Resin and composition comprising the same

Abstract

Provided is a novel resin which exhibits a high refractive index and excellent heat resistance. The present invention relates to a resin having a repeating unit represented by formula (I). In formula (I),-S-Z-S-represents a structural unit derived from a monomer represented by formula (II), and L represents a single bond or a divalent group. In formula (II), n represents an integer of 0-3, and a plurality of n may be the same as or different from each other. R represents a monovalent substituent, and if a plurality of R are present, the plurality of R may be the same as or different from each other. The two-SH groups in formula (II) are bonded to the 1-position and 6-position, or the 2-position and 7-position of the naphthalene ring.

Description

Technical Field

[0001] This invention relates to resins and compositions comprising the same. Furthermore, the invention also relates to molded articles formed from the resin or the composition, light guide plates formed from the resin or the composition, display devices comprising the molded articles, and solid-state imaging elements comprising the molded articles. Background Technology

[0002] High-refractive-index materials are desired in the field of optical devices. Lenses can be made using high-refractive-index materials, and lenses can be used to control the optical path within optical devices. Lenses are used in solid-state imaging devices to improve the light-gathering efficiency for each photoelectric conversion element, and in display devices to improve the efficiency of light extraction from pixels. Various high-refractive-index materials have been developed in the past, and adding inorganic fillers is known as one method for increasing refractive index. However, there are also various problems caused by the addition of inorganic fillers, such as light scattering due to the aggregation of inorganic fillers and contamination of surrounding surfaces due to metal ions during processing. In addition, organic high-refractive-index materials, for example, compositions containing specific (meth)acrylate compounds, are known (e.g., Patent Document 1).

[0003] Existing technical documents Patent documents Patent Document 1: International Publication No. 2011 / 102258 Summary of the Invention

[0004] The problem that the invention aims to solve One object of the present invention is to provide a novel resin capable of displaying high refractive index and excellent heat resistance. Another object of the present invention is to provide a composition comprising the resin, a molded article formed from the resin or the composition, a light guide plate formed from the resin or the composition, a display device comprising the molded article, and a solid-state imaging element comprising the molded article.

[0005] This invention includes the following:

[0006] [1] A resin having repeating units represented by formula (I).

[0007] In formula (I), -SZS- represents the structural unit derived from the monomer represented by equation (II). L represents a single bond or a divalent group. In formula (II), n represents any integer from 0 to 3. There can be multiple n values, which can be the same or different.

[0008] R represents a monovalent substituent. When there are multiple Rs, they can be the same or different.

[0009] In formula (II), the two -SH groups are bonded to positions 1 and 6, or positions 2 and 7, of the naphthalene ring. [2] The resin as described in [1], wherein L is a divalent hydrocarbon group selected from the group consisting of divalent aliphatic chain hydrocarbon groups that may have substituents, divalent alicyclic hydrocarbon groups that may have substituents, and divalent groups that are combinations thereof. The aforementioned divalent hydrocarbon group containing one or more -CH2- groups can be -O-, -S-, or -NR-. 1A -(R) 1A It indicates the substitution of -CO- or -SO2- for hydrogen atoms or alkyl groups with 1 to 6 carbon atoms.

[0010] [3] The resin as described in [2], wherein the aforementioned divalent aliphatic chain hydrocarbon group and the aforementioned divalent alicyclic hydrocarbon group are both saturated hydrocarbon groups.

[0011] [4] The resin as described in any one of [1] to [3] has a linear molecular structure.

[0012] [5] The resin as described in [2], wherein the number of carbon atoms of the aforementioned divalent aliphatic chain hydrocarbon group and the aforementioned divalent alicyclic hydrocarbon group is 20 or less.

[0013] [6] A composition comprising any one of [1] to [5].

[0014] [7] The composition as described in [6] further comprises a solvent.

[0015] [8] A molded article formed from any one of the resins described in [1] to [5] or the composition described in [6] or [7].

[0016] [9] A light guide plate formed from any one of the resins described in [1] to [5] or the composition described in [6] or [7].

[0017]

[10] A display device comprising the molded article described in [8].

[0018]

[11] A solid-state imaging element comprising the molded material described in [8].

[0019] Invention Effects According to the present invention, a novel resin capable of displaying high refractive index and excellent heat resistance can be provided. Furthermore, a composition comprising the resin, a molded article formed from the resin or the composition, a light guide plate formed from the resin or the composition, a display device comprising the molded article, and a solid-state imaging element comprising the molded article can be provided. Detailed Implementation

[0020] <Resin> The resin involved in this invention is a resin having repeating units represented by formula (I) (hereinafter also referred to as "resin (I)"). Resin (I) exhibits a high refractive index and excellent heat resistance. Furthermore, resin (I) exhibits excellent solvent resistance.

[0021] In formula (I), -SZS- represents the structural unit derived from the monomer represented by equation (II). L represents a single bond or a divalent group.

[0022] S represents a sulfur atom. In formula (II), n represents any integer from 0 to 3. There can be multiple n values, which can be the same or different.

[0023] R represents a monovalent substituent. When there are multiple Rs, they can be the same or different.

[0024] In formula (II), the two -SH groups are bonded to positions 1 and 6, or positions 2 and 7, of the naphthalene ring. In equation (I), Z represents the structural part other than the two -SH bases present in equation (II).

[0025] The monomer represented by formula (II) can have 0 to 6 monovalent substituents represented by R. When such substituents are present, they are bonded to positions in the naphthalene ring where the -SH group is not bonded. When formula (II) has one or more monovalent substituents represented by R, it means that the one or more monovalent substituents can be bonded to any position from 1 to 8 of the naphthalene ring, except for positions where the -SH group is bonded.

[0026] Regarding resin (I), it can have multiple repeating units that are different from each other (Z), it can have multiple repeating units that are different from each other (L), and it can have multiple repeating units that are different from each other (Z and L).

