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

Abstract

The purpose of the present invention is to provide a composition with which it is possible to improve nonlinear optical characteristics of a nonlinear optically active material, and a nonlinear optical film. The present invention relates to a composition comprising a nonlinear optically active material, a surfactant, and a solvent, the surfactant containing a silicone-based surfactant, the composition including, as the nonlinear optically active material, at least one compound selected from the group consisting of a compound represented by formula (1) and a nonlinear optically active polymer compound that contains a monovalent or polyvalent group obtained by removing at least one hydrogen atom from a compound represented by formula (1), and the content of the silicone-based surfactant relative to the total solid content in the composition being 3 mass% or less. (The definitions of the groups in formula (1) are as described in the specification.)

Description

Composition, nonlinear optical film, method for forming a nonlinear optical film, and optical modulator

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

[0002] The technique of converting electrical signals into optical signals by shifting the phase of light passing through a nonlinear optical material, which utilizes the property of nonlinear optical materials where the refractive index changes upon application of 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 a nonlinear optically active compound is generally used, or a polymer compound having nonlinear optical activity is used in which groups derived from the nonlinear optically active compound are attached as side chains to the main chain of PMMA or similar material. Such nonlinear optical materials are used after orienting the nonlinear optically active compound in a certain direction in order to exhibit nonlinear optical properties (generally expressed as nonlinear optical coefficients). To create this orientation, a method is employed in which a film containing the nonlinear optical material is heated (generally to near the glass transition temperature) to improve the fluidity of the film, and then a voltage is applied to align the dipoles in a certain direction. The voltage to the nonlinear optical material is applied by arranging electrodes so as to sandwich the layer containing the nonlinear optical material. This operation to create the orientation is called the polling process.

[0003] However, due to their large dipole moments, nonlinear optically active compounds tend to associate in directions that cancel each other's dipole moments, making orientation in a specific direction difficult. Furthermore, when nonlinear optically active compounds are associated, the nonlinear optical effects are also canceled out, so despite poling treatment, the nonlinear optical properties of the nonlinear optically active material do not fully manifest, and for example, the nonlinear optical coefficient of the nonlinear optical material may be low. In order to fully manifest the nonlinear optical properties of a nonlinear optically active material and, for example, increase the nonlinear optical coefficient of the nonlinear optical material, it is necessary to suppress the association of nonlinear optically active compounds. In particular, there is a desire for additives that can improve the nonlinear optical properties of a nonlinear optical material by being added to a composition containing a nonlinear optically active compound without altering the structure of the nonlinear optically active compound.

[0004] Patent documents 1 and 2 list additives that may be included in compositions for nonlinear optical materials.

[0005] Japanese Patent Publication No. 2014-130196 Japanese Patent Publication No. 2015-129780

[0006] However, neither Patent Document 1 nor 2 contains any specific disclosure of the additives listed in each document, nor does it offer any indication of the relationship between the additives and the nonlinear optical properties of the nonlinear optical material. It was also unclear whether the additives could improve the nonlinear optical properties of the nonlinear optical material.

[0007] Therefore, the object of the present invention is to provide a composition and a nonlinear optical film that can improve the nonlinear optical properties of a nonlinear optically active material.

[0008] The present inventors have discovered that by applying a composition comprising a nonlinear optically active material, a surfactant, and a solvent, wherein the surfactant includes a silicone-based surfactant and the content of the silicone-based surfactant is within a predetermined range, a nonlinear optical film with improved nonlinear optical properties can be obtained, thus completing the present invention.

[0009] In other words, the present invention is intended to convey the following:

[0010] Aspect 1 of the present invention includes a non-linear optical active material, a surfactant, and a solvent. The surfactant includes a silicone-based surfactant. The non-linear optical active material includes at least one selected from the group consisting of a compound represented by the following formula (1) and a non-linear optical active polymer compound containing a monovalent or polyvalent group obtained by removing at least one hydrogen atom from the compound represented by the following formula (1). Regarding a composition in which the content of the silicone-based surfactant with respect to the total solid content in the composition is 3% by mass or less.

[0011]

[0012] [In formula (1), Ar ３１ is 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. R ３１ and R ３３ are each independently a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, and a part of its carbon atoms may be substituted with an oxygen atom, a sulfur atom, and / or a silicon atom, a group selected from 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, and is a divalent group. R ３２ and R ３４ 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, and a part of its carbon atoms may be substituted with an oxygen atom, a sulfur atom, and / or a silicon atom, a group selected from 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. Y ３１ is each independently a divalent π-conjugated linking group which may have a substituent. Z ３１ is a group represented by the following formula (2). m ３１ is an integer from 0 to 5. m ３２ is an integer from 1 to 5. m ３３n is an integer between 0 and 5. ３１ [This is an integer between 1 and 15.]

