Composition, method for producing composition, non-linear optical film, method for forming non-linear optical film, and optical modulator

Abstract

The purpose of the present invention is to provide: a composition which can improve the heat resistance and dissolution resistance of a formed film without altering electrooptical characteristics; a method for producing said composition; and a non-linear optical film. The present invention relates to a composition containing a non-linear optically active polymer compound, a metal element-containing compound and a solvent. The metal element is at least one element selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium and aluminum. The total content of metal elements selected from among said group is 10-200 ppm by mass relative to the total amount of solid content in the composition. The non-linear optically active polymer compound has a side chain. The side chain includes a urethane bond or urea bond.

Description

Composition, method for producing composition, nonlinear optical film, method for forming nonlinear optical film, and optical modulator

[0001] The present invention relates to a composition, a method for producing a composition, a nonlinear optical film, a method for forming a nonlinear optical film, and an optical modulator.

[0002] The technology of converting electrical signals into optical signals by shifting the phase of light passing through a nonlinear optical material, whose refractive index changes with the application of a voltage, is applied to devices such as optical modulators and optical switches. In such devices, particularly in the case of nonlinear optical materials utilizing organic compounds, a mixture of a polymer material such as polymethyl methacrylate (PMMA) and an organic compound with nonlinear optical activity (hereinafter sometimes referred to as a "nonlinear optically active compound") is generally used, or a polymer compound with nonlinear optical activity in which a group derived from a nonlinear optically active compound is attached as a side chain to the main chain of a polymer such as PMMA (hereinafter sometimes referred to as a "nonlinear optically active polymer compound") is used. Such nonlinear optical materials are used after being oriented in a certain direction to exhibit their nonlinear optical properties (generally expressed as the nonlinear optical coefficient). To achieve this orientation, a film containing the nonlinear optical material is heated (generally to near the glass transition temperature) to increase the fluidity of the film, and then an electric field is applied to align dipoles in a certain direction, creating an orientation state. The application of a voltage to the nonlinear optical material is carried out by placing electrodes on either side of the layer containing the nonlinear optical material. The process of creating this oriented state is called poling.

[0003] However, in the above-mentioned nonlinear optical material that has been subjected to a poling operation, the molecular orientation of the nonlinear optical material is relaxed by thermal energy at a finite temperature, and the electro-optic effect decreases over time. To prevent this, for example, when a nonlinear optically active polymer compound is used as the nonlinear optical material, the rate of orientation relaxation at a certain temperature becomes faster the closer the temperature is to the glass transition temperature. Therefore, in order to exhibit a large electro-optic effect over a long period of time, the nonlinear optically active polymer compound is required to have a high glass transition temperature.

[0004] In order to improve the glass transition temperature of a nonlinear optically active polymer compound, Patent Documents 1 and 2 use a base polymer copolymerized with a cycloalkyl methacrylate such as dicyclopentanyl methacrylate or adamantyl methacrylate. Patent Document 2 also proposes ensuring the film-forming ability that was a drawback of cycloalkyl methacrylate. Furthermore, Patent Document 3 proposes a method of improving heat durability by utilizing a (4+2) crosslink.

[0005] Japanese Patent Publication No. 2015-178544 International Publication No. 2017 / 159815 International Publication No. 2021 / 003296

[0006] However, the application of cycloalkyl methacrylate alone was insufficient to suppress the orientation relaxation of the nonlinear optical material. Furthermore, when (4+2) crosslinks were utilized, the optical properties of the nonlinear optical material changed, making it impossible to utilize its original properties.

[0007] Therefore, an object of the present invention is to provide a composition that can improve the thermal durability and dissolution resistance of the film formed without changing the electro-optical properties, a method for producing the composition, and a nonlinear optical film.

[0008] The present inventors have found that by applying a composition comprising a nonlinear optically active polymer compound, a metal element-containing compound, and a solvent, wherein the metal element is at least one selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum, the total content of the metal elements selected from the group is 10 to 200 mass ppm relative to the total solid content of the composition, and the nonlinear optically active polymer compound has side chains, the side chains containing urethane bonds or urea bonds, or by applying a nonlinear optical film in which the total content of the metal elements selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum is 10 to 200 mass ppm, the thermal durability after poling treatment can be improved without changing the electro-optical performance, and have completed the present invention.

[0009] That is, the present invention has the following gist.

[0010] A first aspect of the present invention relates to a composition comprising a nonlinear optically active polymer compound, a metal element-containing compound, and a solvent, wherein the metal element is at least one selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum, the total content of the metal elements selected from the group being 10 to 200 ppm by mass relative to the total solid content of the composition, and the nonlinear optically active polymer compound has a side chain, and the side chain contains a urethane bond or a urea bond.

[0011] A second aspect of the present invention relates to the composition according to the first aspect, wherein the total content of the metal elements selected from the above group is 50 to 200 ppm by mass relative to the total solid content.

[0012] A third aspect of the present invention relates to the composition of the first or second aspect, wherein the metal element comprises at least one selected from the group consisting of tin, titanium, bismuth, and zinc.

[0013] A fourth aspect of the present invention relates to the composition of any one of the first to third aspects, wherein the metal element-containing compound is an organometallic compound.

[0014] A fifth aspect of the present invention relates to the composition of the fourth aspect, wherein the organometallic compound is at least one selected from the group consisting of organotin compounds, organotitanium compounds, organobismuth compounds, and organozinc compounds.

[0015] A sixth aspect of the present invention relates to the composition of any one of the first to fifth aspects, wherein the side chain contains at least one group represented by the following formula (1):

[0016]

[0017] [In formula (1), X １１ is O or N-R １２ and R １１ and R １２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, or a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula (3), and * represents a bonding position. １１ and R １２ At least one of the groups is a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula (3):

[0018]

[0019] [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３are each independently a divalent group selected from a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom, ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ is a group represented by the following formula (4), ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 1 to 15.

[0020]

[0021] [In formula (4), *J ４１ Is Y ３１ represents the bonding position with ４１ and R ４２ each independently represents a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms; an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent; or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ４１ and R ４２ may be bonded to form a ring, or R ４１ and R ４２is R ４１ and R ４２ and may form a carbonyl group together with the carbon atom to which they are attached, R ４３ and R ４４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent; ４１ is O, S or N-Q ４１ represents, ４１ represents a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have a substituent.]

[0022] A seventh aspect of the present invention relates to the composition of the sixth aspect, wherein the side chain further comprises at least one group represented by the following formula (2):

[0023]

[0024] [In formula (2), X ２１ is O or N-R ２２ and R ２１ and R ２２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent, and * represents a bonding position.]

[0025] Aspect 8 of the present invention relates to the composition according to any one of Aspects 1 to 7, wherein the nonlinear optically active polymer compound is a compound having the side chain in at least one selected from the group consisting of poly(meth)acrylic acid ester, polyvinyl chloride, polystyrene, polyimide, polycarbonate, and copolymers thereof.

[0026] A ninth aspect of the present invention relates to the composition according to any one of the first to eighth aspects, further comprising a nonlinear optically active compound represented by the following formula (3):

[0027]

[0028] [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom, ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ is a group represented by the following formula (4), ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 1 to 15.

[0029]

[0030] [In formula (4), *J ４１ Is Y ３１ represents the bonding position with４１ and R ４２ each independently represents a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms; an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent; or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ４１ and R ４２ may be bonded to form a ring, or R ４１ and R ４２ is R ４１ and R ４２ and may form a carbonyl group together with the carbon atom to which they are attached, R ４３ and R ４４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent; ４１ is O, S or N-Q ４１ represents, ４１ represents a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have a substituent.]

[0031] A tenth aspect of the present invention relates to a method for producing the composition of any one of the first to nine aspects, comprising purifying at least one of the components of said composition or a mixture thereof by treatment with an adsorbent.

[0032] An eleventh aspect of the present invention relates to a nonlinear optical film formed from the composition of any one of the first to ninth aspects.

[0033] A twelfth aspect of the present invention relates to the nonlinear optical film of Aspect 11, wherein the total content of metal elements selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum is 10 to 200 ppm by mass relative to the total solid content.

[0034] A thirteenth aspect of the present invention relates to the nonlinear optical film of the twelfth aspect, wherein the total content of the metal elements selected from the above group relative to the total solid content is 50 to 200 ppm by mass.

[0035] A fourteenth aspect of the present invention relates to the nonlinear optical film of any one of the eleventh to thirteenth aspects, wherein the metal element includes at least one selected from the group consisting of tin, titanium, bismuth, and zinc.

[0036] A fifteenth aspect of the present invention relates to an optical modulator comprising the nonlinear optical film according to any one of the eleventh to fourteenth aspects.

[0037] A sixteenth aspect of the present invention relates to a method for forming a nonlinear optical film, comprising the steps of: applying the composition of any one of Aspects 1 to 9 onto a substrate; drying the applied composition; and baking the dried composition at 100 to 200°C, in this order.

[0038] A seventeenth aspect of the present invention relates to a nonlinear optical film, in which the total content of metal elements selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum is 10 to 200 ppm by mass relative to the total solid content.

[0039] An eighteenth aspect of the present invention relates to the nonlinear optical film of the seventeenth aspect, wherein the total content of the metal elements selected from the above group relative to the total solid content is 50 to 200 ppm by mass.

[0040] A nineteenth aspect of the present invention relates to the nonlinear optical film of the seventeenth or eighteenth aspect, wherein the metal element comprises at least one selected from the group consisting of tin, titanium, bismuth, and zinc.

[0041] A twentieth aspect of the present invention relates to an optical modulator comprising the nonlinear optical film according to any one of the seventeenth to nineteenth aspects.

[0042] According to the present invention, it is possible to provide a composition that can improve the thermal durability and dissolution resistance of the film formed without changing the electro-optical properties, a method for producing the composition, and a nonlinear optical film.

[0043] The following describes in detail the embodiments of the present invention, but the present invention is not limited to the following description and can be practiced with any modifications within the scope of the gist of the present invention. In this specification, when a numerical value or physical property value is enclosed before and after "...", the value before and after the "..." is used to include the values ​​before and after the "...". In this specification, the total solid content of a composition means components contained in the composition other than the solvent, and even if the components other than the solvent are liquid at room temperature, they are included in the solid content.

[0044] <Explanation of Terms> The terms used in this specification will be explained.

[0045] [Polymer Compound] In this specification, a polymer compound refers to a compound having a molecular weight of 2000 or more and containing four or more identical repeating units in the molecule. The polymer compound is not particularly limited, but is preferably a polymer, and may be any of a homopolymer, block copolymer, random copolymer, alternating copolymer, or graft copolymer, or may be in other forms. The polymer compound according to an embodiment of the present invention can be used as a polymer compound having nonlinear optical activity. In this specification, the polymer compound according to an embodiment of the present invention may be referred to as a nonlinear optically active polymer compound.