[0027] The monomer of the -SZS- structural part in the repeating unit represented by formula (I) is the monomer (II) represented by formula (II) above.

[0028] In formula (II), R represents a monovalent substituent. Examples of monovalent substituents include monovalent hydrocarbon groups and other substituents. When there are multiple Rs representing monovalent hydrocarbon groups, each is independent. Examples of monovalent hydrocarbon groups include monovalent aliphatic chain hydrocarbon groups that may have substituents, monovalent alicyclic hydrocarbon groups that may have substituents, monovalent aromatic hydrocarbon groups that may have substituents, and monovalent groups (aralkyl groups, etc.) formed by combinations of two or more of them.

[0029] A monovalent hydrocarbon group containing more than one -CH2- group can be -O-, -S-, or -NR1. B -(R1 B This indicates the substitution of hydrogen atoms or alkyl groups with 1 to 6 carbon atoms, such as -CO- or -SO2-. It should be noted that groups obtained by replacing -CH2- with -O- in monovalent hydrocarbon groups include alkoxy groups with 1 to 12 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, and octoxy; and alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, and methoxyethyl.

[0030] The substituents that a monovalent aliphatic chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group can have refer to atoms or groups of atoms that bond to the main chain as side chains when the longest molecular chain of these hydrocarbon groups is used as the main chain.

[0031] Examples of monovalent aliphatic chain hydrocarbon groups include saturated or unsaturated aliphatic chain hydrocarbon groups, specifically alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl.

[0032] The number of carbon atoms in a monovalent aliphatic chain hydrocarbon group is typically 1 to 20, preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 or 2.

[0033] Specific examples of substituents that a monovalent aliphatic chain hydrocarbon group may have, for example, include substituents that a divalent aliphatic chain hydrocarbon group may have, which will be described later. A monovalent aliphatic chain hydrocarbon group may have one or more substituents.

[0034] The same applies to the substituents that a monovalent alicyclic hydrocarbon group can have, and the substituents that a monovalent aromatic hydrocarbon group can have.

[0035] As monovalent alicyclic hydrocarbon groups, examples include saturated or unsaturated alicyclic hydrocarbon groups. Specifically, examples include monocyclic alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl; bicyclic [1.1.0]butyl, tricyclic [2.2.1.0]heptyl, bicyclic [3.2.1]octyl, bicyclic [2.2.2.]octyl, and tricyclic [3.3.1.1]... 3,7 Decyl (adamantyl), tricyclic [5.2.1.0] 2,6 [Decyl, bicyclic [4.3.2]undecyl, tricyclic [5.3.1.1]dodecyl and other polycyclic alicyclic hydrocarbon groups, etc.

[0036] The number of carbon atoms in a monovalent alicyclic hydrocarbon group is typically 3 to 20, preferably 3 to 10, more preferably 3 to 6, and even more preferably 5 or 6.

[0037] The monovalent aromatic hydrocarbon group can be monocyclic or polycyclic, for example, phenyl, naphthyl, anthraceneyl, fluorenyl, etc. The number of carbon atoms in the monovalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0038] Other examples of R in formula (II) include multiple Rs, each independent of the others. Examples include hydroxyl groups; amino groups such as amino, monomethylamino, monoethylamino, dimethylamino, diethylamino, methylethylamino, etc., which can be substituted by one or two alkyl groups having 1 to 6 carbon atoms; heterocyclic groups such as pyrrolidinyl, pyrrolinyl, imidazolinyl, imidazolinyl, oxazolinyl, thiazolyl, piperidinyl, morpholinyl, piperazine, indole, isoindole, quinolinyl, thiophene, pyrrolidinyl, and furanyl, which are aliphatic heterocyclic groups having 4 to 20 carbon atoms or aromatic heterocyclic groups having 3 to 20 carbon atoms; halogen atoms; nitro groups; cyano groups; carboxyl groups; sulfonyl groups; thiol groups; formyl groups; -SF3 groups; -SF5 groups.

[0039] Examples of monomers (II) include monomer (II-1) represented by formula (II-1) and monomer (II-2) represented by formula (II-2). Monomer (II-1) is a 1,6-naphthodithiol that may have a substituent R, and monomer (II-2) is a 2,7-naphthodithiol that may have a substituent R.

[0040] [In equations (II-1) and (II-2), the meanings of n and R are the same as in equation (II).] In formula (I), L represents a single bond or a divalent group. Examples of divalent groups L include, for example, aliphatic chain hydrocarbon groups that may have substituents, alicyclic hydrocarbon groups that may have substituents, aromatic hydrocarbon groups that may have substituents, and divalent groups (such as arylene alkyl groups) that are combinations of two or more of these.

[0041] A divalent hydrocarbon group containing more than one -CH2- group can be -O-, -S-, or -NR-. 1A -(R) 1A It indicates the substitution of -CO- or -SO2- for hydrogen atoms or alkyl groups with 1 to 6 carbon atoms.

[0042] Both the divalent aliphatic chain hydrocarbon group and the divalent alicyclic hydrocarbon group can be saturated or unsaturated hydrocarbon groups. Preferably, both the divalent aliphatic chain hydrocarbon group and the divalent alicyclic hydrocarbon group are saturated hydrocarbon groups.

[0043] L, as a divalent group, is preferably a divalent hydrocarbon group selected from the group consisting of divalent aliphatic chain hydrocarbon groups that may have substituents, divalent alicyclic hydrocarbon groups that may have substituents, and divalent groups that are combinations thereof.

[0044] Substituents that can exist in divalent aliphatic chain hydrocarbon groups, divalent alicyclic hydrocarbon groups, and divalent aromatic hydrocarbon groups refer to atoms or groups of atoms that bond to the main chain as side chains when the molecular chain (divalent aliphatic chain hydrocarbon group, divalent alicyclic hydrocarbon group, divalent aromatic hydrocarbon group, or divalent group as a combination of two or more of them) that bonds between two S atoms is used as the main chain.