[0013]

[0014] [In formula (2), *J ４１ Y ３１ This is the bonding position with R ４１ and R ４２ Each is independently a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, which may have substituents, and some of the carbon atoms 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 substituents; or an aromatic heterocyclic group having 3 to 50 carbon atoms, which may have substituents. ４１ and R ４２ They may be bonded together to form a ring, or R ４１ and R ４２ R ４１ and R ４２ These may also form a carbonyl group together with the carbon atom to which they are bonded, R ４３ and R ４４ Each of these is independently a cyano group, a C1-C10 alkyloxycarbonyl group which may have substituents, or a C1-C10 alkylsulfonyl group which may have substituents, X ４１ is O, S, or N-Q ４１ Q ４１ This refers to a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, which may have substituents, and in which some carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have substituents.

[0015] Aspect 2 of the present invention relates to a composition of Aspect 1 in which the silicone-based surfactant is at least one selected from the group consisting of polyether-modified silicone-based surfactants and aralkyl-modified silicone-based surfactants.

[0016] Aspect 3 of the present invention relates to a composition according to aspect 1 or 2, wherein the silicone-based surfactant is an aralkyl-modified silicone-based surfactant.

[0017] Aspect 4 of the present invention relates to a composition comprising a nonlinear optically active polymer compound in any one of aspects 1 to 3, which includes a monovalent group obtained by removing one hydrogen atom from the compound represented by formula (1).

[0018] Aspect 5 of the present invention relates to a composition of Aspect 4 in which the silicone-based surfactant is at least one selected from the group consisting of polyether-modified silicone-based surfactants and aralkyl-modified silicone-based surfactants.

[0019] Aspect 6 of the present invention relates to a composition of aspect 4 or 5 in which the silicone-based surfactant is an aralkyl-modified silicone-based surfactant.

[0020] Embodiment 7 of the present invention relates to a nonlinear optical film formed from any one composition of Embodiments 1 to 6.

[0021] Aspect 8 of the present invention relates to an optical modulator comprising the nonlinear optical film of Aspect 7.

[0022] Aspect 9 of the present invention relates to a method for forming a nonlinear optical film, comprising the steps of: applying one of the compositions from aspects 1 to 6 onto a substrate; drying the applied composition; and firing the dried composition at 100 to 200°C, in this order.

[0023] Aspect 10 of the present invention relates to a nonlinear optical film comprising at least one selected from the group consisting of a compound represented by the following formula (1) and a nonlinear optically active polymer compound containing a monovalent or multivalent group obtained by removing at least one hydrogen atom from the compound represented by the following formula (1), and a silicone-based surfactant, wherein the silicon atom concentration measured by X-ray photoelectron spectroscopy (XPS) is 3 at% or less.

[0024]

[0025] [In formula (1), Ar ３１Each of these is independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have substituents, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have substituents, and R ３１ and R ３３ Each is 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 substituents, in which some carbon atoms 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 substituents; or an aromatic heterocyclic group having 3 to 50 carbon atoms, which may have substituents. ３２ and R ３４ Each is independently a hydrogen atom, a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have substituents, a group which may have some carbon atoms substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have substituents, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom, Y ３１ Each is independently a divalent π-conjugated linkage group which may have substituents, and Z ３１ This is a group represented by the following formula (2), m ３１ m is an integer between 0 and 5. ３２ m is an integer between 1 and 5. ３３ n is an integer between 0 and 5. ３１ [This is an integer between 1 and 15.]

[0026]

[0027] [In formula (2), *J ４１ Y ３１ This is the bonding position with R ４１ and R ４２Each is independently a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, which may have substituents, and some of the carbon atoms 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 substituents; or an aromatic heterocyclic group having 3 to 50 carbon atoms, which may have substituents. ４１ and R ４２ They may be bonded together to form a ring, or R ４１ and R ４２ R ４１ and R ４２ These may also form a carbonyl group together with the carbon atom to which they are bonded, R ４３ and R ４４ Each of these is independently a cyano group, a C1-C10 alkyloxycarbonyl group which may have substituents, or a C1-C10 alkylsulfonyl group which may have substituents, X ４１ is O, S, or N-Q ４１ Q ４１ This refers to a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, which may have substituents, and in which some carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have substituents.

[0028] Aspect 11 of the present invention relates to a nonlinear optical film of aspect 10, wherein the silicone-based surfactant is at least one selected from the group consisting of polyether-modified silicone-based surfactants and aralkyl-modified silicone-based surfactants.

[0029] Aspect 12 of the present invention relates to a nonlinear optical film according to aspect 10 or 11, wherein the silicone-based surfactant is an aralkyl-modified silicone-based surfactant.

[0030] Aspect 13 of the present invention relates to a nonlinear optical film in any one of aspects 10 to 12, which includes a nonlinear optically active polymer compound containing a monovalent group obtained by removing one hydrogen atom from the compound represented by formula (1).

