Japan Ltd., Omnirad TPO-L (product name, manufactured by IGM Resins BV) is available), a case where Irgacure 819 (product name, manufactured by BASF Japan Ltd., Omnirad 819 (product name, manufactured by IGM Resins BV) is available), and a case where ADEKA ARKLS NCI-831E (product name, manufactured by ADEKA CORPORATION) is used.

[0358] The curable composition obtained in this manner was evaluated for crystal precipitation by the method described in Evaluation 4. As a result, the amount of crystal precipitation was suppressed to a level equivalent to or lower than that of each sample described in Table 2.

[0359] Among these curable compositions, about 30 mg of the curable composition obtained by using sample No. 202 to 211 in which crystal precipitation was suppressed was placed on a glass slide, and another glass slide was overlapped to sandwich the sample, and after it was unfolded to a thickness of 150 μm, UV curing was performed under the conditions described in Example 2. It was confirmed that a cured film suitable for optical components could be obtained. That is, with respect to the produced cured film (cured product), the refractive index (nD) at a wavelength of 589 nm was measured by the method described in Evaluation 1 of Example 2. The refractive index nD of the cured product was 1.71 or more in all forms of the three forms in which the type of photoradical polymerization initiator was changed, and any one of sample No. 202 to 211 was used, thereby obtaining a cured film suitable for optical components.

[0360] In the examples shown in Table 2, which illustrate specific examples in which the type of the photoradical polymerization initiator was changed, sample No. 210 (Irgacure 819, a product name manufactured by BASF Japan Ltd., also available as Omnirad 819 (a product name manufactured by IGM Resins BV)) was blended at a ratio of 99.7 mass % to 0.3 mass %. The refractive index (nD) of the cured product at a wavelength of 589 nm, as measured by the method described in Evaluation 1 of Example 2, was 1.717. Furthermore, in the example described in Table 2, sample No. 211 (Irgacure 819, a product name manufactured by BASF Japan Ltd., also available as Omnirad 819 (a product name manufactured by IGM Resins BV)) was blended at a ratio of 99.7 mass % to 0.3 mass %, the refractive index (nD) of the cured product at a wavelength of 589 nm, as measured by the method described in Evaluation 1 of Example 2, was 1.713.

[0361] The present invention has been described in conjunction with its embodiments, but it is intended that the present invention should not be limited to any details in the description unless otherwise indicated, but should be broadly interpreted without departing from the spirit and scope of the invention as shown in the appended claims.

[0362] This application claims priority based on Japanese Patent No. 2023-012624 filed in Japan on January 31, 2023, Japanese Patent No. 2023-123517 filed in Japan on July 28, 2023, and Japanese Patent No. 2024-005032 filed in Japan on January 17, 2024, the contents of which are incorporated herein by reference.

[0363] Explanation of symbols

[0364] 1-Curable composition, 3-Substrate, 5-Mold, 7-Cured product.

Claims

1. A curable composition comprising a compound represented by the following general formula (1) or (2), [Chemical Formula 1] In the above formula, Q 1 represents a group represented by the following formula (q1a) or (q1b), Q 2 represents a group represented by the following formula (q2), Q 3 represents a group represented by the following formula (q3), [Chemical Formula 2] In the above formula, R 1 represents a (meth)acryloyl group, a vinyl group or an allyl group, and * represents a bonding bond.

2. The curable composition according to claim 1, wherein The compound represented by the general formula (1) or (2) contains the substituent (Q 1 ,Q 3 ) is substituted at the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring, and the substituent (Q 2 ,Q 3 ) is substituted at the (1,5) position, (1,6) position, (2,7) position, (5,1) position, (6,1) position or (7,2) position of the naphthalene ring, or at least one of the compounds.

3. The curable composition according to claim 2, wherein The compound represented by the general formula (1) or (2) includes at least one compound represented by any one of the following general formulas (3) to (6), [Chemical Formula 3] In the above formula, R 1 The meaning of R 1 The same meaning as R 2 represents a hydrogen atom or a methylsulfanyl group.

4. The curable composition according to claim 1, further comprising a compound represented by the following general formula (7): [Chemical Formula 4] In the above formula, Q 4 and Q 5 represents a group represented by any of the following formulas (q1a), (q1b), (q2) or (q3), but Q is absent 4 and Q 5 When one of them is a group represented by any one of the following formulas (q1a), (q1b) or (q2) and the other is a group represented by the following formula (q3), [Chemical Formula 5] In the above formula, R 1 represents a (meth)acryloyl group, a vinyl group or an allyl group, and * represents a bonding bond. The curable composition according to claim 1 , which is used for imprinting. A cured product obtained from the curable composition according to any one of claims 1 to 5. 7 . An optical material comprising the cured product according to claim 6 . 8 . A diffractive optical element comprising a surface having a diffraction grating shape formed from the cured product according to claim 6 .

9. A compound represented by the following general formula (1) or (2): [Chemical Formula 6] In the above formula, Q 1 represents a group represented by the following formula (q1a) or (q1b), Q 2 represents a group represented by the following formula (q2), Q 3 represents a group represented by the following formula (q3), [Chemical Formula 7] In the above formula, R 1 represents a (meth)acryloyl group, a vinyl group or an allyl group, and * represents a bonding bond.

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