[0045] Examples of divalent aliphatic chain hydrocarbon groups include saturated or unsaturated aliphatic chain hydrocarbon groups, specifically including methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, undecanediyl, dodecanediyl, tridecanediyl, tetradecanediyl, pentadecanediyl, hexadecanediyl, heptadecanediyl, octadecanediyl, nonadecanediyl, eicosanediyl, and other chain alkyl diyl groups.

[0046] The number of carbon atoms in the divalent aliphatic chain hydrocarbon group is usually 1 to 30, preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4. It can be 1 or 2.

[0047] Substituents that can be present in a divalent aliphatic chain hydrocarbon group include, for example, halogen atoms such as fluorine, chlorine, bromine, and iodine, hydroxyl, amino, acetyl, benzoyl, carboxyl, carboxylic acid ester groups (e.g., alkyloxycarbonyl), cyano, monovalent aliphatic chain hydrocarbon groups, monovalent alicyclic hydrocarbon groups, and monovalent aromatic hydrocarbon groups. A divalent aliphatic chain hydrocarbon group can have one or more substituents.

[0048] The same applies to the substituents that can be present in divalent alicyclic hydrocarbon groups and divalent aromatic hydrocarbon groups.

[0049] The monovalent aliphatic chain hydrocarbon group and the monovalent alicyclic hydrocarbon group that serve as substituents can each be either straight-chain or branched.

[0050] As for specific examples of monovalent aliphatic chain hydrocarbon groups, monovalent alicyclic hydrocarbon groups and monovalent aromatic hydrocarbon groups as substituents, examples can be given for example the groups described above as specific examples of monovalent aliphatic chain hydrocarbon groups, monovalent alicyclic hydrocarbon groups and monovalent aromatic hydrocarbon groups as R in formula (II).

[0051] As divalent alicyclic hydrocarbon groups, examples include saturated or unsaturated alicyclic hydrocarbon groups. Specifically, examples include monocyclic alicyclic hydrocarbon groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cyclooctanediyl, cyclononanediyl, and cyclodecanediyl; bicyclic [1.1.0]butanediyl, tricyclic [2.2.1.0]heptanediyl, bicyclic [3.2.1]octanediyl, bicyclic [2.2.2.]octanediyl, and tricyclic [3.3.1.1]octanediyl. 3,7 [Decanediyl (adamantide diyl), tricyclic [5.2.1.0]] 2 ,6 [Decanediyl, bicyclic [4.3.2]undecanediyl, tricyclic [5.3.1.1]dodecanediyl and other polycyclic alicyclic hydrocarbon groups.

[0052] The number of carbon atoms in a divalent alicyclic hydrocarbon group is usually 3 to 30, preferably 3 to 20, more preferably 3 to 10, and can be 5 or 6.

[0053] The divalent aromatic hydrocarbon group can be monocyclic or polycyclic, for example, phenylene, naphthylene, anthracenediyl, fluorenediyl, etc.

[0054] The number of carbon atoms in a divalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0055] In a preferred embodiment, L in formula (I) is a divalent aliphatic chain hydrocarbon group or a divalent alicyclic hydrocarbon group that may have substituents, preferably a divalent aliphatic chain hydrocarbon group that may have substituents, and more preferably a dialkyl alkane that may have substituents. The divalent aliphatic chain hydrocarbon group, the divalent alicyclic hydrocarbon group, and the dialkyl alkane group may contain one or more -CH2- groups that can be -O-, -S-, or -NR. 1A -(R) 1A It indicates the substitution of -CO- or -SO2- for hydrogen atoms or alkyl groups with 1 to 6 carbon atoms.

[0056] The number of carbon atoms in the divalent aliphatic chain hydrocarbon group and the alkyl diene group is generally 1 to 30, preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4, and can be 1 or 2. The number of carbon atoms in the divalent alicyclic hydrocarbon group is generally 3 to 30, preferably 3 to 20, more preferably 3 to 10, and can be 5 or 6.

[0057] Preferred examples of L are, for example, the following structures.

[0058] a) L is a dialkyl chain with 1 to 4 carbon atoms.

[0059] The number of carbon atoms in an alkyl diester can be more than 1 and less than 3, and can be 1 or 2. Alkyl diesters may have substituents.

[0060] b) L is an alkyl diester with 1 to 4 carbon atoms, and the alkyl diester contains one or more -CH2- atoms that are surrounded by -O-, -S-, or -NR-. 1A -(R) 1A It indicates the substitution of -CO- or -SO2- for hydrogen atoms or alkyl groups with 1 to 6 carbon atoms.

[0061] The number of carbon atoms in the alkyl diester can be 1 to 3, and can be 1 or 2. The alkyl diester may have substituents. Preferably, one or more -CH2- atoms in the alkyl diester are replaced by -O-, -S-, -CO-, or -SO2-. The number of replaced -CH2- atoms can be 1 to 3, and can be 1 or 2.

[0062] c) L is a saturated alicyclic hydrocarbon group with 3 to 10 carbon atoms, or a combination of the alicyclic hydrocarbon group and an alkane dimethyl group with 1 to 4 carbon atoms.

[0063] The combination can be one or more of the alicyclic hydrocarbon group and one or more of the alkyl diene group. The alkyl diene group can have 1 to 3 carbon atoms, and can have 1 or 2 carbon atoms. Both the alicyclic hydrocarbon group and the alkyl diene group can have substituents.

[0064] d) L is a saturated alicyclic hydrocarbon group with 3 to 10 carbon atoms, or a combination of such alicyclic hydrocarbon group and an alkyl diester with 1 to 4 carbon atoms, wherein one or more -CH2- atoms contained in the alkyl diester are surrounded by -O-, -S-, or -NR. 1A -(R) 1A It indicates the substitution of -CO- or -SO2- for hydrogen atoms or alkyl groups with 1 to 6 carbon atoms.