[0046] [Copolymer] A copolymer refers to a polymer compound having two or more types of structural units in the molecule.

[0047] [Substituents] Unless otherwise specified, the substituents are any groups, but are preferably those selected from the following substituent group W １ The substituents that may be present are selected from the group W １ The substituents selected from or optionally having are those in the substituent group W １ In the case where it is stated that the substituent is preferably selected from the following substituent group W １ As stated in the

[0048] [Substituent group W １ ] Substituent group W １ is a group consisting of a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aromatic oxy group, an aralkyloxy group, an alkylthio group, an aromatic thio group, an aralkylthio group, an alkyloxycarbonyl group, a dialkylamino group, a diarylamino group, an arylalkylamino group, an acyl group, a halogen atom, a haloalkyl group, an alkylthio group, an arylthio group, a silyl group, a siloxy group, a cyano group, an aralkyl group, an aromatic hydrocarbon group, and an aromatic heterocyclic group. These substituents may have any of a linear, branched, and cyclic structure.

[0049] Substituent group W １ More specifically, the following structures can be mentioned: A linear, branched, or cyclic alkyl group having 1 or more carbon atoms, preferably 4 or more, and usually 24 or less, preferably 12 or less, more preferably 8 or less, and even more preferably 6 or less. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, a dodecyl group, an adamantyl group, and the like. A linear, branched, or cyclic alkenyl group having usually 2 or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include a vinyl group, and the like. A linear or branched alkynyl group having usually 2 or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include an ethynyl group, and the like. A linear, branched, or cyclic alkoxy group having 1 or more carbon atoms and usually 24 or less, preferably 12 or less, specifically methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-hexyloxy, cyclohexyloxy, dodecyloxy, and adamantyloxy.

[0050] An aromatic oxy group having 4 or more carbon atoms, preferably 5 or more, and usually 36 or less, preferably 24 or less. Specific examples include a phenoxy group, a naphthoxy group, and a pyridyloxy group. An aralkyloxy group having 4 or more carbon atoms, preferably 5 or more, and usually 50 or less, preferably 30 or less. Specific examples include a benzyloxy group, a tolylmethoxy group, a thiophenylmethoxy group, a 2-phenylethyloxy group, a 2-phenylpropyl-2-yloxy group, a 2-phenylbutyl-2-yloxy group, a 3-phenylpentyl-3-yloxy group, a 3-phenyl-1-propyloxy group, a 4-phenyl-1-butyloxy group, a 5-phenyl-1-pentyoxyl group, a 6-phenyl-1-hexyloxy group, a 7-phenyl-1-heptyloxy group, and an 8-phenyl-1-octyloxy group.

[0051] An alkylthio group having 1 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include a methylthio group, an ethylthio group, an n-propylthio group, an iso-propylthio group, an n-butylthio group, an iso-butylthio group, a sec-butylthio group, a tert-butylthio group, an n-hexylthio group, a cyclohexylthio group, a dodecylthio group, and an adamantylthio group. An aromatic thio group having 3 or more carbon atoms, preferably 4 or more, and usually 50 or less, preferably 30 or less. Specific examples include a benzylthio group, a tolylthio group, and a thiophenylthio group. An aralkylthio group having 4 or more carbon atoms and usually 50 or less, preferably 30 or less. Specific examples include a benzylthio group, a tolylmethylthio group, a 2-phenylethylthio group, a 2-phenylpropyl-2-ylthio group, a 2-phenylbutyl-2-ylthio group, a 3-phenylpentyl-3-ylthio group, a 3-phenyl-1-propylthio group, a 4-phenyl-1-butylthio group, a 5-phenyl-1-pentylthio group, a 6-phenyl-1-hexylthio group, a 7-phenyl-1-heptylthio group, and an 8-phenyl-1-octylthio group.

[0052] An alkyloxycarbonyl group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include a methoxycarbonyl group and an ethoxycarbonyl group. A dialkylamino group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include a dimethylamino group and a diethylamino group. A diarylamino group having 10 or more carbon atoms, preferably 12 or more, and usually 36 or less, preferably 24 or less. Specific examples include a diphenylamino group, a ditolylamino group, an N-carbazolyl group, etc. An arylalkylamino group having 7 or more carbon atoms and usually 36 or less, preferably 24 or less. A specific example includes a phenylmethylamino group. An acyl group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include an acetyl group and a benzoyl group.

[0053] Halogen atoms such as fluorine, chlorine, bromine, and iodine atoms. Fluorine atoms are preferred. Haloalkyl groups having 1 or more carbon atoms and usually 12 or less, preferably 6 or less. Specific examples include a trifluoromethyl group. Alkylthio groups having 1 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include a methylthio group and an ethylthio group. Arylthio groups having 4 or more carbon atoms, preferably 5 or more, and usually 36 or less, preferably 24 or less. Specific examples include a phenylthio group, a naphthylthio group, and a pyridylthio group. Silyl groups having 2 or more carbon atoms, preferably 3 or more, and usually 36 or less, preferably 24 or less. Specific examples include a trimethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, and a triphenylsilyl group. Siloxy groups having 2 or more carbon atoms, preferably 3 or more, and usually 36 or less, preferably 24 or less, more preferably 18 or less. Specific examples include a trimethylsiloxy group, a tert-butyldimethylsiloxy group, a tert-butyldiphenylsiloxy group, and a triphenylsiloxy group.

[0054] An aralkyl group having usually 7 or more, preferably 9 or more, and usually 30 or less, preferably 18 or less, and more preferably 10 or less, carbon atoms. Specific examples include a benzyl group, a 2-phenylethyl group, a 2-phenylpropyl-2-yl group, a 2-phenylbutyl-2-yl group, a 3-phenylpentyl-3-yl group, a 3-phenyl-1-propyl group, a 4-phenyl-1-butyl group, a 5-phenyl-1-pentyl group, a 6-phenyl-1-hexyl group, a 7-phenyl-1-heptyl group, and an 8-phenyl-1-octyl group. An aromatic hydrocarbon group having 6 or more, usually 36 or less, preferably 24 or less, carbon atoms. Specific examples include a phenyl group, a naphthyl group, and a group in which multiple phenyl groups are linked. An aromatic heterocyclic group having 3 or more, preferably 4 or more, carbon atoms and usually 36 or less, preferably 24 or less, carbon atoms. Specific examples include a thienyl group, a pyridyl group, and the like.

[0055] The substituents may have any of a linear, branched, or cyclic structure. When the substituents are adjacent to each other, the adjacent substituents may be bonded to each other to form a ring. The preferred ring size is a 4-membered ring, a 5-membered ring, or a 6-membered ring, and specific examples include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

[0056] [Alkyl Group] The alkyl group may have a substituent, and may be linear, branched, or cyclic. The number of carbon atoms is not usually limited, but preferably has 1 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 30 or less, and even more preferably 10 or less. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, a dodecyl group, an adamantyl group, and the like. The substituents that these groups may have are included in the substituent group W. １ is selected from.

[0057] [Aromatic Group] The aromatic group may have a substituent and represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and refers to a monovalent, divalent, or trivalent or higher valent structure depending on the bonding state in the structure of the compound to be described later. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0058] [Aromatic Hydrocarbon Group] The aromatic hydrocarbon group refers to a monovalent, divalent, or trivalent or higher aromatic hydrocarbon ring structure, depending on the bonding state in the structure of the compound to be described later. In the aromatic hydrocarbon ring structure, the number of carbon atoms is generally not limited, but is preferably 6 to 60 carbon atoms, with the upper limit of the carbon number being more preferably 48 or less carbon atoms, and even more preferably 30 or less carbon atoms. Specific examples include 6-membered monocyclic rings or fused ring groups containing 2 to 5 rings, such as benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings, as well as structures in which multiple groups selected from these are linked. When multiple aromatic hydrocarbon rings are linked, typically, structures in which 2 to 10 rings are linked are exemplified, with structures in which 2 to 5 rings are linked being preferred. When a plurality of aromatic hydrocarbon rings are linked, the linked rings may have the same structure or different structures.

[0059] [Aromatic heterocyclic group] The aromatic heterocyclic group refers to a monovalent, divalent, or trivalent or higher aromatic heterocyclic structure depending on the bonding state in the structure of the compound to be described later. In the heteroaromatic ring structure, the number of carbon atoms is not usually limited, but is preferably 3 to 50, and the upper limit of the carbon number is more preferably 45 or less, and even more preferably 30 or less. Specific examples thereof include a 5- or 6-membered single ring or a fused ring group containing 2 to 4 rings, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, or a quinazolinone ring, or a group in which a plurality of these rings are linked together. When a plurality of heteroaromatic rings are linked, the heteroaromatic rings may have the same structure or different structures. When a plurality of heteroaromatic rings are linked, typically, a structure in which 2 to 10 rings are linked is mentioned, and a structure in which 2 to 5 rings are linked is preferred.

[0060] [Amino Group] The amino group may have a substituent, and is preferably a secondary amino group, and more preferably a tertiary amino group. The substituent on the amino group is preferably an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group, and these groups may have a substituent. Furthermore, when the amino group has a plurality of substituents, these may be the same or different, and may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded. Specific examples include a dimethylamino group, a diethylamino group, an ethylmethylamino group, an n-propylmethylamino group, a di-isopropylamino group, a di-n-butylamino group, a di-n-hexylamino group, a di-n-butylamino group, a methylphenylamino group, an ethylphenylamino group, a butylphenylamino group, a hexylphenylamino group, a diphenylamino group, a 2,6-dimethylphenylphenylamino group, and a 2,4,6-trimethylphenylphenylamino group. The substituents that these groups may have are included in the substituent group W. １ is selected from.