[0031] Aspect 14 of the present invention relates to a nonlinear optical film of the present invention, wherein the silicone-based surfactant is at least one selected from the group consisting of polyether-modified silicone-based surfactants and aralkyl-modified silicone-based surfactants.

[0032] Aspect 15 of the present invention relates to a nonlinear optical film according to aspect 13 or 14, wherein the silicone-based surfactant is an aralkyl-modified silicone-based surfactant.

[0033] Aspect 16 of the present invention relates to an optical modulator comprising a nonlinear optical film according to any one of aspects 10 to 15.

[0034] According to the present invention, it is possible to provide a composition and a nonlinear optical film that can improve the nonlinear optical properties of a nonlinear optically active material.

[0035] Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following description and can be modified and implemented as appropriate without departing from the spirit of the invention. In this specification, when "~" is used to express a value with numerical values ​​or physical properties before and after it, it is intended to include the values ​​before and after it.

[0036] <Explanation of Terms> This section explains the terms used in this specification.

[0037] [Copolymer] A copolymer is a polymer compound that has two or more structural units in its molecule.

[0038] [Polymer Compounds] 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 its molecule. The polymer compound is not particularly limited, but is preferably a polymer, and may be a homopolymer, block copolymer, random copolymer, alternating copolymer, or graft copolymer, or in any other form.

[0039] [Polymer Materials] In this specification, polymer materials refer to polymer compounds that do not have nonlinear optical activity. Polymer materials are not particularly limited, but are preferably polymers, and may be homopolymers, block copolymers, random copolymers, alternating copolymers, or graft copolymers, or in other forms.

[0040] While not particularly limited, examples of polymer materials include poly(meth)acrylic acid esters (e.g., polymethyl methacrylate (PMMA), polydicyclopentanyl methacrylate (poly DCPMA), polyadamantyl methacrylate (poly AdMA), poly(DCPMA-co-MMA), poly(AdMA-co-MMA), polycarbonylaminoethyl methacrylate, etc.), polyamides, polycarbonates, polystyrene, polyethylene, polymethylpentene, polypropylene, polyvinyl alcohol (PVA), polyethylene terephthalate, polysulfone, polyethersulfone, polyesters, polyolefins, polyphenylene sulfide, aromatic polyamines, polyamines, polyureas, silicone resins, epoxy resins, polyvinyl chloride, fluoropolymers, and copolymers thereof. (Meth)acrylic means at least one selected from acrylic and methacrylic. The same applies to (meth)acrylates, etc.

[0041] [Substituents] Unless otherwise specified, substituents are any group, but preferably the substituent group W described below. １ The group is selected from the substituent group W. The substituents that may be present are also the substituent group W. １ A substituent selected from, or which may have, is substituent group W. １ If it is stated that selection from is preferable, the preferred substituents are also the substituent group W below. １ As stated therein.

[0042] [Substituent group W １ ] Substituent group W １This group consists of hydroxyl groups, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aromatic oxy groups, aralkyloxy groups, alkylthio groups, aromatic thio groups, aralkylthio groups, alkyloxycarbonyl groups, dialkylamino groups, diarylamino groups, arylalkylamino groups, acyl groups, halogen atoms, haloalkyl groups, alkylthio groups, arylthio groups, silyl groups, siloxy groups, cyano groups, aralkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups. These substituents may include linear, branched, or cyclic structures.

[0043] Substituent group W １ More specifically, the following structure can be cited.

[0044] A linear, branched, or cyclic alkyl group having one or more carbon atoms, preferably four or more, usually 24 or less, preferably 12 or less, more preferably 8 or less, and even more preferably 6 or less. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl group, adamantyl group, etc.

[0045] A linear, branched, or cyclic alkenyl group having typically two or more carbon atoms, typically 24 or less, preferably 12 or less. A specific example is a vinyl group. A linear or branched alkynyl group having typically two or more carbon atoms, typically 24 or less, preferably 12 or less. A specific example is an ethynyl group. A linear, branched, or cyclic alkoxy group having one or more carbon atoms, typically 24 or less, preferably 12 or less. Specific examples include a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, cyclohexyloxy group, dodecyloxy group, adamantyloxy group, etc.

[0046] Aromatic oxy groups having 4 or more carbon atoms, preferably 5 or more, and usually 36 or less, preferably 24 or less. Specific examples include phenoxy group, naphthoxy group, pyridyloxy group, etc. Aralkyloxy groups having 4 or more carbon atoms, preferably 5 or more, and usually 50 or less, preferably 30 or less. Specific examples include benzyloxy group, tolylmethoxy group, thiophenylmethoxy group, 2-phenylethyloxy group, 2-phenylpropyl-2-yloxy group, 2-phenylbutyl-2-yloxy group, 3-phenylpentyl-3-yloxy group, 3-phenyl-1-propyloxy group, 4-phenyl-1-butyloxy group, 5-phenyl-1-pentioxyl group, 6-phenyl-1-hexyloxy group, 7-phenyl-1-heptyloxy group, 8-phenyl-1-octyloxy group, etc.