[0065] The combination can be one or more of the alicyclic hydrocarbon group and one or more of the alkyl diene group. The alkyl diene group can have 1 to 3 carbon atoms, or 1 or 2 carbon atoms. Both the alicyclic hydrocarbon group and the alkyl diene group can have substituents. One or more -CH2- atoms in the alkyl diene group are preferably replaced by -O-, -S-, -CO-, or -SO2-. The number of replaced -CH2- atoms can be 1 to 3, or 1 or 2 carbon atoms.

[0066] In resin (I), specific examples of L as a divalent group include the following groups. However, L is not limited to the groups described below. In the following formula, This indicates the bond between the S atom and the -SH group derived from monomer (II).

[0067] As a resin (I) having repeating units represented by formula (I), examples can be given where -SZS- in formula (I) is a structural unit derived from the monomer represented by formula (II-1), and L in formula (I) is selected from the resins of the specific examples described above. In addition, examples can be given where -SZS- in formula (I) is a structural unit derived from the monomer represented by formula (II-2), and L in formula (I) is selected from the resins of the specific examples described above.

[0068] Furthermore, as resin (I), examples include resins in which -SZS- in formula (I) is derived from the structural unit of the monomer represented by formula (II-1) and L in formula (I) is a single bond; and resins in which -SZS- in formula (I) is derived from the structural unit of the monomer represented by formula (II-2) and L in formula (I) is a single bond.

[0069] Regarding resin (I), for example, when monomer (II) is monomer (II-1), it can have a bonding structure in which the S atom at position 1 of the naphthalene ring is bonded to the S atom at position 6 of the naphthalene ring via an L-bond (also called "1,6-bonded structure"), a bonding structure in which the S atom at position 1 is bonded to the S atom at position 1 via an L-bond (also called "1,1-bonded structure"), and a bonding structure in which the S atom at position 6 is bonded to the S atom at position 6 via an L-bond (also called "6,6-bonded structure"). Resin (I) can have one or more bonding structures selected from the group consisting of 1,6-bonded structure, 1,1-bonded structure, and 6,6-bonded structure.

[0070] Resin (I) preferably has a linear molecular structure. A linear molecular structure means that the repeating units represented by formula (I) are linked in a linear fashion. Resin (I) preferably does not have a cross-linked structure that binds the main chains of the polymer constituting it.

[0071] As described below, resin (I) can be manufactured by reacting monomer (II) with monomer (III) of formula (I) containing L. In order for resin (I) to have a linear molecular structure, monomer (III) is preferably a compound having two functional groups that can react with the -SH group of monomer (II) to form a bond between the S atom and L.

[0072] Regarding resin (I), the weight-average molecular weight (Mw) converted from standard polystyrene by gel permeation chromatography (GPC) is preferably 500 to 1,000,000, more preferably 750 to 100,000, even more preferably 1,000 to 50,000, and particularly preferably 1,500 to 25,000. A weight-average molecular weight (Mw) within the above range is advantageous in improving the heat resistance and / or solvent resistance of resin (I).

[0073] GPC-based molecular weight determination can be performed according to the description of the items in the examples described later.

[0074] <Resin Manufacturing Method> Resin (I) can be manufactured by reacting monomer (II) with monomer (III) that can form L in formula (I). Monomer (III) is a compound having a site (functional group) that can react with the -SH group of monomer (II) to form a bond between the S atom and L. Hereinafter, this site (functional group) is also referred to as a "reactive functional group". Monomer (III) is a repeating unit represented by formula (I) and has two or more reactive functional groups, preferably two reactive functional groups. In the above reaction, two or more monomers (III) and two or more monomers (II) can be used.

[0075] The first example of monomer (III) is a monomer (III) whose reactive functional group is a leaving group. Examples of leaving groups include halogen atoms such as fluorine, chlorine, bromine, and iodine, trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, and imidazole-1-yl. In the first example, monomer (III) preferably has two leaving groups, and more preferably has two halogen atoms. In the first example, monomer (III) is, for example, a compound represented by LV-L-LV. L has the same meaning as L in formula (I), and LV is a leaving group.

[0076] As a specific example of a monomer (III) whose reactive functional group is a halogen atom, one can cite the specific examples of L as a divalent group listed above. Compounds obtained by introducing halogen atoms into the position of the halogen atom. The preferred halogen atoms are chlorine, bromine, or iodine.

[0077] The second example of monomer (III) is a monomer (III) whose reactive functional group is a reactive unsaturated group. Examples of reactive unsaturated groups include vinyl, allyl, (meth)acryloyl, vinylsulfonyl, etc. In the second example, monomer (III) preferably has two reactive unsaturated groups, and more preferably has two vinyl groups. When a monomer (III) whose reactive functional group is a reactive unsaturated group is used, for example, if the reactive unsaturated group is vinyl, the vinyl group is converted into a -CH2-CH2- group through a reaction with the -SH group of monomer (II), and this group becomes part of L.

[0078] The amount of monomer (III) used relative to 1 mole of monomer (II) is, for example, 0.5 to 50 moles, preferably 0.6 to 40 moles. Where monomer (III) also serves as a solvent, it is not limited to the above and monomer (III) can be used in excess.

[0079] The reaction between monomer (II) and monomer (III) can be carried out in the presence of a base. Two or more bases can be used together. Examples of bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium hydride, lithium aluminum hydride, sodium borohydride, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, and cesium bicarbonate; metal alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium tert-butoxide, and potassium tert-butoxide; and organic bases such as ammonia, methylamine, dimethylamine, trimethylamine, diethylmethylamine, triethylamine, diisopropylethylamine, triisopropylamine, DBU, DABCO, pyridine, 2,6-dimethylpyridine, 2,6-di-tert-butylpyridine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, and tetramethylammonium chloride.