[0061] [Halogen Atom] Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0062] [Alkyloxycarbonyl Group] The alkyloxycarbonyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 2 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 30 or less, and even more preferably 20 or less. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an iso-propoxycarbonyl group, an n-butoxycarbonyl group, an iso-butoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an n-hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a dodecyloxycarbonyl group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0063] [Alkylsulfonyl Group] The alkylsulfonyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 2 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an iso-propylsulfonyl group, an n-butylsulfonyl group, an iso-butylsulfonyl group, a sec-butylsulfonyl group, a tert-butylsulfonyl group, an n-hexylsulfonyl group, a cyclohexylsulfonyl group, and a dodecylsulfonyl group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0064] [Aralkyl Group] The aralkyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 2 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 30 or less, and even more preferably 20 or less. Specific examples include a benzyl group, a 2-phenylethyl group, a 2-phenylpropyl-2-yl group, a 2-phenylbutyl-2-yl group, a 3-phenylpentyl-3-yl group, a 3-phenyl-1-propyl group, a 4-phenyl-1-butyl group, a 5-phenyl-1-pentyl group, a 6-phenyl-1-hexyl group, a 7-phenyl-1-heptyl group, and an 8-phenyl-1-octyl group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0065] [Boryl Group] The boryl group may have a substituent, and is preferably a secondary boryl group, more preferably a tertiary boryl group. The substituent that the boryl group has is preferably a hydroxy group, an alkyloxycarbonyl group, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group, and these groups may have a substituent. Furthermore, when the boryl group has a plurality of substituents, they may be the same or different, and may be bonded to each other to form a ring together with the boron atom to which each is bonded. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0066] [Acyl group] The acyl group may have a substituent, and the number of carbon atoms is not usually limited, but preferably has 2 to 50 carbon atoms, and the upper limit of the carbon number is more preferably 24 or less, and even more preferably 12 or less. Specific examples include a benzoyl group and an acetyl group. The substituents that these groups may have are included in the substituent group W. １ is selected from.

[0067] [Alkoxy Group] The alkoxy group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 1 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-hexyloxy group, a cyclohexyloxy group, and a dodecyloxy group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0068] [Aromatic Oxy Group] The aromatic oxy group may have a substituent, and the number of carbon atoms is not usually limited, but preferably has 3 to 50 carbon atoms, and the upper limit of the carbon number is more preferably 30 or less, and even more preferably 20 or less. Specific examples include a naphthoxy group and a thiophenyloxy group. The substituents that these groups may have are included in the substituent group W. １ is selected from.

[0069] [Aralkyloxy Group] The aralkyloxy group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 4 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a benzyloxy group, a tolylmethoxy group, a thiophenylmethoxy group, a 2-phenylethyloxy group, a 2-phenylpropyl-2-yloxy group, a 2-phenylbutyl-2-yloxy group, a 3-phenylpentyl-3-yloxy group, a 3-phenyl-1-propyloxy group, a 4-phenyl-1-butyloxy group, a 5-phenyl-1-pentyloxy group, a 6-phenyl-1-hexyloxy group, a 7-phenyl-1-heptyloxy group, and an 8-phenyl-1-octyloxy group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0070] [Alkylthio Group] The alkylthio group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 1 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, an n-hexylthio group, a cyclohexylthio group, and a dodecylthio group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0071] [Aromatic Thio Group] The aromatic thio group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, and the upper limit of the carbon number is more preferably 30 or less, and even more preferably 20 or less. Specific examples include a benzylthio group, a tolylthio group, and a thiophenylthio group. The substituents that these groups may have are included in the substituent group W. １ is selected from.

[0072] [Aralkylthio Group] The aralkyloxy group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 4 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a benzylthio group, a tolylmethylthio group, a 2-phenylethylthio group, a 2-phenylpropyl-2-ylthio group, a 2-phenylbutyl-2-ylthio group, a 3-phenylpentyl-3-ylthio group, a 3-phenyl-1-propylthio group, a 4-phenyl-1-butylthio group, a 5-phenyl-1-pentylthio group, a 6-phenyl-1-hexylthio group, a 7-phenyl-1-heptylthio group, and an 8-phenyl-1-octylthio group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0073] [Silyl Group] The silyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a trimethylsilyl group, a triethylsilyl group, a propyldimethylsilyl group, a tert-butyldimethylsilyl group, and a tert-butyldiphenylsilyl group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0074] [Hydrocarbon Ring Group] The hydrocarbon ring group is a cyclic hydrocarbon group which may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 20 or less, and even more preferably 10 or less. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a group in which a plurality of these groups are linked together.

[0075] [Branched, linear, or cyclic saturated or unsaturated hydrocarbon chain, some of whose carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms] The branched, linear, or cyclic saturated or unsaturated hydrocarbon chain, some of whose carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, refers to a carbon chain consisting of a branched, linear, or cyclic alkyl group, alkenyl group, or alkynyl group having 1 to 15 carbon atoms, in which part of the carbon chain may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms. Specific examples include the following groups.

[0076] Specific examples of unsubstituted groups include hydrocarbon chains of 1 to 15 carbon atoms, more specifically methyl groups, ethyl groups, 1-butyl groups, tert-butyl groups, cyclopentyl groups, 4-ethyl-1-cyclohexyl groups, 2-penten-1-yl groups, 1-octyl groups, 1-decyl groups, etc., with methyl groups, ethyl groups, and 1-butyl groups being preferred. Specific examples of groups substituted with oxygen atoms include 2-ethoxyethyl groups, 2-(2-ethoxyethoxy)ethyl groups, 2-hydroxyethyl groups, and tetrahydropyranyloxypropyl groups, with 2-ethoxyethyl groups and 2-hydroxyethyl groups being preferred, and 2-hydroxyethyl groups being particularly preferred. Specific examples of groups substituted with sulfur atoms include 2-ethylthioethyl groups, tetrahydrothienyl groups, and 2-(2-ethylthioethylthio)ethyl groups. Specific examples of groups substituted with silicon atoms include trimethylsilyl groups and tert-butyldimethylsilyl groups. These may also be substituted with oxygen atoms or silicon atoms at the same time, and specific examples thereof include a 2-(trimethylsilyloxy)ethyl group, a 2-(tert-butyldimethylsilyloxy)ethyl group, a 4-(tert-butyldimethylsilyloxy)butyl group, a 2-(tert-butyldiphenylsilyloxy)ethyl group, and a 2-(tert-butyldimethylsilyloxy)hexyl group, and preferably a 2-(tert-butyldimethylsilyloxy)ethyl group and a 4-(tert-butyldimethylsilyloxy)butyl group. The substituents that these groups may have are those in the substituent group W１ is selected from.

[0077] [Heterocyclic Group] The heterocyclic group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a thiane group, a 1,4-dithiane group, a tetrahydrofuran group, a tetrahydropyran group, a pyran group, a 1,4-dioxane group, or a group in which a plurality of these groups are linked together. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0078] [π-conjugated linking group] The π-conjugated linking group is a divalent group in the structure of a compound to be described later, which is composed of alternately connected single bonds and multiple bonds and has delocalized electrons (π electrons). The π-conjugated linking group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 2 to 50 carbon atoms, and the upper limit of the carbon number is more preferably 30 or less, and even more preferably 20 or less. In addition, the substituents possessed by multiple π-conjugated groups may be bonded to form a cyclic structure. Specific examples include vinylene, thiophene, furan, pyrrole, etc. The substituents that these groups may have are represented by the substituent group W. １ is selected from.

[0079] [Blocked Isocyanate Group] A blocked isocyanate group represents a group in which an isocyanate group is protected with a blocking agent. It is characterized by remaining stable under normal conditions and dissociating the blocking agent upon heat treatment, resulting in the regeneration of the isocyanate group. The group selected as the blocking agent is not particularly limited, but may have from 1 to 50 carbon atoms, with the upper limit of the carbon number being preferably 30 or less, and even more preferably 20 or less. Furthermore, the substituents of multiple π-conjugated groups may be bonded to form a cyclic structure. Specific examples include a methylethyloxime group, a 3,5-dimethylpyrazolyl group, and an ε-caprolactam group. A dimethylpyrazole group is preferred. The heat treatment temperature required for dissociating the blocking agent is not particularly limited, as it varies depending on the catalyst and reaction conditions, but is generally 20°C to 250°C. The lower limit is preferably 40°C or higher, more preferably 60°C or higher, and most preferably 100°C or higher, while the upper limit is preferably 250°C or lower, more preferably 200°C or lower.

[0080] [Nonlinear Optical Material] The nonlinear optical material according to the embodiment of the present invention comprises a nonlinear optically active compound, a nonlinear optically active polymer compound, or both.

[0081] [Nonlinear Optically Active Compound] The nonlinear optically active compound according to the embodiment of the present invention is a compound represented by formula (3) described below.

[0082] [Group represented by formula (1)] The group represented by formula (1) according to the embodiment of the present invention is shown below.

[0083]

[0084] [In formula (1), X １１ is O or N-R １２ and R １１ and R １２are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, or a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula (3), and * represents a bonding position. １１ and R １２ At least one of the groups is a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula (3):

[0085] [X １１ ] X １１ is O or N-R １２ From the viewpoint of manufacturing stability, X １１ is preferably O.

[0086] [R １１ and R １２ ] R １１ and R １２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, or a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula (3) described below, provided that R １１ and R １２ At least one of R is a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula (3): １１ is preferably a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula (3): １２is preferably a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or a phenyl group, more preferably a hydrogen atom, or a branched, linear or cyclic saturated or unsaturated hydrocarbon chain which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, particularly preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. １１ and R １２ The substituents which may be contained in the group W １ It is preferably selected from:

[0087] [*] * indicates the bond position.

[0088] [Specific examples of groups represented by formula (1)] Specific examples of groups represented by formula (1) according to embodiments of the present invention are shown below. The groups represented by formula (1) are not limited to these. In the formula, * represents the bonding position with the main chain or side chain of the nonlinear optically active polymer compound, and # represents the bonding position with the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3).

[0089]

[0090]

[0091] [Compound Represented by Formula (3)] The compound represented by formula (3) according to an embodiment of the present invention is shown below.

[0092]

[0093] [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３are each independently a divalent group selected from a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom, ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ is a group represented by the following formula (4), ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 1 to 15.

[0094] (Ar ３１ ) Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent.

[0095] Examples of the aromatic hydrocarbon group include rings having a carbon number of usually 6 or more and usually 60 or less, preferably 30 or less, more preferably 18 or less, and even more preferably 10 or less, such as a benzene ring, naphthalene ring, anthracene ring, tetraphenylene ring, phenanthrene ring, chrysene ring, pyrene ring, benzanthracene ring, or perylene ring. In order to fix the molecular structure by hydrogen bonding with the adjacent π-conjugated linking group, a benzene ring or naphthalene ring having an alkoxy group or aralkyloxy group is particularly preferred.