[0047] Alkylthio groups having 1 or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, tert-butylthio group, n-hexylthio group, cyclohexylthio group, dodecylthio group, adamantylthio group, etc. Aromatic thio groups having 3 or more carbon atoms, preferably 4 or more, usually 50 or less, preferably 30 or less. Specific examples include benzylthio group, tolylthio group, thiophenylthio group, etc. Aralkylthio groups having 4 or more carbon atoms, usually 50 or less, preferably 30 or less. Specific examples include benzylthio group, tolylmethylthio group, 2-phenylethylthio group, 2-phenylpropyl-2-ylthio group, 2-phenylbutyl-2-ylthio group, 3-phenylpentyl-3-ylthio group, 3-phenyl-1-propylthio group, 4-phenyl-1-butylthio group, 5-phenyl-1-pentylthio group, 6-phenyl-1-hexylthio group, 7-phenyl-1-heptylthio group, and 8-phenyl-1-octylthio group.

[0048] Alkyloxycarbonyl groups having 2 or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include methoxycarbonyl groups and ethoxycarbonyl groups. Dialkylamino groups having 2 or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include dimethylamino groups and diethylamino groups. Diarylamino groups having 10 or more carbon atoms, preferably 12 or more, usually 36 or less, preferably 24 or less. Specific examples include diphenylamino groups, ditolylamino groups, and N-carbazolyl groups. Arylalkylamino groups having 7 or more carbon atoms, usually 36 or less, preferably 24 or less. Specific example is phenylmethylamino groups. Acyl groups having 2 or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include acetyl groups and benzoyl groups.

[0049] Halogen atoms such as fluorine, chlorine, bromine, and iodine atoms. Preferably fluorine atoms. Haloalkyl groups having 1 or more carbon atoms, usually 12 or less, preferably 6 or less. Specific examples include trifluoromethyl groups. Alkylthio groups having 1 or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include methylthio groups and ethylthio groups. Arylthio groups having 4 or more carbon atoms, preferably 5 or more, usually 36 or less, preferably 24 or less. Specific examples include phenylthio groups, naphthylthio groups, and pyridylthio groups. Silyl groups having 2 or more carbon atoms, preferably 3 or more, usually 36 or less, preferably 24 or less. Specific examples include trimethylsilyl groups, tert-butyldimethylsilyl groups, tert-butyldiphenylsilyl groups, and triphenylsilyl groups. Siloxy groups having 2 or more carbon atoms, preferably 3 or more, usually 36 or less, preferably 24 or less, more preferably 18 or less. Specific examples include trimethylsiloxy group, tert-butyldimethylsiloxy group, tert-butyldiphenylsiloxy group, and triphenylsiloxy group.

[0050] Aralkyl groups having 7 or more carbon atoms, preferably 9 or more, usually 30 or less, preferably 18 or less, and more preferably 10 or less. Specific examples include benzyl group, 2-phenylethyl group, 2-phenylpropyl-2-yl group, 2-phenylbutyl-2-yl group, 3-phenylpentyl-3-yl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, 7-phenyl-1-heptyl group, and 8-phenyl-1-octyl group. Aromatic hydrocarbon groups having 6 or more carbon atoms, usually 36 or less, and preferably 24 or less. Specific examples include phenyl group, naphthyl group, and groups in which multiple phenyl groups are linked. Aromatic heterocyclic groups having 3 or more carbon atoms, preferably 4 or more, usually 36 or less, and preferably 24 or less. Specific examples include thienyl group and pyridyl group.

[0051] The substituents may include linear, branched, or cyclic structures. When the substituents are adjacent, they may bond to each other to form a ring. Preferred ring sizes are four-membered, five-membered, and six-membered rings, with specific examples including cyclobutane rings, cyclopentane rings, and cyclohexane rings.

[0052] [Alkyl group] The alkyl group may have substituents and may be linear, branched, or cyclic. While the number of carbon atoms is generally not limited, it is preferably between 1 and 50 carbon atoms, more preferably 30 carbon atoms or less, and even more preferably 10 carbon atoms or less. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl group, adamantyl group, etc. The substituents that these groups may have are categorized as substituent group W. １ Selected from.

[0053] [Aromatic Group] An aromatic group may have substituents and represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and refers to a monovalent, divalent, or trivalent or more structure depending on the bonding state in the structure of the compound to be described below. The substituents that these groups may have are the substituent group W. １ Selected from.