[0080] The amount of base used is, for example, 0.01 to 10 moles of monomer (II), preferably 0.5 to 5 moles, relative to 1 mole of monomer (II).

[0081] The reaction between monomer (II) and monomer (III) can be carried out in the presence of a capping agent used to end-cap the polymer formed. The capping agent can be present from the beginning of the reaction or introduced midway through the reaction. Examples of capping agents include compounds having a group that can react with an L-reactive functional group. Examples of such groups include the -SH group. When using a capping agent, the amount of the capping agent relative to 1 mole of monomer (II) is, for example, 0.001 to 0.5 moles, preferably 0.05 to 0.3 moles.

[0082] The reaction between monomer (II) and monomer (III) can be carried out in a solvent. Monomer (III) can also act as a solvent. Besides water, other organic solvents include ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, alcohols, glycol dimethyl ethers, esters, aliphatic nitriles, sulfoxides, and amides. Two or more solvents can also be used together. Specifically, the following solvents can be cited as examples of organic solvents.

[0083] Ketones: Acetone, methyl ethyl ketone, diethyl ketone, butyl methyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone, etc. Aromatic hydrocarbons: benzene, toluene, xylene, mesitylene, naphthalene, anisole, nitrobenzene, aniline, tetrahydronaphthalene, mesitylene, etc. Halogenated aromatic hydrocarbons: chlorobenzene, dichlorobenzene, chloronaphthalene, etc. Aliphatic hydrocarbons: pentane, hexane, heptane, etc. Halogenated aliphatic hydrocarbons: dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, etc. Ethers: Diethyl ether, diisopropyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, dioxane, tetrahydrofuran, etc. Alcohols: methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, hexafluoroisopropanol, etc. Diethylene glycol dimethyl ethers: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, etc. Esters: Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc. Aliphatic nitriles: acetonitrile, etc. Sulfoxides: dimethyl sulfoxide, sulfolane, etc. Amides: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0084] The reaction temperature between monomer (II) and monomer (III) is, for example, -80 to 200°C, preferably 0 to 150°C. The resulting resin (I) can be separated and purified by conventional methods.

[0085] <Composition> The composition of the present invention (hereinafter also referred to as "composition (I)") comprises resin (I) and other components besides resin (I). Composition (I) may contain two or more resins (I). Composition (I) can be used to form molded articles containing resin (I). A molded article refers to an object molded into a desired shape.

[0086] Composition (I) contains resin (I), and therefore exhibits a high refractive index and excellent heat resistance. In addition, composition (I) exhibits excellent solvent resistance.

[0087] The content of resin (I) in composition (I) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, in addition to being 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, and may be 90% by mass or less or 80% by mass or less.

[0088] The total amount of solid components in composition (I) refers to the sum of all components contained in composition (I), excluding the solvent. The content of each component in the solid components of the composition can be determined by known analytical methods such as liquid chromatography or gas chromatography. The content of each component in the solid components of composition (I) can be calculated from the formulation used in preparing the composition.

[0089] Other components included in composition (I) may include, for example, resins other than resin (I), solvents, additives, etc. Additives may include, for example, inorganic particles, fillers, polymerization initiators, sensitizers, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, UV absorbers, antioxidants, dispersants, etc. Composition (I) may contain two or more of the aforementioned other components. When composition (I) contains additives, two or more additives may be used together.

[0090] Other than resin (I), high refractive index resins can be cited. High refractive index resins are those with a refractive index of 1.60 or higher at a wavelength of 550 nm.

[0091] The composition (I) may contain one or more solvents. The solvent is preferably a solvent capable of dissolving or dispersing the resin (I), and more preferably a solvent capable of dissolving or dispersing other components besides the resin (I). As a solvent, for example, the organic solvents exemplified above may be used.

[0092] The solvent content in composition (I) is the proportion of the total mass of all solvents contained in composition (I) relative to the total amount of composition (I). When composition (I) contains solvent, the solvent content in composition (I) is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, and preferably 2000 parts by mass or less, more preferably 1000 parts by mass or less, relative to 100 parts by mass of the solid component of composition (I). When composition (I) contains solvent, the concentration of the solid component of composition (I) is preferably 1 to 60% by mass, more preferably 2 to 50% by mass.

[0093] <Molded product> This invention provides a molded article formed from a resin (I) or a composition (I). The molded article contains resin (I). The shape of the molded article is not particularly limited and can be any shape corresponding to the intended use of the molded article, including film-like, plate-like, lens-like, powder-like, granular, non-spherical particle-like, broken particle-like, porous, blocky continuous, fibrous, tubular, hollow fibrous, etc.

[0094] The molded product contains resin (I), thus exhibiting a high refractive index and excellent heat resistance. Furthermore, the molded product exhibits excellent solvent resistance.

[0095] There are no particular limitations on the method for obtaining a molded article from the composition (I), and examples include methods for forming a film on a substrate, methods for molding by etching or the like after forming a film on a substrate, injection molding, casting polymerization molding, etc.

[0096] In the case of forming a film as a molded article on a substrate, composition (I) is coated onto the substrate and dried as needed to form a resin film, thereby obtaining the molded article. The molded article can be a patterned resin film. Patterning can be performed by methods such as photolithography, inkjet printing, or printing, thereby obtaining a patterned resin film. The preferred patterning method is photolithography.

[0097] As a substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass with silica coating can be used; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate can be used; silicon can be used; and substrates on which aluminum, silver, or silver / copper / palladium alloy films are formed can be used. As a method for coating composition (I) onto the substrate, spin coating, slot coating, and slit and spin coating methods can be used.

[0098] The resin (I), composition (I), and molded article exhibit high refractive index. Furthermore, the refractive index of the composition (I) and the molded article can be controlled to a desired refractive index by adjusting the composition of the composition (I), etc. Regarding the resin (I), composition (I), and molded article, the refractive index at a wavelength of 550 nm can be 1.65 or higher, 1.68 or higher, 1.70 or higher, 1.72 or higher, 1.75 or higher, and 1.80 or higher. The refractive index at a wavelength of 550 nm can be, for example, 1.90 or lower, and can be 1.85 or lower.