[0096] Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, or a quinazolinone ring, each of which typically has 3 or more carbon atoms and typically has 50 or less, preferably 45 or less, more preferably 30 or less, and even more preferably 12 or less. A thiophene ring is particularly preferred for shifting the absorption wavelength of the dye to a longer wavelength. In order to fix the molecular structure by hydrogen bonding with the adjacent π-conjugated linking group, a heterocycle having an alkoxy group or an aralkyloxy group is particularly preferred. ３１ The substituents which may be contained in the group W １ It is preferably selected from:

[0097] (R ３１ and R ３３ ) R ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent. ３１ and R ３３ The substituents which may be contained in the group W １ It is preferably selected from:

[0098] (R ３２ and R ３４ ) R ３２ and R ３４R each independently represents a hydrogen atom, a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group, or a halogen atom. From the viewpoint of production stability, a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms is preferred, and a linear saturated carbon chain having 1 to 5 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms is more preferred. ３２ and R ３４ The substituents which may be contained in the group W １ It is preferably selected from:

[0099] (Y ３１ ) Y ３１ Each of Y is independently a divalent π-conjugated linking group which may have a substituent. ３１ If there are multiple Y ３１ may have the same structure or different structures. ３１ The plurality of substituents of may form a bond to form a cyclic structure. Examples of the π-conjugated linking group include groups having carbon atoms of usually 2 or more and usually 50 or less, preferably 30 or less, and more preferably 20 or less, such as vinylene which may have a substituent, thiophene which may have a substituent, furan which may have a substituent, and pyrrole which may have a substituent. ３１ The substituents which may be contained in the group W １ It is preferably selected from:

[0100] (Z ３１ ) Z ３１ is a group represented by formula (4) described below.

[0101] (m ３１ ~m ３３ , n３１ ) m ３１ are each independently an integer of 0 to 5, and m ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, and n ３１ is an integer from 1 to 15. ３１ is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and even more preferably an integer of 0 to 2. ３２ is preferably an integer of 1 to 4, more preferably an integer of 1 to 3. ３３ is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and even more preferably an integer of 0 to 2. From the viewpoint of improving the nonlinear optical properties of the dye, n ３１ is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and from the viewpoint of reducing absorption loss, is preferably 14 or less, more preferably 13 or less, and even more preferably 10 or less.

[0102] [Group represented by formula (4)]

[0103] [In formula (4), *J ４１ Is Y ３１ represents the bonding position with ４１ and R ４２ each independently represents a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms; an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent; or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ４１ and R ４２ may be bonded to form a ring, or R ４１ and R ４２ is R ４１ and R ４２ and may form a carbonyl group together with the carbon atom to which they are attached, R ４３ and R ４４each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent; ４１ is O, S or N-Q ４１ represents, ４１ represents a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have a substituent.]

[0104] (*J ４１ ) *J ４１ Is Y ３１ This is the bonding position with

[0105] (R ４１ and R ４２ ) R ４１ and R ４２ each independently represents a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms; an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent; or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ４１ and R ４２ may be bonded to form a ring, or R ４１ and R ４２ is R ４１ and R ４２ and may form a carbonyl group together with the carbon atom to which they are bonded. ４１ and R ４２ The substituent of R is preferably a fluorine atom, a chlorine atom, a bromine atom, or a cyano group. ４１ and R ４２ The substituents which may be contained in the group W １ It is preferably selected from:

[0106] (R ４３ and R ４４ ) R ４３ and R４４ R are each independently a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent. ４３ and R ４４ is preferably a cyano group. ４３ and R ４４ The substituents which may be contained in the group W １ It is preferably selected from:

[0107] (X ４１ ) X ４１ is O, S or N-Q ４１ Preferably O or NQ ４１ and more preferably O.

[0108] (Q ４１ ) Q ４１ is a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, or an aralkyl group which may have a substituent. ４１ The substituents which may be contained in the group W １ It is preferably selected from:

[0109] [Specific Examples of Compounds Represented by Formula (3)] Specific examples of compounds represented by formula (3) according to the embodiment of the present invention are shown below. The compounds represented by formula (3) are not limited to these.

[0110]

[0111]

[0112]

[0113]

[0114]

[0115] [Group represented by formula (2)] The group represented by formula (2) according to the embodiment of the present invention is shown below.

[0116]

[0117] [In formula (2), X ２１ is O or N-R ２２ and R ２１ and R ２２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent, and * represents a bonding position.]

[0118] (X ２１ ) X ２１ is O or N-R ２２ From the viewpoint of manufacturing stability, X ２１ is preferably O.

[0119] (R ２１ and R ２２ ) R ２１ and R ２２ are each independently a hydrogen atom, a branched, linear, or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. In terms of the thermal stability of the compound, a branched, linear, or cyclic, saturated or unsaturated hydrocarbon chain which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or a phenyl group is preferred, and a branched, linear, or cyclic, saturated or unsaturated hydrocarbon chain which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms is more preferred, and a methyl group or an adamantyl group is particularly preferred. ２１ and R ２２ The substituents which may be contained in the group W １ It is preferably selected from:

[0120] (*) * indicates the bond position.

[0121] [Specific Examples of the Group Represented by Formula (2)] Specific examples of the group represented by formula (2) according to the embodiment of the present invention are shown below. The group represented by formula (2) is not limited to these.

[0122]

[0123] <Composition> A composition according to an embodiment of the present invention is a composition comprising a nonlinear optically active polymer compound, a metal element-containing compound, and a solvent, wherein the metal element is at least one selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum, the total content of the metal elements selected from the group being 10 to 200 ppm by mass relative to the total solid content of the composition, and the nonlinear optically active polymer compound has a side chain, which contains a urethane bond or a urea bond.

[0124] [Nonlinear Optically Active Polymer Compound] The nonlinear optically active polymer compound that can be used in the composition according to the embodiment of the present invention is not particularly limited as long as it has a side chain and the side chain contains a urethane bond or a urea bond. Here, the term "nonlinear optical activity" as used herein refers to the exhibiting of a nonlinear optical effect, and the term "nonlinear optically active polymer compound" refers to a polymer compound that exhibits such activity.

[0125] The side chain of the nonlinear optically active polymer compound preferably contains at least one group represented by the above formula (1). By containing such a group, a better nonlinear optical effect can be obtained. In order to obtain uniformity in film thickness when a film containing the nonlinear optically active polymer compound is formed, it is more preferable that the side chain of the nonlinear optically active polymer compound further contains at least one group represented by the above formula (2) in addition to the group represented by the above formula (1). In such a case, the group represented by the above formula (1) and the group represented by the above formula (2) may be contained in the same side chain or in different side chains, but it is preferable that they be contained in different side chains for reasons of production stability.

[0126] In this specification, a group that can be represented by formula (1) and also by formula (2) is referred to as a group represented by formula (1).

[0127] The group represented by formula (1) or (2) may be bonded to the main chain or side chain of the polymer compound, and is preferably bonded to the side chain from the viewpoint of the stability of the compound. The group represented by formula (1) or (2) may be bonded to the polymer compound directly or via a linking group, and is preferably bonded via a linking group from the viewpoint of the stability of the compound.

[0128] When the group represented by formula (1) or formula (2) is bonded via a linking group, the linking group is not particularly limited, and examples thereof include a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or a divalent group selected from an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent. From the viewpoint of film stability, among these, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms is preferred, and an ethyloxy group is more preferred.

[0129] The nonlinear optically active polymer compound preferably has at least one main chain selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimides, polycarbonates, and copolymers thereof, more preferably at least one main chain selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polycarbonates, and copolymers thereof, and even more preferably at least one main chain selected from the group consisting of poly(meth)acrylic acid esters, polystyrene, polycarbonates, and copolymers thereof. Having such a main chain is preferable from the viewpoint of compound stability. In one embodiment, the nonlinear optically active polymer compound may be a compound having the side chain in at least one main chain selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimides, polycarbonates, and copolymers thereof.

[0130] When the nonlinear optically active polymer compound contains a monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3), the content of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) can be expressed as the ratio of the mass of the entire nonlinear optically active polymer compound to the mass of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3), or can be expressed as the molar percentage of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) relative to the total of each repeating unit of the nonlinear optically active polymer compound. When expressed as a mass ratio, there is no particular limitation on the content of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) in the nonlinear optically active polymer compound, but from the viewpoint of the balance between the electro-optical effect and solubility, when the mass of the entire nonlinear optically active polymer compound is taken as 100, the mass of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) is preferably 1 or more, more preferably 10 or more, even more preferably 20 or more, preferably 80 or less, more preferably 60 or less, and even more preferably 50 or less. When expressed as a molar percentage, there is no particular limitation, but from the viewpoint of the balance between the electro-optical effect and solubility, the molar percentage of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) relative to the total of each repeating unit of the nonlinear optically active polymer compound is preferably 0.1 mol% or more, more preferably 1 mol% or more, even more preferably 2 mol% or more, preferably 60 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less.

[0131] The content of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) in the nonlinear optically active polymer compound is １ It is calculated by H-NMR, absorbance measurement, gel permeation chromatography (GPC) or the like, but preferably, １ H-NMR, absorbance measurement, most preferably １ Calculated by H-NMR.

[0132] １ ​A specific method for calculating the content of a monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) in a nonlinear optically active polymer compound by H-NMR is to use the spectral integral value derived from a specific hydrogen atom of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) as a reference and determine the ratio of the spectral integral value derived from a specific hydrogen atom of the group possessed by each repeating unit of the nonlinear optically active polymer compound, thereby calculating the molar ratio of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) to each repeating unit of the nonlinear optically active polymer compound. From this molar ratio, the apparent mass ratio can be calculated, and the content of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) in the nonlinear optically active polymer compound can be calculated.

[0133] A specific method for calculating the content of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) in a nonlinear optically active polymer compound by absorbance measurement is to calculate the content from the ratio of the maximum absorbance obtained by measuring the absorbance of the nonlinear optically active polymer compound in the same manner to the concentration obtained by dividing the maximum absorbance obtained by measuring the absorbance of the nonlinear optically active polymer compound using a solution in which a monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) is dissolved at a predetermined concentration. The absorbance is measured using an ultraviolet-visible-near-infrared spectrophotometer.

[0134] The content of the groups represented by formula (1) and formula (2) in a nonlinear optically active polymer compound can be expressed as a molar percentage of the total of repeating units containing the groups represented by formula (1) and formula (2) relative to the total of each repeating unit of the nonlinear optically active polymer compound. There are no particular restrictions on the total content of the groups represented by formula (1) and formula (2) in a nonlinear optically active polymer compound, but from the viewpoint of the balance between the electro-optical effect and heat resistance, the total molar percentage of the groups represented by formula (1) and formula (2) relative to the total of each repeating unit of the nonlinear optically active polymer compound is preferably 0.01 mol% or more, more preferably 0.1 mol% or more. Also, it is preferably 50 mol% or less, more preferably 40 mol% or less, particularly preferably 30 mol% or less, and most preferably 20 mol% or less. The content of the groups represented by formula (1) and formula (2) in a nonlinear optically active polymer compound is the same as the content of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (3) described above, for example, １ It can be determined by H-NMR.

[0135] The weight-average molecular weight of the nonlinear optically active polymer compound is not particularly limited, but is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 30,000 or more, in order to improve durability. Also, in order to maintain solubility, it is preferably 500,000 or less, more preferably 400,000 or less, and even more preferably 300,000 or less. The weight-average molecular weight of the nonlinear optically active polymer compound is confirmed by measuring the weight-average molecular weight using GPC when polystyrene is used as a standard.