[0054] [Aromatic Hydrocarbon Groups] Aromatic hydrocarbon groups refer to monovalent, divalent, or trivalent or more structures of hydrocarbon aromatic rings, depending on the bonding state within the structure of the compounds described below. In the structure of hydrocarbon aromatic rings, the number of carbon atoms is not usually limited, but preferably it is 6 or more and 60 or less, more preferably 48 or less as the upper limit of the number of carbon atoms, and even more preferably 30 or less. Specifically, examples include monocyclic rings of 6 members 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, fluorantene rings, and fluorene rings, or structures in which multiple groups selected from these are linked. When multiple hydrocarbon aromatic rings are linked, a structure in which 2 to 10 rings are linked is usually given, and a structure in which 2 to 5 rings are linked is preferred. When multiple hydrocarbon aromatic rings are linked together, the same structure may be linked, or different structures may be linked together.

[0055] [Aromatic Heterocyclic Groups] Aromatic heterocyclic groups refer to monovalent, divalent, or trivalent or more heteroaromatic ring structures, depending on the bonding state within the structure of the compounds described below. In the structure of heteroaromatic rings, the number of carbon atoms is not usually limited, but preferably it is 3 to 50 carbon atoms, more preferably 45 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 30 carbon atoms or less. Specifically, examples include monocyclic rings with 5 to 6 members or fused ring groups containing 2 to 4 rings, such as furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrrole rings, pyrrolopyrrole rings, thienopyrrole rings, thienopyrrole rings, phlopyrrole rings, phlofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinnoline rings, quinoxaline rings, phenantholidine rings, perimidine rings, quinazoline rings, and quinazolinone rings, or groups in which multiple such rings are linked together. When multiple heteroaromatic rings are linked together, the same structure may be linked together, or different structures may be linked together. When multiple heteroaromatic rings are linked together, typically a structure consisting of 2 to 10 linked rings is common, and a structure consisting of 2 to 5 linked rings is preferred.

[0056] [Amino Group] The amino group may have substituents, preferably a secondary amino group, and more preferably a tertiary amino group. Preferred substituents on the amino group are alkyl groups, cycloalkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups, and these groups may also have substituents. Furthermore, if there are multiple substituents on the amino group, they may be the same or different, and they may be bonded to each other, forming a ring with the nitrogen atom to which each is bonded. Specific examples include dimethylamino group, diethylamino group, ethylmethylamino group, n-propylmethylamino group, di-iso-propylamino group, di-n-butylamino group, di-n-hexylamino group, di-n-butylamino group, methylphenylamino group, ethylphenylamino group, butylphenylamino group, hexylphenylamino group, diphenylamino group, 2,6-dimethylphenylphenylamino group, and 2,4,6-trimethylphenylphenylamino group. The substituents that these groups may have are substituted group W. １ Selected from.

[0057] [Halogen atoms] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0058] [Alkyloxycarbonyl group] The alkyloxycarbonyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 2 or more carbon atoms and 50 or less, more preferably 30 or less carbon atoms as the upper limit of the number of carbon atoms, and even more preferably 20 or less carbon atoms. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group, iso-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0059] [Alkylsulfonyl Group] The alkylsulfonyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 2 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 20 carbon atoms or less. Specific examples include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, dodecylsulfonyl group, etc. The substituents that these groups may have are substituted group W. １ Selected from.

[0060] [Aralkyl group] The aralkyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 2 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 20 carbon atoms or less. Specific examples include benzyl group, 2-phenylethyl group, 2-phenylpropyl-2-yl group, 2-phenylbutyl-2-yl group, 3-phenylpentyl-3-yl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, 7-phenyl-1-heptyl group, 8-phenyl-1-octyl group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0061] [Boryl group] The boryl group may have substituents, preferably a secondary boryl group, and more preferably a tertiary boryl group. Preferred substituents on the boryl group are hydroxyl groups, alkyloxycarbonyl groups, alkyl groups, cycloalkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups, and these groups may also have substituents. Furthermore, if there are multiple substituents on the boryl group, they may be the same or different, and they may be bonded to each other, forming a ring with the boron atom to which each is bonded. The substituents that these groups may have are substituted group W. １ Selected from.

[0062] [Acyl group] The acyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 2 to 50 carbon atoms, more preferably 24 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 12 carbon atoms or less. Specific examples include the benzoyl group and the acetyl group. The substituents that these groups may have are the substituent group W. １ Selected from.