[0099] <Applications of Molded Products> According to the present invention, it is possible to obtain molded articles with high refractive index or molded articles with a desired refractive index. Applications of molded products include, for example, glass substitutes and their surface coating materials; coating materials for window glass, skylights, and light source protection glass for houses, facilities, and transportation equipment; window films for houses, facilities, and transportation equipment; interior and exterior materials and coatings for houses, facilities, and transportation equipment, and coatings formed by such coatings; alkyd resin paints and coatings formed by such paints; acrylic paints and coatings formed by such paints; components for light sources emitting ultraviolet light, such as fluorescent lamps and mercury lamps; materials for blocking electromagnetic waves generated from components of precision machinery, electronic and electrical equipment, and various displays; containers or packaging materials for food, chemicals, and pharmaceuticals; bottles, boxes, blister packs, cups, special packaging, compact disc coats, and agricultural and industrial sheets or films; fading prevention agents for printed materials, dyed materials, dyes, and pigments; protective films for polymer supports (e.g., for plastic parts such as machinery and automotive parts); outer coatings for printed materials; inkjet media coatings; laminated matting; and optical films. Film); safety glass / windshield interlayer; electrochromic / photochromic applications; over laminate film; solar control film; cosmetics such as sunscreen, shampoo, conditioner, and hair styling products; textiles and fibers for clothing such as sportswear, stockings, and hats; household interior decorations such as curtains, carpets, and wallpaper; medical devices such as plastic lenses, contact lenses, and prosthetic eyes; optical products such as filters, backlight display films, prisms, lenses (e.g., spectacle lenses, camera lenses, and microlenses, pickup lenses, etc. described later), mirrors, and photographic materials; stationery such as mold films, transfer stickers, anti-graffiti films, tapes, and inks; indicator boards, indicators, and their surface coating materials; substrates for optical devices; diffraction gratings for optical waveguides (e.g., light guide plates); prisms; beam splitters; holograms; LED sealing materials; etc.

[0100] The molded material is suitable for use as a lens in optical devices. Examples of optical devices include solid-state imaging elements and display devices. Lenses are used in solid-state imaging elements to improve the light-gathering efficiency for each photoelectric conversion element, and lenses are used in display devices to improve the efficiency of light extraction from pixels. The lens can be a microlens. As a display device, it is suitable for liquid crystal displays, organic EL displays, etc.

[0101] Inorganic compounds such as zirconium oxide and titanium oxide are known as high-refractive-index materials. However, when manufacturing molded articles containing high-refractive-index materials formed from inorganic compounds, there are difficulties in molding, such as difficulty in etching, and there is also the problem of high-refractive-index material scattering and causing contamination during molding. By using the high-refractive-index material of the present invention, which is an organic compound, the above problems can be solved.

[0102] <Light guide plate> This invention provides a light guide plate formed from resin (I) or composition (I). The light guide plate comprises resin (I). The shape of the light guide plate can be film-like, plate-like, etc., and it can have an uneven surface. Furthermore, the thickness of the light guide plate can be appropriately designed according to the application, for example, 0.05 mm to 3.0 mm, and preferably 0.1 mm to 1.0 mm for AR (Augmented Reality) display applications.

[0103] The refractive index of the light guide plate at 550 nm is preferably 1.2 to 2.2, more preferably 1.4 to 2.0, and even more preferably 1.5 to 1.9.

[0104] The average transmittance of the light guide plate with a thickness of 100mm to 200mm and a wavelength of 380 to 780nm is preferably above 85%.

[0105] For light guide plates with a thickness of 100mm to 200mm, the tristimulus values ​​X, Y, and Z of transmittance are preferably above 85%. The tristimulus values ​​X, Y, and Z can be determined based on the isochromatic function of XYZ in CIE 1931 and the transmittance of the light guide plate.

[0106] That is, the transmittance of the light guide plate is used as the spectral radiance for calculation.

[0107] The wavelength λ is 380~780nm.

[0108] The light guide plate can be obtained by molding resin (I) or composition (I). As a molding method, known methods such as sheet extrusion molding, injection molding, and compression molding can be used.

[0109] Example The present invention is illustrated below with examples and comparative examples, but the invention is not limited to these examples. In the examples, unless otherwise specified, the percentage or parts of content or usage are indicated on a quality basis.

[0110] [Example 1: Synthesis of Resin (I-1)] A nitrogen atmosphere was created in a four-necked flask equipped with a Demroth cooling tube and a thermometer. Three parts of 1,6-naphthalenedithiol, 75 parts of N,N-dimethylformamide, 2.5 parts of bis(chloromethyl)sulfide, and 15 parts of cesium carbonate were added to the flask, and the mixture was stirred at 50°C for 5 hours. The resulting mixture was purified to obtain 2.7 parts of resin (I-1).

[0111] The resin (I-1) has repeating units represented by formula (I), where -SZS- is a structural unit derived from 1,6-naphthalenedithiol and L is -CH2-S-CH2-.

[0112] The weight-average molecular weight (Mw) of resin (I-1) determined by GPC was 11,000, and the number-average molecular weight (Mn) was 5,300.

[0113] GPC measurements were performed under the following conditions. GPC measurements were also performed under the same conditions for other embodiments.