[0136] There are no particular limitations on the molecular weight distribution of the nonlinear optically active polymer compound, but it is preferably 3 or less, more preferably 2.8 or less, and even more preferably 2.5 or less. From the viewpoint of orientation control, it is preferable that the molecular weight distribution of the nonlinear optically active polymer compound is 3 or less. The molecular weight distribution of the nonlinear optically active polymer compound is confirmed by measuring the ratio of the number average molecular weight to the weight average molecular weight using GPC with polystyrene as a standard.

[0137] The glass transition temperature (Tg) of the nonlinear optically active polymer compound is not particularly limited, but is generally 40°C to 300°C. To improve heat resistance, it is preferably 45°C or higher, more preferably 50°C or higher, and even more preferably 80°C or higher. From the viewpoint of the influence of the nonlinear optically active compound during poling, it is preferably 280°C or lower, more preferably 250°C or lower, and even more preferably 230°C or lower. The Tg of the nonlinear optically active polymer compound is confirmed by measuring the temperature corresponding to the intersection of the slope of the rising part of the endothermic process and the baseline of the baseline shift of the DSC curve accompanying the glass transition using a differential scanning calorimeter (DSC).

[0138] The decomposition temperature (Td) of the nonlinear optically active polymer compound is not particularly limited, but is preferably 0°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. It is also preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 300°C or lower. The Td of the nonlinear optically active polymer compound is confirmed by measuring the temperature at which the mass decreases by 5% using a thermogravimetric differential thermal analyzer (TG-DTA).

[0139] Specific examples of nonlinear optically active polymer compounds according to embodiments of the present invention are shown below. However, the nonlinear optically active polymer compounds are not limited to these. In the following formulas, v, w, x, y, and z represent the molar ratios of the respective repeating units constituting the nonlinear optically active compound.

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154] The content of the nonlinear optically active polymer compound in the composition is not particularly limited, but is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more, per 100 parts by mass of the composition. Also, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of the composition. It is preferable that the content of the nonlinear optically active polymer compound is 1 part by mass or more, per 100 parts by mass of the composition, from the viewpoint of ensuring a film thickness. It is also preferable that the content is 50 parts by mass or less, since it has good coatability.

[0155] The content of the nonlinear optically active polymer compound and the metal element-containing compound in the total solid content of the composition is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 99% by mass or more, based on the total solid content. There is no particular upper limit, and for example, it is preferable that the total solid content of the composition is only the nonlinear optically active polymer compound and the metal element-containing compound, that is, 100% by mass. Furthermore, when the composition contains solid content other than the nonlinear optically active polymer compound and the metal element-containing compound, the content of the nonlinear optically active polymer compound is preferably 99.9% by mass or less. It is preferable that the content of the nonlinear optically active polymer compound in the total solid content of the composition is 80% by mass or more, from the viewpoint of ensuring a film thickness.

[0156] [Metal Element-Containing Compound] The metal element-containing compound contained in the composition according to the embodiment of the present invention contains at least one metal element selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum. Examples of such metal element-containing compounds include carboxylates such as acetate, oleate, octoate, and neodecanoate of at least one metal element selected from the group; sulfides, nitrates, and sulfates; and halides such as bromides, chlorides, and iodides.

[0157] More specifically, stannous chloride, tetra-n-butyltin, stannic chloride, trimethyltin hydroxide, dimethyltin dichloride, di-n-butyltin laurate, dibutyltin diacetate, titanium 2-ethylhexoxide, titanium ethylacetoacetate, bismuth trisacetate, bismuth sulfide, bismuth tris(neodecanoate), bismuth nitrate, Zinc bisacetylacetonate, zinc bis3,5-heptanedionate, zinc bis1,1,1-trifluoro-2,4-pentanedionate, zinc bis1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, zinc bismethyl acetoacetate, zinc bisethyl acetoacetate, zinc bisn-propyl acetoacetate, zinc bisisopropyl acetoacetate, zinc bisdimethyl malonate, zinc bisdiethyl malonate, zinc bisacetoacetanilide, zinc bisacetic acid, zinc bispropionic acid, zinc bisbutanoic acid, zinc bispentanoic acid, zinc bishexanoic acid, zinc bisheptanoic acid, zinc bisoctanoic acid, zinc bis2-ethylhexanoic acid, zirconium acetylacetate, zirconium pentanedionate, iron acetylacetonate, iron tris(N,N-diethyl-3-oxobutanamidate), manganese bisacetylacetonate, copper acetylacetonate, lead naphthenate, lead 2-ethylhexanoate, nickel acetylacetonate, cobalt naphthenate, cobalt 2-ethylhexanoate, antimony trichloride, hafnium pentanedionate, hafnium acetylacetate, aluminum trisacetylacetonate, aluminum bisacetylacetonate isopropoxide, aluminum bisacetylacetonate n-propoxide, aluminum bisacetylacetonate methoxide, aluminum bisacetylacetonate ethoxide, aluminum bisacetylacetonate n-butoxide, aluminum bisacetylacetonate sec-butoxide, aluminum bisacetylacetonate tert-butoxide, aluminum tris(3,5-heptanedionate), or mixtures thereof.

[0158] In one embodiment, the metal element-containing compound is preferably an organometallic compound, and the organometallic compound may be at least one selected from the group consisting of organotin compounds, organotitanium compounds, organobismuth compounds, and organozinc compounds. The organometallic compound may also be a metal catalyst compound. Examples of the metal catalyst compound include metal catalyst compounds used in the formation of urethane bonds. Examples of the organometallic compound include the compounds shown in the following diagram.

[0159]

[0160] The reason why the effects of the present invention are exhibited in a film formed from a composition comprising a nonlinear optically active polymer compound containing a urethane bond or urea bond in its side chain, a metal element-containing compound, and a solvent, wherein the metal element is at least one selected from a specific group, and the total content of the metal elements selected from the specific group is 10 to 200 ppm by mass is not clear, but is presumed to be as follows. That is, it is thought that by performing the poling treatment, in the presence of the metal contained in the metal element-containing compound, the isocyanate groups generated from the urethane bond or the urea bond undergo a slight reverse reaction, and the reactive groups react with each other, thereby strengthening the polymer network. It is presumed that this improves the thermal durability of a film formed from a composition according to an embodiment of the present invention without changing its optical performance.

[0161] The content of the metal element-containing compound in the composition is not particularly limited, but is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.05 parts by mass or more, relative to 100 parts by mass of the composition. Also, it is preferably 10 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, and particularly preferably 0.5 parts by mass or less, relative to 100 parts by mass of the composition. It is preferable that the content of the metal element-containing compound is 0.001 parts by mass or more relative to 100 parts by mass of the composition, since it can improve heat resistance. It is also preferable that it is 3 parts by mass or less, since it can ensure uniformity of the film thickness.

[0162] [Solvent] There are no particular limitations on the solvent that can be used in the composition according to the embodiment of the present invention, as long as it can dissolve the nonlinear optically active polymer compound and the metal element-containing compound. The solvent is preferably an organic solvent, for example, aromatic hydrocarbons such as toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, and styrene; aliphatic hydrocarbons such as n-hexane and n-heptane; halogenated hydrocarbons such as chlorobenzene, orthodichlorobenzene, chloroform, dichloromethane, dibromomethane, 1,2-dichloroethane, trifluoromethylbenzene, and 3-methoxybenzotrifluoride; ketones such as acetone, ethyl methyl ketone, isopropyl methyl ketone, isobutyl methyl ketone, butyl methyl ketone, diacetone alcohol, diethyl ketone, cyclopentanone, and cyclohexanone; esters such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, ethyl lactate, γ-butyrolactone, ethyl benzoate, methyl benzoate, benzoyl benzoate, 2-ethylhexyl benzoate, and ethyl 4-methylbenzoate; amides such as N-cyclohexyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone; alcohols such as methanol, ethanol, propanol, 2-propanol, allyl alcohol, butanol, isobutyl alcohol, tert-butyl alcohol, pentanol, 2-methylbutanol, 2-methyl-2-butanol, cyclohexanol, 2-methylpentanol, octanol, 2-ethylhexanol, benzyl alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; glycols such as ethylene glycol, propylene glycol, hexylene glycol, trimethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether;Examples of suitable organic solvents include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; and anisole. These organic solvents may be used alone or in combination of two or more.

[0163] Of the above solvents, from the viewpoint of coatability, chlorobenzene, orthodichlorobenzene, 1,2-dichloroethane, trifluoromethylbenzene, 3-methoxybenzotrifluoride, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are more preferable, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are even more preferable, and cyclopentanone, cyclohexanone, toluene, anisole, and dibromomethane are particularly preferable.

[0164] The content of the solvent in the composition is not particularly limited, but is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more, relative to 100 parts by mass of the composition. Also, it is preferably 99 parts by mass or less, more preferably 97 parts by mass or less, and even more preferably 96 parts by mass or less, relative to 100 parts by mass of the composition. If the content of the solvent is 50 parts by mass or more, relative to 100 parts by mass of the composition, it is preferable because it has good coatability. Also, if it is 99 parts by mass or less, it is preferable from the viewpoint of ensuring film thickness.

[0165] [Metal Elements] The total content of metal elements selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum relative to the total solid content of the composition according to an embodiment of the present invention is 10 to 200 ppm by mass. The total content of metal elements selected from the above group relative to the total solid content of the composition is preferably 20 ppm by mass or more, more preferably 30 ppm by mass or more, even more preferably 40 ppm by mass or more, even more preferably 50 ppm by mass or more, particularly preferably 60 ppm by mass or more, and particularly preferably 80 ppm by mass or more. It is also preferably 200 ppm by mass or less, more preferably 150 ppm by mass or less, and even more preferably 100 ppm by mass or less. In one embodiment, the total content of metal elements selected from the above group relative to the total solid content of the composition can be 50 to 200 ppm by mass. If the total content of the metal elements selected from the above group relative to the total solid content of the composition is less than 10 ppm by mass, the thermal retention of the electro-optic coefficient of the film formed from the composition may be reduced, while if it exceeds 200 ppm by mass, the retention and / or solubility may be reduced.

[0166] The metal element contained in the composition is at least one selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum. Of these, it is preferable that the composition contains at least one selected from the group consisting of tin, titanium, bismuth, and zinc.

[0167] The composition may contain metallic elements other than tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium and aluminum. Examples of such metal elements include lithium, beryllium, boron, sodium, magnesium, aluminum, phosphorus, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, strontium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, barium, hafnium, tantalum, tungsten, rhenium, iridium, platinum, gold, mercury, thallium, lead, bismuth, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. From the viewpoint of uniformity of the film, the total content of metal elements other than tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum relative to the total solid content of the composition is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, and even more preferably 50 ppm by mass or less.