[0063] [Alkoxy Groups] Alkoxy groups may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 1 or more and 50 or less, more preferably 20 or less as the upper limit of the number of carbon atoms, and even more preferably 10 or less. Specific examples include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, cyclohexyloxy group, dodecyloxy group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0064] [Aromatic oxy group] The aromatic oxy group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 3 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the carbon number, and even more preferably 20 carbon atoms or less. Specific examples include naphthoxy group, thiophenyloxy group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0065] [Aralkyloxy group] The aralkyloxy group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 4 or more carbon atoms and 50 or less, more preferably 30 or less carbon atoms as the upper limit of the number of carbon atoms, and even more preferably 20 or less carbon atoms. Specific examples include benzyloxy group, tolylmethoxy group, thiophenylmethoxy group, 2-phenylethyloxy group, 2-phenylpropyl-2-yloxy group, 2-phenylbutyl-2-yloxy group, 3-phenylpentyl-3-yloxy group, 3-phenyl-1-propyloxy group, 4-phenyl-1-butyloxy group, 5-phenyl-1-pentioxyl group, 6-phenyl-1-hexyloxy group, 7-phenyl-1-heptyloxy group, 8-phenyl-1-octyloxy group, etc. The substituents that these groups may have are substituted group W. １ Selected from.

[0066] [Alkylthio Group] The alkylthio group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 1 to 50 carbon atoms, more preferably 20 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 10 carbon atoms or less. Specific examples include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, tert-butylthio group, n-hexylthio group, cyclohexylthio group, dodecylthio group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0067] [Aromatic Thio Group] The aromatic thio group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 3 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the carbon number, and even more preferably 20 carbon atoms or less. Specific examples include the benzylthio group, tolylthio group, thiophenylthio group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0068] [Aralkylthio group] The aralkylthio group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 4 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 20 carbon atoms or less. Specific examples include benzylthio group, tolylmethylthio group, 2-phenylethylthio group, 2-phenylpropyl-2-ylthio group, 2-phenylbutyl-2-ylthio group, 3-phenylpentyl-3-ylthio group, 3-phenyl-1-propylthio group, 4-phenyl-1-butylthio group, 5-phenyl-1-pentylthio group, 6-phenyl-1-hexylthio group, 7-phenyl-1-heptylthio group, 8-phenyl-1-octylthio group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0069] [Silyl Group] The silyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 3 to 50 carbon atoms, more preferably 20 carbon atoms or less as the upper limit of the carbon number, and even more preferably 10 carbon atoms or less. Specific examples include trimethylsilyl group, triethylsilyl group, propyldimethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0070] [Hydrogen ring group] A hydrocarbon ring group is a cyclic hydrocarbon group that may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 3 or more and 50 or less, more preferably 20 or less as the upper limit of the number of carbon atoms, 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 multiple of these are linked together.

[0071] [Branched, linear, or cyclic saturated or unsaturated hydrocarbon chains in which some carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms] Branched, linear, or cyclic saturated or unsaturated hydrocarbon chains in which some carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms are groups in which part of a carbon chain consisting of branched, linear, or cyclic alkyl, alkenyl, or alkynyl groups having 1 to 15 carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms. Specifically, the following groups can be listed.

[0072] Specific examples of unsubstituted hydrocarbon chains include 1 to 15 hydrocarbon chains, more specifically methyl, ethyl, 1-butyl, tert-butyl, cyclopentyl, 4-ethyl-1-cyclohexyl, 2-penten-1-yl, 1-octyl, and 1-decyl groups, with methyl, ethyl, and 1-butyl groups being preferred. Specific examples of substituted oxygen atoms include 2-ethoxyethyl, 2-(2-ethoxyethoxy)ethyl, 2-hydroxyethyl, and tetrahydropyranyloxypropyl groups, with 2-ethoxyethyl and 2-hydroxyethyl groups being preferred, and 2-hydroxyethyl groups being particularly preferred. Specific examples of substituted sulfur atoms include 2-ethylthioethyl, tetrahydrothienyl, and 2-(2-ethylthioethylthio)ethyl groups. Specific examples of substituted silicon atoms include trimethylsilyl and tert-butyldimethylsilyl groups. Furthermore, these groups may also be substituted with oxygen atoms and silicon atoms simultaneously. Specific examples include 2-(trimethylsilyloxy)ethyl group, 2-(tert-butyldimethylsilyloxy)ethyl group, 4-(tert-butyldimethylsilyloxy)butyl group, 2-(tert-butyldiphenylsilyloxy)ethyl group, and 2-(tert-butyldimethylsilyloxy)hexyl group, with 2-(tert-butyldimethylsilyloxy)ethyl group and 4-(tert-butyldimethylsilyloxy)butyl group being preferred. The substituents that these groups may have are the substituent group W.１ Selected from.

[0073] [π-conjugated linkage group] A π-conjugated linkage group is a divalent group in the structure of a compound described below, consisting of alternating single and multiple bonds and possessing delocalized electrons (π electrons). A π-conjugated linkage group may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 2 or more and 50 or less, more preferably 30 or less as the upper limit of the number of carbon atoms, and even more preferably 20 or less. Furthermore, substituents on multiple π-conjugated groups may bond together to form a cyclic structure. Specific examples include a vinylene group, a divalent thiophene ring group, a divalent furan ring group, a divalent pyrrole ring group, etc. The substituents that these groups may have are categorized as substituent group W. １ Selected from.