[0114] Device: K2479 (manufactured by Shimadzu Corporation) Chromatographic column: TSKgel SuperAWM-H×2 (6.0mm I.D.×150mm×2 columns) Column temperature: 40℃ Solvent: N-methylpyrrolidone (10mM lithium bromide) Flow rate: 0.4 mL / min Injection volume: 10 μL Detector: RI Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH CORPORATION) [Example 2: Synthesis of Resin (I-2)] A nitrogen atmosphere was created in a four-necked flask equipped with a Demroth cooling tube and a thermometer. One part of 1,6-naphthalenedithiol, 20 parts of dichloromethane, 0.03 parts of sodium 2-mercaptoethanesulfonate, and 1.1 parts of diethylmethylamine were added to the flask, and the mixture was stirred at room temperature for 5 hours. The resulting mixture was purified to obtain 1.0 part of resin (I-2).

[0115] Resin (I-2) has repeating units represented by formula (I), where -SZS- is a structural unit derived from 1,6-naphthalenedithiol and L is -CH2-. Furthermore, resin (I-2) is synthesized in the presence of a small amount of sodium 2-mercaptoethanesulfonate, thus having -S-CH2-CH2-SO3H as terminal groups at both ends of the polymer chain.

[0116] The weight-average molecular weight (Mw) of resin (I-2) determined by GPC was 3100, and the number-average molecular weight (Mn) was 990.

[0117] [Example 3: Synthesis of Resin (I-3)] A nitrogen atmosphere was created in a four-necked flask equipped with a Demroth cooling tube and a thermometer. Three parts of 1,6-naphthalenedithiol, 60 parts of tetrahydrofuran, and 2.6 parts of carbonyl diimidazole were added to the flask, and the mixture was stirred at room temperature for 5 hours. The resulting mixture was purified to obtain 3.3 parts of resin (I-3).

[0118] The resin (I-3) has repeating units represented by formula (I), where -SZS- is a structural unit derived from 1,6-naphthalenedithiol and L is -CO-.

[0119] The weight-average molecular weight (Mw) of resin (I-3) determined by GPC was 520, and the number-average molecular weight (Mn) was 370.

[0120] [Example 4: Synthesis of Resin (I-4)] A nitrogen atmosphere was created in a four-necked flask equipped with a Demroth cooling tube and a thermometer. Three parts of 1,6-naphthalenedithiol, 20 parts of dichloromethane, 0.11 parts of thioglycolic acid, and 5.4 parts of diethylmethylamine were added to the flask, and the mixture was stirred at room temperature for 5 hours. The resulting mixture was purified to obtain 2.8 parts of resin (I-4).

[0121] Resin (I-4) has repeating units represented by formula (I), where -SZS- is a structural unit derived from 1,6-naphthalenedithiol and L is -CH2-. In addition, resin (I-4) is synthesized in the presence of a small amount of thioglycolic acid, and therefore has -S-COOH as terminal groups at both ends of the polymer chain.

[0122] The weight-average molecular weight (Mw) of resin (I-4) determined by GPC was 34,000, and the number-average molecular weight (Mn) was 2,400.

[0123] [Example 5: Synthesis of Resin (I-5)] A nitrogen atmosphere was created in a four-necked flask equipped with a Demroth cooling tube and a thermometer. Three parts of 1,6-naphthalenedithiol, 60 parts of dichloromethane, and 5.4 parts of diethylmethylamine were added to the flask, and the mixture was stirred at room temperature for 5 hours. The resulting mixture was purified to obtain 2.9 parts of resin (I-5).

[0124] The resin (I-5) has repeating units represented by formula (I), where -SZS- is a structural unit derived from 1,6-naphthalenedithiol and L is -CH2-.

[0125] The weight-average molecular weight (Mw) of resin (I-5) determined by GPC was 22,000, and the number-average molecular weight (Mn) was 2,500.

[0126] [Example 6: Synthesis of Resin (I-6)] A nitrogen atmosphere was created in a four-necked flask equipped with a Demroth cooling tube and a thermometer. 1.5 parts of 1,6-naphthalenedithiol, 15 parts of dimethylformamide, 2.2 parts of methyl dichloroacetate, and 1.5 parts of diethylmethylamine were added to the flask, and the mixture was stirred at room temperature for 5 hours. The resulting mixture was purified to obtain 1.7 parts of resin (I-6).

[0127] The resin (I-6) has repeating units represented by formula (I), where -SZS- is a structural unit derived from 1,6-naphthalenedithiol and L is -CH(COOCH3)-.

[0128] The weight-average molecular weight (Mw) of resin (I-6) determined by GPC was 14,000, and the number-average molecular weight (Mn) was 7,900.

[0129] [Example 7: Synthesis of Resin (I-7)] A nitrogen atmosphere was created in a four-necked flask equipped with a Demroth cooling tube and a thermometer. 1.5 parts of 1,6-naphthalenedithiol, 15 parts of dimethylformamide, 2.2 parts of dichloroacetic acid, and 2 parts of diethylmethylamine were added to the flask, and the mixture was stirred at room temperature for 5 hours. The resulting mixture was purified to obtain 1.0 part of resin (I-7).

[0130] The resin (I-7) has repeating units represented by formula (I), where -SZS- is a structural unit derived from 1,6-naphthalenedithiol and L is -CH(COOH)-.

[0131] The weight-average molecular weight (Mw) of the resin (I-7) determined by GPC was 830, and the number-average molecular weight (Mn) was 420.

[0132] [Example 8: Synthesis of Resin (I-8)] A nitrogen atmosphere was created inside a four-necked flask equipped with a Demroth cooling tube and a thermometer. 1.5 parts of 1,6-naphthalenedithiol, 37 parts of acetone, 5 parts of pure water, 0.7 parts of sodium hydroxide, and bis(vinyl sulfone)tricyclo[5.2.1.0] were then added. 2,6 Add 2.5 parts of decane to the above flask and stir at room temperature for 5 hours. Purify the resulting mixture to obtain 1.0 part of resin (I-8).

[0133] Resin (I-8) has repeating units represented by formula (I), where -SZS- is a structural unit derived from 1,6-naphthalenedithiol, and L is -CH2-CH2-SO2- (tricyclic [5.2.1.0]). 2,6 [decanediyl)-SO2-CH2-CH2-.