[0168] The content of metal elements in the composition can be calculated using techniques such as inductively coupled plasma optical emission spectrometry, inductively coupled plasma mass spectrometry, atomic absorption spectrometry, and X-ray fluorescence spectrometry.

[0169] [Nonlinear Optically Active Compound] From the viewpoint of improving the nonlinear optical effect, the composition according to the embodiment of the present invention preferably further contains a nonlinear optically active compound represented by the above formula (3).

[0170] The content of the nonlinear optically active compound in the composition is not particularly limited, but is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of the nonlinear optically active polymer compound. Also, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of the composition. It is preferable that the content of the nonlinear optically active compound is 0.1 parts by mass or more, per 100 parts by mass of the nonlinear optically active polymer compound, because the nonlinear optical effect is improved. It is also preferable that the content is 50 parts by mass or less, because the compatibility of the nonlinear optically active compound with the nonlinear optically active polymer compound is improved.

[0171] [Other Components] In addition to the nonlinear optically active polymer compound, the metal element-containing compound, the solvent, the metal element, and the nonlinear optically active compound, other components may be used in the composition.

[0172] There are no particular restrictions on the other components as long as they do not impair the purpose of using the composition. However, as long as the effects of the present invention are not impaired, the composition may contain, as necessary, antioxidants such as hydroquinone, ultraviolet absorbers such as benzophenone, rheology modifiers such as silicone oil and surfactants, adhesion aids such as silane coupling agents, crosslinkers for the polymer matrix, compatibilizers, curing agents, pigments, storage stabilizers, antifoaming agents, and the like.

[0173] The content of other components in the composition is not particularly limited, but from the viewpoint of uniformity of the film thickness, the content is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the composition.

[0174] [Method for Producing Composition] A method for producing a composition according to an embodiment of the present invention can include dissolving the nonlinear optically active polymeric compound and the metal element-containing compound in the solvent. One embodiment includes a method for producing a composition, including the steps of mixing the nonlinear optically active polymeric compound and the metal element-containing compound with the solvent, heating and stirring to dissolve, mixing the resulting solution with the nonlinear optically active compound, stirring to dissolve, and filtering the resulting solution. Another embodiment includes a method for producing a composition, including the steps of mixing a mixture of the nonlinear optically active polymeric compound and the metal element-containing compound, or a mixture of the nonlinear optically active polymeric compound and the residue of the metal element-containing compound used in synthesizing the nonlinear optically active polymeric compound, with the solvent, heating and stirring to dissolve, and filtering the resulting solution.

[0175] Furthermore, for the purpose of preventing unwanted components from being mixed into the composition or for the purpose of adjusting the content of metal elements in the composition, the method for producing the composition may include a step of purifying the components of the composition or a mixture thereof. The purification method used in the step of purifying the components of the composition or a mixture thereof is not particularly limited, and purification methods such as washing, adsorption, chromatography, and crystallization can be used. From the viewpoint of compound stability, it is preferable to use adsorption or crystallization as the purification method. In one embodiment, the method for producing the composition may include a step of purifying the components of the composition or a mixture thereof by adsorption treatment using an adsorbent such as activated carbon or activated clay, or by crystallization treatment that utilizes differences in solubility to precipitate crystals. From the viewpoint of improving compound stability and film durability, it is preferable that the method for producing the composition include a step of purifying at least one of the components of the composition or a mixture thereof by treatment with an adsorbent.

[0176] However, when the residue of the metal element-containing compound used in the synthesis of the nonlinear optically active polymer compound is very large, for example, when the amount of the metal element-containing compound used as a reaction catalyst is very large, it may not be possible to bring the metal element-containing compound within the predetermined range even by the above-mentioned purification method, so care must be taken. Whether the amount of the metal element-containing compound used is very large or not depends on the combination with an adsorbent in the adsorption treatment when removing the metal element-containing compound by purification and / or the combination with a solvent in the crystallization treatment.

[0177] [Uses of the Composition] There are no particular limitations on the uses of the composition according to the embodiment of the present invention, but it is generally used to form a nonlinear optically active polymer compound into a film or thin film. The nonlinear optically active polymer compound formed into a film or thin film can be used in nonlinear optical elements such as optical modulators or electric field sensors. For example, the composition can be used as an ink for forming nonlinear optical elements.

[0178] <Nonlinear Optical Film> The nonlinear optical film according to the first embodiment of the present invention is a nonlinear optical film formed from the above-described composition.

[0179] The components contained in the nonlinear optical film and their preferred ranges are the same as those described for the composition above, except that the nonlinear optical film generally does not contain a solvent.

[0180] The total content of metal elements selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum relative to the total solid content of the nonlinear optical film according to the first embodiment of the present invention is preferably 10 to 200 ppm by mass. The total content of metal elements selected from the above group relative to the total solid content of the nonlinear optical film is more preferably 20 ppm by mass or more, even more preferably 30 ppm by mass or more, even more preferably 40 ppm by mass or more, even more preferably 50 ppm by mass or more, particularly preferably 60 ppm by mass or more, and most preferably 80 ppm by mass or more. It is also more preferably 200 ppm by mass or less, even more preferably 150 ppm by mass or less, and particularly preferably 100 ppm by mass or less. In one aspect, the total content of metal elements selected from the above group relative to the total solid content of the nonlinear optical film according to the first embodiment of the present invention can be 50 to 200 ppm by mass. The total content of the metal elements selected from the above group relative to the total solid content of the nonlinear optical film is preferably 10 ppm by mass or more, since the heat resistance can be improved, and preferably 200 ppm by mass or less, since the uniformity of the film thickness can be ensured.

[0181] Furthermore, the nonlinear optical film according to the second embodiment of the present invention is a nonlinear optical film in which the total content of metal elements selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum is 10 to 200 mass ppm relative to the total solid content.

[0182] The preferred aspects of the total content of the metal elements selected from the above group relative to the total solid content of the nonlinear optical film according to the second embodiment of the present invention and the reasons for this are the same as those described for the total content of the metal elements selected from the above group relative to the total solid content of the nonlinear optical film according to the first embodiment.

[0183] Furthermore, the metal element contained in the nonlinear optical film according to the first and second embodiments of the present invention preferably includes at least one selected from the group consisting of tin, titanium, bismuth, and zinc.

[0184] Furthermore, the nonlinear optical film according to the first and second embodiments of the present invention may contain metal elements other than tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum. Preferred examples of such metal elements and preferred aspects such as the total content are the same as those described for the composition.

[0185] In addition, when the nonlinear optical film is produced, if the process of adding additional components to the composition is not included, and the solvent of the composition is only removed, it can be said that the content of the metal element in the nonlinear optical film is the same as the content of the metal element relative to the total solid content in the composition.From the viewpoint of manufacturing stability, in the method of forming a nonlinear optical film described later, it is preferable that the process of adding additional components to the composition is not included, and the solvent of the composition is only removed.

[0186] [Method for forming a nonlinear optical film] There are no particular limitations on the method for forming a nonlinear optical film or a nonlinear optical thin film (hereinafter, both are collectively referred to as "nonlinear optical film") from the composition according to an embodiment of the present invention, and examples thereof include known methods such as injection molding, press molding, soft lithography, wet coating, etc. Among these, wet coating methods such as spin coating, blade coating, dip coating, and inkjet coating can be mentioned from the viewpoints of simplicity of the manufacturing equipment, mass productivity, film quality (uniformity of film thickness, few defects such as bubbles, etc.), etc.

[0187] One embodiment includes a method of coating a composition obtained by dissolving the nonlinear optically active polymer compound and the metal element-containing compound in the solvent onto a substrate and drying the composition. Here, "drying" refers to, for example, a process of drying by placing the substrate on a heating device such as a hot plate and heating it, or a process of drying by placing the coated substrate in a chamber and evacuating it, or a combination of both processes. Another embodiment includes a method of coating a composition obtained by dissolving the nonlinear optically active polymer compound and the metal element-containing compound in the solvent onto a substrate and drying it under vacuum. A preferred method of forming a nonlinear optical film can include, in this order, a process of coating the composition onto a substrate, a process of drying the coated composition, and a process of baking the dried composition at 100 to 200°C.

[0188] <Nonlinear Optical Element> A nonlinear optical element according to an embodiment of the present invention comprises the nonlinear optical film described above. The nonlinear optical element is not particularly limited as long as it comprises the nonlinear optical film described above and operates based on the nonlinear optical effect, and examples thereof include wavelength conversion elements, photorefractive elements, and electro-optical elements. Of these, nonlinear optical elements that operate based on the electro-optic effect are preferred, and more specifically, electro-optical elements such as optical switches, optical modulators, and phase shifters are preferred. In one aspect, the nonlinear optical element can be an optical modulator comprising the nonlinear optical film described above.

[0189] The electro-optical element is preferably an element having a structure in which a nonlinear optical film is formed on a substrate and sandwiched between a pair of electrodes for inputting electrical signals.

[0190] Examples of materials that can be used to form such substrates include metals such as aluminum, gold, iron, nickel, chromium, and titanium; semiconductors such as silicon, titanium oxide, zinc oxide, and gallium arsenide; glass; and plastics such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polysulfone, polyether ketone, and polyimide.

[0191] A conductive film may be formed on the surface of the substrate. Examples of materials for such a conductive film include metals such as aluminum, gold, nickel, chromium, and titanium; conductive oxides such as tin oxide, indium oxide, ITO (tin oxide-indium oxide composite oxide), and IZO (indium oxide-zinc oxide composite oxide); and conductive polymers such as polythiophene, polyaniline, polyparaphenylene vinylene, and polyacetylene. The conductive film is formed using a known dry film formation method such as vapor deposition or sputtering, or a known wet film formation method such as dip coating or electrolytic deposition, and may be patterned as needed. The conductive substrate, or the conductive film formed on the substrate as described above, is used as an electrode (hereinafter also referred to as the "lower electrode") during poling or during operation as a device.

[0192] On the surface of the substrate, if necessary, an adhesive layer for improving the adhesion between the film formed thereon and the substrate, a leveling layer for smoothing the unevenness of the substrate surface, or some intermediate layer that provides these functions all at once may be formed.The material for forming such a film is not particularly limited, and known materials such as acrylic resin, methacrylic resin, amide resin, vinyl chloride resin, vinyl acetate resin, phenolic resin, urethane resin, vinyl alcohol resin, acetal resin, etc. and their copolymers; zirconium chelate compound, titanium chelate compound, crosslinked material of silane coupling agent, etc. and their co-crosslinked material can be used.

[0193] The electro-optical element is preferably formed to include a waveguide structure, and it is particularly preferable to include the above-mentioned nonlinear optical film in the core layer of the waveguide.