[0074] [Blocked Isocyanate Group] A blocked isocyanate group represents an isocyanate group protected by a blocking agent, which remains stable under normal conditions, and is characterized by the regeneration of the isocyanate group by dissociation of the blocking agent upon heat treatment. The group selected as the blocking agent is not particularly limited, but has 1 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the carbon number, and even more preferably 20 carbon atoms or less. Furthermore, substituents on multiple π-conjugated groups may bond to form a cyclic structure. Specific examples include methylethyloxime group, 3,5-dimethylpyrazolyl group, ε-caprolactam group, etc. Preferably, it is a dimethylpyrazole group. The heat treatment temperature required for dissociation of 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, most preferably 100°C or higher, and the upper limit is preferably 250°C or lower, more preferably 200°C or lower.

[0075] [Total Solid Content] The total solid content of a composition is the sum of the nonlinear optically active material and polymer material contained in the composition, and other additives such as solvents and surfactants are not included in the solid content. For example, a composition containing a total of 100 parts by mass of nonlinear optically active material and polymer material, and 3 parts by mass of surfactant can be said to be a composition in which the surfactant content is 3% by mass relative to the total solid content of the composition.

[0076] [Nonlinear Optically Active Materials, Nonlinear Optical Materials] Nonlinear optically active materials as used herein consist of nonlinear optically active compounds, nonlinear optically active polymer compounds, or both. Nonlinear optical materials as used herein also include materials containing nonlinear optically active materials, and for example, compositions containing a nonlinear optically active compound and a polymer material.

[0077] <Nonlinear Optically Active Compounds> In embodiments of the present invention, the nonlinear optically active compound is represented, for example, by the compound shown in formula (1) described later.

[0078] [Compound represented by formula (1)]

[0079]

[0080] [In formula (1), Ar ３１ Each of these is independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have substituents, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have substituents, and R ３１ and R ３３ Each is 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 substituents, in which some carbon atoms 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 substituents; or an aromatic heterocyclic group having 3 to 50 carbon atoms, which may have substituents. ３２ and R ３４Each is independently a hydrogen atom, a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have substituents, a group which may have some carbon atoms substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have substituents, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom, Y ３１ Each is independently a divalent π-conjugated linkage group which may have substituents, and Z ３１ This is a group represented by the following formula (2), m ３１ m is an integer between 0 and 5. ３２ m is an integer between 1 and 5. ３３ n is an integer between 0 and 5. ３１ [This is an integer between 1 and 15.]

[0081] (Ar ３１ ) Ar ３１ Each of these is independently selected from a divalent group consisting of an aromatic hydrocarbon group having 6 to 60 carbon atoms, which may have substituents, and an aromatic heterocyclic group having 3 to 50 carbon atoms, which may have substituents.

[0082] Examples of aromatic hydrocarbon ring structures include benzene rings, naphthalene rings, anthracene rings, tetraphenylene rings, phenanthrene rings, chrysene rings, pyrene rings, benzoanthracene rings, or perylene rings, which typically have 6 or more carbon atoms, typically 60 or less, preferably 30 or less, more preferably 18 or less, and even more preferably 10 or less. Benzene rings and naphthalene rings having alkoxy groups or aralkyloxy groups are particularly preferred in order to fix the molecular structure through hydrogen bonding with adjacent π-conjugated linking groups.

[0083] As the heteroaromatic ring structure of the aromatic heterocyclic group, there are furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, or quinazolinone ring, etc. The ring having usually 3 or more, usually 50 or less, preferably 45 or less, more preferably 30 or less, still more preferably 12 or less carbon atoms is exemplified. The thiophene ring is particularly preferred for lengthening the absorption wavelength of the dye. The heterocyclic ring having an alkoxy group or an aralkyloxy group is particularly preferred for fixing the molecular structure by hydrogen bonding with an adjacent π-conjugated linking group. Ar ３１ The substituent which Ar １ may have is preferably selected from the aforementioned substituent group W

[0084] (R ３１ and R ３３ ) R ３１ and R ３３ are each independently a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, a group in which some of its carbon atoms may be substituted with an oxygen atom, a sulfur atom, and / or a silicon atom, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or a divalent group selected from aromatic heterocyclic groups having 3 to 50 carbon atoms which may have a substituent. The substituent which R ３１ and R ３３ may have is preferably selected from the aforementioned substituent group W １ .

[0085] (R ３２ and R ３４ ) R ３２ and R ３４Each of these independently comprises a hydrogen atom, a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms (which may have substituents), a group in which some carbon atoms 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 substituents), an aromatic heterocyclic group having 3 to 50 carbon atoms (which may have substituents), an amino group, a hydroxyl group, or a halogen atom (which may have substituents). ３２ and R ３４ The substituents that may be present are the aforementioned substituent group W １ It is preferable to select from the following.