[0134] The weight-average molecular weight (Mw) of resin (I-8) determined by GPC is 65,000, and the number-average molecular weight (Mn) is 12,000.

[0135] [Example 9: Preparation of the composition] Ten parts by mass of resin (I-1) and 90 parts by mass of 1,1,2,2-tetrachloroethane as solvent were added to a flask and stirred to obtain a liquid composition. The composition was visually inspected and found to be transparent, confirming that the complexing components had been uniformly dissolved.

[0136] [Examples 10-13, Comparative Example 1: Preparation of the Composition] The type of resin used was changed from resin (I-1) to the resin shown in Table 1, and otherwise the same procedure was followed as in Example 1 to obtain a liquid composition. As for the compositions of Examples 10-13 and Comparative Example 1, the visual result was transparent, confirming that the complexing components had been uniformly dissolved.

[0137] The resin (Y1) contained in the composition of Comparative Example 1 is poly(acenaphthene) (manufactured by Sigma-Aldrich) having the following structure.

[0138] [Evaluation Experiment] (1) Refractive index of resin Approximately 3 cc of the composition prepared above was dropped onto alkali-free glass (Eagle XG, 0.7 mm thickness, Corning Corporation). The glass was then spin-coated at 700 rpm for 20 seconds using a spin coater (MS-B100, Mikasa Corporation) to form a coating layer. The alkali-free glass plate with the coating layer was heated to 60°C for 2 minutes, and then to 100°C for 3 minutes to dry the coating layer, resulting in alkali-free glass with a resin film. The thickness of the resin film on the alkali-free glass was measured using a stylus-type film thickness gauge (DekTak XT, Bruker Corporation), and the result was approximately 1.0 μm.

[0139] For alkali-free glass with a resin film, the transmission and reflection spectra from 300 nm to 800 nm were measured using a UV-Vis spectrophotometer (V-650, Japanese Spectrophotometer) with an integrating sphere (ISV-922, manufactured by Nippon Spectrophotometer). Using the 550 nm wavelength value from the true reflection spectrum obtained by subtracting the increase or decrease caused by interference in the reflection spectrum from the transmission and reflection spectra and smoothing the data, and the refractive index of the alkali-free glass (Eagle XG, Corning), the refractive index of the resin film at 550 nm was calculated based on the Fresnel equation (Hecht Optics I, 5th edition, Maruzen Publishing, 2018, pp. 209-226). The results are shown in Table 1.

[0140] (2) Heat resistance of resin Alkali-free glass with a resin film formed by the same method as described in (1) above was placed on a hot plate heated to 260°C for 5 minutes. The change in transmittance of the resin film at a wavelength of 450 nm before and after heating with the hot plate was calculated (transmittance change = transmittance before heating - transmittance after heating), and the heat resistance of the resin was evaluated according to the following evaluation criteria. The results are shown in Table 1.

[0141] A: Transmittance change is above 0% and less than 2%. B: Transmittance change is above 2% and less than 5%. C: Transmittance change is above 5% (3) Solvent resistance Alkali-free glass with a resin film (approximately 1.0 μm thick) prepared using the same method as described in (1) above was immersed in acetone at 23°C for 10 minutes. The appearance changes of the resin film before and after immersion were observed, and the film thickness retention rate before and after immersion was calculated (film thickness retention rate = film thickness after immersion ÷ film thickness before immersion). The solvent resistance of the resin was evaluated according to the following evaluation criteria. The results are shown in Table 1.

[0142] A: No change in appearance; film thickness retention rate is between 90% and 100%. B: No change in appearance, film thickness retention rate is less than 90% but above 80%. C: No change in appearance, film thickness retention rate less than 80%. D: The cured film after impregnation is cloudy, and the film thickness retention rate is less than 80%. [Table 1] [Example 14: Manufacturing of the light guide plate] 1g of the resin (I-5) prepared in Example 5 was placed on a 4cm square glass plate. A 0.5mm thick glass plate was used as a spacer, and a 4cm square glass plate was placed on top. The plate was heated at 120°C with a hot plate to make a light guide plate with a thickness of 0.5mm.

Claims

1. A resin having repeating units represented by formula (I), In formula (I), -SZS- represents the structural unit derived from the monomer represented by equation (II). L represents a single bond or a divalent group. In formula (II), n represents any integer from 0 to 3. There can be multiple n's, which can be the same or different. R represents a monovalent substituent. When there are multiple Rs, they can be the same or different. In formula (II), the two -SH groups are bonded to the 1st and 6th positions, or the 2nd and 7th positions of the naphthalene ring.

2. The resin as described in claim 1, wherein, L is a divalent hydrocarbon group selected from the group consisting of divalent aliphatic chain hydrocarbon groups that may have substituents, divalent alicyclic hydrocarbon groups that may have substituents, and divalent groups that are combinations of them. The divalent hydrocarbon group containing one or more -CH2- groups can be -O-, -S-, or -NR-. 1A -(R) 1A It indicates the substitution of -CO- or -SO2- for hydrogen atoms or alkyl groups with 1 to 6 carbon atoms.

3. The resin as described in claim 2, wherein, Both the divalent aliphatic chain hydrocarbon group and the divalent alicyclic hydrocarbon group are saturated hydrocarbon groups.

4. The resin according to claim 1, wherein it has a linear molecular structure.

5. The resin as described in claim 2, wherein, The number of carbon atoms in the divalent aliphatic chain hydrocarbon group and the divalent alicyclic hydrocarbon group is 20 or less.

6. A composition comprising the resin of claim 1.

7. The composition of claim 6, further comprising a solvent.

8. A molded article formed from the resin of claim 1 or the composition of claim 6 or 7.

9. A light guide plate formed from the resin of claim 1 or the composition of claim 6 or 7.

10. A display device comprising the molded article of claim 8.

11. A solid-state imaging element comprising the molded article of claim 8.

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