[0194] A clad layer (hereinafter also referred to as a "lower clad layer") may be formed between the substrate and the core layer containing the nonlinear optical film. This lower clad layer may be any material as long as it has a lower refractive index than the core layer and is not affected during core layer formation. Preferred materials for forming the lower clad layer include UV-curable or thermosetting resins such as acrylic, epoxy, oxetane, thiirane, and silicone resins; polyimide; and glass.

[0195] After forming the core layer using the nonlinear optical film described above, a clad layer (hereinafter sometimes referred to as an "upper clad layer") may be formed on top of it in the same manner as the lower clad layer, thereby forming a slab waveguide having a structure of substrate / lower clad layer / core layer / upper clad layer.

[0196] After forming the core layer, the core layer can be patterned by a known method using semiconductor process technology such as reactive ion etching (RIE), photolithography, electron beam lithography, etc. to form a channel waveguide or a ridge waveguide. Alternatively, a channel waveguide can be formed by patterning and irradiating part of the core layer with UV light, electron beam, etc., to change the refractive index of the irradiated part.

[0197] A basic electro-optical element can be formed by forming an electrode (hereinafter referred to as an "upper electrode") for applying an input electrical signal to the surface of the upper clad layer in a desired region of the upper clad layer.

[0198] When a channel waveguide or a ridge waveguide is formed as described above, the core layer pattern can be configured to have a known device structure such as a straight, Y-branch, directional coupler, or Mach-Zehnder type, and can be applied to known optical information communication devices such as optical switches, optical modulators, and phase shifters. One example of the application to an optical information communication device is an optical modulator equipped with a nonlinear optical element that operates based on the above-mentioned electro-optic effect.

[0199] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples, and the present invention can be practiced with any modifications without departing from the gist of the present invention.

[0200] Example 1 (Cleaning of ITO Substrate) A thin-film ITO substrate (manufactured by EHC Corporation; having a 9 nm thick ITO film on one side of a 0.7 mm thick glass plate; sheet resistance of the ITO film side: 519 to 578 Ω / □) was cleaned in ultrapure water using an ultrasonic cleaner to obtain an ITO substrate to be used for coating the composition. Here, the glass plate included in the ITO substrate corresponds to the carrier, and the ITO film corresponds to the electrode. The film thickness was measured using an optical interferometer (VertScan optical interferometer, manufactured by Hitachi High-Tech Corporation).

[0201] (Preparation of Film 1) A mixture of the following Compound 1-1 and Compound 1-2 (Dibutyltin Dilaurate, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in cyclohexanone so that the content (ppm by mass) of each metal element relative to the total solid content of the composition represented by the following formula (A) was the value shown in Table 1, and the total solid content concentration was 11.5% by mass, and the mixture was filtered through a PTFE (polytetrafluoroethylene) filter with a pore size of 0.22 μm, thereby obtaining Composition 1.

[0202] The results of elemental analysis of Composition 1 using an inductively coupled plasma optical emission spectrometer (iCAP7600Duo, manufactured by Thermo Fisher Scientific) are shown in Table 1. Composition 1 was applied onto the surface of the ITO substrate on which the ITO film was formed using a spin coater (MS-A150, manufactured by Mikasa Co., Ltd.).

[0203]

[0204]

[0205] The ITO substrate coated with Composition 1 was prebaked on a hot plate (HP-1SA, manufactured by AS ONE Corporation) at 60°C for 1 minute. The prebaked ITO substrate was subjected to a thermal drying treatment at 85°C for 15 hours in a vacuum constant temperature dryer (DP-23, manufactured by Yamato Scientific Co., Ltd.) to remove the solvent, thereby obtaining a film-coated substrate (Substrate 1) of Example 1. Substrate 1 is a substrate containing a nonlinear optically active polymer compound, in which a film (Film 1, thickness 1.2 μm) containing a nonlinear optically active polymer compound is formed on an ITO substrate.

[0206] (Preparation of Substrate with Electrode) For the prepared substrate 1, a film containing a nonlinear optically active polymer compound was applied to a portion of the surface thereof with a thickness of 50 nm and an area of ​​30 mm. ２ Gold electrodes were formed by depositing gold using a vacuum deposition apparatus (EX-400-C08, manufactured by ULVAC, Inc.) so that the gold electrodes were formed, thereby obtaining electrode-attached substrate 1. Electrode-attached substrate 1 had the following layer structure and was used to evaluate the electro-optic coefficient. Layer structure: ITO substrate (glass plate carrier + ITO film) / film containing a nonlinear optically active polymer compound / gold electrode

[0207] (Poling Treatment) The prepared electrode-attached substrate 1 was heated to 155°C using a temperature controller (Model 3060, manufactured by Lake Shore Cryotronics), and cooled to room temperature with liquid nitrogen while applying a voltage of 100 V / µm using a voltage application device (2470 Source Meter, manufactured by Keithley Corporation), thereby obtaining a poled substrate 1 in which the nonlinear optically active polymer compound in the electrode-attached substrate 1 was electrically oriented. The poled substrate 1 was composed of an ITO substrate / poled film 1 (with gold electrodes formed on a portion of the surface).

[0208] [Electro-optic coefficient] The electro-optic coefficient (hereinafter referred to as "electro-optic coefficient (initial value)") at a wavelength of 1.31 μm (laser light source: TSL-570, manufactured by Santec Corporation) of the prepared poled substrate 1 was measured by a method similar to that disclosed in C. C. Teng et al., Appl. Phys. Lett., 56, p. 1734 (1990) and Y. Shuto et al., J. Appl. Phys., 77, p. 4632 (1995). A function generator (T3AFG10, manufactured by Teledyne LeCroy) was used to apply the AC voltage, and a lock-in amplifier (LI5600, digital lock-in amplifier, manufactured by NF Corporation) was used to evaluate the intensity. The results are shown in Table 1.

[0209] [Electro-optic coefficient maintenance rate] The substrate on which the electro-optic coefficient measurement had been performed was heated on a hot plate (HP-1SA, manufactured by AS ONE Corporation) at 125°C for 20 minutes, and the electro-optic coefficient (after heating) was measured again to calculate the electro-optic coefficient maintenance rate. The electro-optic coefficient maintenance rate was calculated using the following formula: Electro-optic coefficient maintenance rate = Electro-optic coefficient (after heating) / Electro-optic coefficient (initial value) The results are shown in Table 1.

[0210] [Content of Each Metal Element Relative to the Total Solid Content of the Composition] Elemental analysis by inductively coupled plasma atomic emission spectrometry was performed on the compositions of Example 1, and the compositions of Examples 2 to 7 and Comparative Examples 1 to 11 described below (Composition 1, Compositions 2 to 7, and Compositions C1 to C11, respectively). The content of each metal element in the resulting composition was then divided by the total solid content concentration of the composition to determine the content of each metal element relative to the total solid content of the composition. In Table 1, the notation [n.d.] indicates that the respective metal elements were below the detection limit. In other words, for metal elements represented as [n.d.] in Table 1, the elemental analysis performed in the Examples and Comparative Examples showed that the contents of tin, titanium, bismuth, and / or zinc were below the detection limit (10 ppm by mass, 3 ppm by mass, 30 ppm by mass, and 2 ppm by mass, respectively). Metal elements other than those shown in Table 1, namely zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium and aluminum, were all below the detection limit. The same can be said for Tables 2 and 3.

[0211] The content of each metal element was calculated based on the following formula: The results are shown in Table 1.

[0212]

[0213]

[0214]

[0215] Example 2 A film (Film 2, thickness 1.1 μm) of Example 2 containing a nonlinear optically active polymer compound and a film-coated substrate (Substrate 2) were obtained in the same manner as in the preparation of Film 1, except that Composition 2 was used, in which the content of metal elements relative to the total solid content of the composition was adjusted to the value shown in Table 1 by adjusting the amount of Compound 1-2 added. Furthermore, poled Substrate 2 obtained from Substrate 2 by the same method as in Example 1 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0216] Example 3 A film (film 3, thickness 1.0 μm) and a film-coated substrate (substrate 3) of Example 3 containing a nonlinear optically active polymer compound were obtained in the same manner as in the preparation of Film 1, except that composition 3 was used in which the content of metal elements relative to the total solid content of the composition was set to the value shown in Table 1 by using the following compound 1-3 (zinc bis(2-ethylhexanoate)-mineral spirit solution, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) instead of compound 1-2 and adjusting the amount added. Furthermore, poled substrate 3 obtained from substrate 3 by the same method as in Example 1 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0217]

[0218] Example 4 A film (Film 4, thickness 1.1 μm) and a film-coated substrate (Substrate 4) of Example 4 containing a nonlinear optically active polymer compound were obtained in the same manner as in the preparation of Film 1, except that Compound 1-4 (Bismuth 2-ethylhexanoate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of Compound 1-2, and the content of metal elements relative to the total solid content of the composition was adjusted to the value shown in Table 1. Furthermore, poled Substrate 4 obtained from Substrate 4 by the same method as in Example 1 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0219]

[0220] Example 5 A film (Film 5, thickness 1.2 μm) and a film-coated substrate (Substrate 5) of Example 5 containing a nonlinear optically active polymer compound were obtained in the same manner as in the preparation of Film 1, except that Compound 1-2 was replaced with Compound 1-5 (Tetrabutyl Orthotitanate, manufactured by Tokyo Chemical Industry Co., Ltd.) and Composition 5 were used, in which the content of metal elements relative to the total solid content of the composition was adjusted to the value shown in Table 1 by adjusting the amount added. Furthermore, poled Substrate 5 obtained from Substrate 5 by the same method as in Example 1 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0221]

[0222] Comparative Example 1 A film (film C1, thickness 1.1 μm) and a film-coated substrate (substrate C1) containing a nonlinear optically active polymer compound of Comparative Example 1 were obtained in the same manner as in the preparation of Film 1, except that composition C1 was used in which the content of metal elements relative to the total solid content of the composition was adjusted to the value shown in Table 1 by adjusting the amount of compound 1-2 added. Furthermore, poled substrate C1 obtained from substrate C1 by the same method as in Example 1 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0223] Comparative Example 2 A film (film C2, thickness 1.1 μm) containing a nonlinear optically active polymer compound and a film-coated substrate (substrate C2) of Comparative Example 2 were obtained in the same manner as in the preparation of Film 1, except that composition C2 was used in which the content of metal elements relative to the total solid content of the composition was adjusted to the value shown in Table 1 by adjusting the amount of compound 1-2 added. Furthermore, poled substrate C2 obtained from substrate C2 by the same method as in Example 1 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0224] Comparative Example 3 A film (film C3, thickness 1.2 μm) containing a nonlinear optically active polymer compound and a film-coated substrate (substrate C3) of Comparative Example 3 were obtained in the same manner as in the preparation of Film 1, except that composition C3 was used in which the content of metal elements relative to the total solid content of the composition was adjusted to the value shown in Table 1 by adjusting the amount of compound 1-2 added. Furthermore, poled substrate C3 obtained from substrate C3 by the same method as in Example 1 was evaluated in the same manner as in Example 1. The film condition of poled substrate C3 was poor, and the electro-optic coefficient could not be measured. The results are shown in Table 1.

[0225] Comparative Example 4 A film (film C4, thickness 1.1 μm) containing a nonlinear optically active polymer compound and a film-coated substrate (substrate C4) of Comparative Example 4 were obtained in the same manner as in the preparation of Film 3, except that composition C4 was used in which the content of metal elements relative to the total solid content of the composition was adjusted to the value shown in Table 1 by adjusting the amount of compound 1-3 added. Furthermore, poled substrate C4 obtained from substrate C4 by the same method as in Example 1 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0226] Comparative Example 5 A film (film C5, thickness 1.1 μm) containing a nonlinear optically active polymer compound and a film-coated substrate (substrate C5) of Comparative Example 5 were obtained in the same manner as in the preparation of Film 4, except that composition C5 was used in which the content of metal elements relative to the total solid content of the composition was adjusted to the value shown in Table 1 by adjusting the amount of compound 1-4 added. Furthermore, poled substrate C5 obtained from substrate C5 by the same method as in Example 1 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0227] Comparative Example 6 A film (film C6, thickness 1.2 μm) containing a nonlinear optically active polymer compound and a film-coated substrate (substrate C6) of Comparative Example 6 were obtained in the same manner as in Film 5, except that composition C6 was used, in which the content of metal elements relative to the total solid content of the composition was adjusted to the value shown in Table 1 by adjusting the amount of compound 1-5 added. Furthermore, poled substrate C6 obtained from substrate C6 by the same method as in Example 1 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0228] Example 6 The film thickness of the poled film 1 (where the gold electrode was not laminated) prepared in Example 1 was measured. Next, cyclopentanone was spin-coated onto the film 1, and the solvent was removed by thermal drying at 85°C for 15 hours in a vacuum constant temperature dryer (DP-23, manufactured by Yamato Scientific Co., Ltd.) in the same manner as in Example 1. Thereafter, the film thickness of the film 1 (where the gold electrode was not laminated) was measured again to determine the film thickness retention rate. The film thickness retention rate was calculated using the following formula. The results are shown in Table 2.

[0229]

[0230]

[0231] Example 7 The film thickness retention rate was determined in the same manner as in Example 6, except that the poled film 2 prepared in Example 2 was used instead of the poled film 1. The results are shown in Table 2.

[0232] Comparative Example 7 The film thickness retention rate was determined in the same manner as in Example 6, except that the poled film C1 prepared in Comparative Example 1 was used instead of the poled film 1. The results are shown in Table 2.

[0233] Comparative Example 8 The film thickness retention rate was determined in the same manner as in Example 6, except that the poled film C2 prepared in Comparative Example 2 was used instead of the poled film 1. The results are shown in Table 2.

[0234] As can be seen from the results in Tables 1 and 2, the improvement in heat resistance is thought to be due to the inclusion of an appropriate amount of metal element, which promotes the crosslinking reaction. At the same time, the progress of the crosslinking reaction is thought to be due to the decrease in the solubility of the film.

[0235] Comparative Example 9 A film (film C9, thickness 1.2 μm) and a film-coated substrate (substrate C9) of Comparative Example 9 containing a nonlinear optically active polymer compound were obtained in the same manner as in the preparation of film 1, except that compound 1-6 below was used instead of compound 1-1 and composition C9 was used, in which the content of metal elements relative to the total solids content of the composition was set to the value shown in Table 3 by adjusting the amount of compound 1-2 added. Furthermore, a poled substrate C9 was obtained from substrate C9 in the same manner as in Example 1, except that the temperature during poling was changed to 120° C. Evaluation of the electro-optic coefficient retention rate of the obtained poled substrate C9 was performed in the same manner as in Example 1, except that the temperature of the heating test was changed from 125° C. to 85° C. The results are shown in Table 3.

[0236]

[0237]

[0238] Comparative Example 10 A film (film C10, thickness 1.0 μm) and a film-coated substrate (substrate C10) containing a nonlinear optically active polymer compound of Comparative Example 10 were obtained in the same manner as in the preparation of film C9, except that composition C10 was used in which the content of metal elements relative to the total solid content of the composition was adjusted to the value shown in Table 3 by adjusting the amount of compound 1-2 added. Furthermore, poled substrate C10 obtained from substrate C10 by the same method as in Comparative Example 9 was evaluated in the same manner as in Comparative Example 9. The results are shown in Table 3.

[0239] Comparative Example 11 A film (film C11, thickness 1.6 μm) and a film-coated substrate (substrate C11) containing a nonlinear optically active polymer compound of Comparative Example 11 were obtained in the same manner as in the preparation of film C9, except that composition C11 was used in which the content of metal elements relative to the total solid content of the composition was adjusted to the value shown in Table 3 by adjusting the amount of compound 1-2 added. Furthermore, poled substrate C11 obtained from substrate C11 by the same method as in Comparative Example 9 was evaluated in the same manner as in Comparative Example 9. The results are shown in Table 3.

[0240] As can be seen from the results in Table 3, the effect of improving heat resistance was not obtained in the composition of Compound 1-6, which is a polymer not containing a urethane bond or a urea bond, and a metal element. This result supports the idea that crosslinking due to the catalytic action of the metal does not proceed in the absence of a urethane bond or a urea bond.

[0241] Furthermore, since the production of the film does not involve the step of adding any further components to the composition, but rather involves only removing the solvent from the composition, it can be said that the content of metal elements in the film is the same as the content of metal elements relative to the total solid content in the composition.

[0242] Although various embodiments have been described above, it goes without saying that the present invention is not limited to such examples. It is clear that a person skilled in the art can conceive of various modifications or alterations within the scope of the claims, and it is understood that these also naturally fall within the technical scope of the present invention. Furthermore, the components of the above embodiments may be combined in any manner as long as they do not deviate from the spirit of the invention.

[0243] This application is based on a Japanese patent application (Patent Application No. 2024-100558) filed on June 21, 2024, the contents of which are incorporated herein by reference.

[0244] The composition of the present invention can be used in nonlinear optical elements, electric field sensors, and the like.

Claims

1. A composition comprising a nonlinear optically active polymer compound, a metal element-containing compound, and a solvent, wherein the metal element is at least one selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum, and the total content of the metal elements selected from the group relative to the total solid content of the composition is 10 to 200 ppm by mass, and the nonlinear optically active polymer compound has a side chain, and the side chain contains a urethane bond or a urea bond.

2. The composition according to claim 1, wherein the total content of the metal elements selected from the group is 50 to 200 ppm by mass relative to the total solid content.

3. The composition according to claim 1, wherein the metallic element comprises at least one selected from the group consisting of tin, titanium, bismuth, and zinc.

4. The composition of claim 1, wherein the metal element-containing compound is an organometallic compound.

5. The composition according to claim 4, wherein the organometallic compound is at least one selected from the group consisting of organotin compounds, organotitanium compounds, organobismuth compounds and organozinc compounds.

6. The composition according to claim 1, wherein the side chain contains at least one group represented by the following formula (1): [In formula (1), X １１ is O or N-R １２ and R １１ and R １２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, or a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula (3), and * represents a bonding position. １１ and R １２ At least one of the groups is a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula (3): [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom, ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ is a group represented by the following formula (4), ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 1 to 15. [In formula (4), *J ４１ Is Y ３１ represents the bonding position with ４１ and R ４２ each independently represents a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms; an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent; or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ４１ and R ４２ may be bonded to form a ring, or R ４１ and R ４２ is R ４１ and R ４２ and may form a carbonyl group together with the carbon atom to which they are attached, R ４３ and R ４４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent; ４１ is O, S or N-Q ４１ represents, ４１ represents a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have a substituent.] 7. The composition according to claim 6, wherein the side chain further contains at least one group represented by the following formula (2): [In formula (2), X ２１ is O or N-R ２２ and R ２１ and R ２２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent, and * represents a bonding position.] 8. The composition according to claim 1, wherein the nonlinear optically active polymer compound is a compound having the side chain in at least one selected from the group consisting of poly(meth)acrylic acid ester, polyvinyl chloride, polystyrene, polyimide, polycarbonate, and copolymers thereof.

9. The composition according to claim 1, further comprising a nonlinear optically active compound represented by the following formula (3): [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom, ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ is a group represented by the following formula (4), ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 1 to 15. [In formula (4), *J ４１ Is Y ３１ represents the bonding position with ４１ and R ４２ each independently represents a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms; an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent; or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ４１ and R ４２ may be bonded to form a ring, or R ４１ and R ４２ is R ４１ and R ４２ and may form a carbonyl group together with the carbon atom to which they are attached, R ４３ and R ４４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent; ４１ is O, S or N-Q ４１ represents, ４１ represents a branched, linear or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have a substituent.] 10. A method for producing a composition according to any one of claims 1 to 9, comprising the step of purifying at least one of the components of said composition or a mixture thereof by treatment with an adsorbent.

11. A nonlinear optical film formed from the composition according to any one of claims 1 to 9.

12. The nonlinear optical film according to claim 11, wherein the total content of metal elements selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum is 10 to 200 ppm by mass relative to the total solid content.

13. The nonlinear optical film according to claim 12, wherein the total content of the metal elements selected from the group is 50 to 200 ppm by mass relative to the total solid content.

14. The nonlinear optical film according to claim 11, wherein the metal element comprises at least one selected from the group consisting of tin, titanium, bismuth, and zinc.

15. An optical modulator comprising the nonlinear optical film according to claim 11.

16. A method for forming a nonlinear optical film, comprising the steps of: applying the composition according to any one of claims 1 to 9 onto a substrate; drying the applied composition; and baking the dried composition at 100 to 200°C, in this order.

17. A nonlinear optical film, in which the total content of metal elements selected from the group consisting of tin, titanium, bismuth, zinc, zirconium, iron, manganese, copper, lead, nickel, cobalt, antimony, hafnium, and aluminum is 10 to 200 mass ppm relative to the total solid content.

18. The nonlinear optical film according to claim 17, wherein the total content of the metal elements selected from the group is 50 to 200 ppm by mass relative to the total solid content.

19. The nonlinear optical film according to claim 17, wherein the metal element comprises at least one selected from the group consisting of tin, titanium, bismuth, and zinc.

20. An optical modulator comprising the nonlinear optical film according to any one of claims 17 to 19.

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