[0086] (Y ３１ ) Y ３１ Each of these is independently a divalent π-conjugated linkage group which may have substituents. ３１ If there are multiple Y ３１ The structures may be the same or different. Also, Y ３１ Multiple substituents on the compound may form bonds to create a cyclic structure. Examples of π-conjugated linking groups include optionally substituted vinylene groups, optionally substituted divalent thiophene ring groups, optionally substituted divalent furan ring groups, optionally substituted divalent pyrrole ring groups, etc., which typically have 2 or more carbon atoms, typically 50 or less, preferably 30 or less, and more preferably 20 or less. ３１ The substituents that may be present are the aforementioned substituent group W １ It is preferable to select from the following.

[0087] (Z ３１ ) Z ３１ This is the base represented by equation (2) described later.

[0088] (m ３１ ~m ３３ , n ３１ ) m ３１ m is an integer between 0 and 5. ３２ m is an integer between 1 and 5. ３３ n is an integer between 0 and 5. ３１ m is an integer between 1 and 15. ３１Preferably, it is an integer between 0 and 4, more preferably an integer between 0 and 3, and even more preferably an integer between 0 and 2. ３２ The integer is preferably an integer between 1 and 4, and more preferably an integer between 1 and 3. ３３ Preferably, it is an integer from 0 to 4, more preferably an integer from 0 to 3, and even more preferably an integer from 0 to 2. From the viewpoint of improving the nonlinear optical properties of the dye, n ３１ Preferably, the value is 1 or more, more preferably 2 or more, even more preferably 3 or more, and from the viewpoint of reducing absorption loss, it is preferably 14 or less, more preferably 13 or less, and even more preferably 10 or less.

[0089] (The base represented by formula (2))

[0090]

[0091] [In formula (2), *J ４１ Y ３１ This is the bonding position with R ４１ and R ４２ Each is independently a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, which may have substituents, and some of the carbon atoms 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 substituents; or an aromatic heterocyclic group having 3 to 50 carbon atoms, which may have substituents. ４１ and R ４２ They may be bonded together to form a ring, or R ４１ and R ４２ R ４１ and R ４２ These may also form a carbonyl group together with the carbon atom to which they are bonded, R ４３ and R ４４ Each of these is independently a cyano group, a C1-C10 alkyloxycarbonyl group which may have substituents, or a C1-C10 alkylsulfonyl group which may have substituents, X ４１ is O, S, or N-Q ４１ Q ４１This refers to a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, which may have substituents, and in which some carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have substituents.

[0092] (*J ４１ ) *J ４１ Y ３１ This is the connection point.

[0093] (R ４１ and R ４２ ) R ４１ and R ４２ Each is independently a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, which may have substituents, and some of the carbon atoms 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 substituents; or an aromatic heterocyclic group having 3 to 50 carbon atoms, which may have substituents. ４１ and R ４２ They may be bonded together to form a ring, or R ４１ and R ４２ R ４１ and R ４２ These may form a carbonyl group together with the carbon atom to which they are bonded. To improve electron-withdrawing properties, R ４１ and R ４２ It is preferable that the substituents on are a fluorine atom, a chlorine atom, a bromine atom, or a cyano group. ４１ and R ４２ The substituents that may be present are the aforementioned substituent group W １ It is preferable to select from the following.

[0094] (R ４３ and R ４４ ) R ４３ and R ４４ Each of these is independently a cyano group, a C1-C10 alkyloxycarbonyl group which may have substituents, or a C1-C10 alkylsulfonyl group which may have substituents. ４３ and R ４４ The group is preferably a cyano group.４３ and R ４４ The substituents that may be present are the aforementioned substituent group W １ It is preferable to select from the following.

[0095] (X ４１ ) X ４１ is O, S, or N-Q ４１ That is. X ４１ Preferably, O, or N-Q ４１ It is, and more preferably, O.

[0096] (Q ４１ ) Q ４１ Q is a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, which may have substituents, and which may have some carbon atoms substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have substituents. ４１ The substituents that may be present are the aforementioned substituent group W １ It is preferable to select from the following.

[0097] From the viewpoint of the electro-optic coefficient, a preferred embodiment of the compound represented by formula (1) is Ar ３１ The benzene ring or naphthalene ring having an alkoxy group or an aralkyloxy group is preferred, Y ３１ Preferably is a vinylene group which may have a substituent, a divalent thiophene ring group which may have a substituent, a divalent furan ring group which may have a substituent, or a divalent pyrrole ring group which may have a substituent, in formula (2), X ４１ O is preferred, R ４１ and R ４２ Preferably, R is a hydrocarbon chain having 1 to 15 carbon atoms having a fluorine atom, a chlorine atom, a bromine atom, or a cyano group as a substituent, or an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have substituents. ４３ and R ４４ A cyano group is preferred.

[0098] [Specific Examples of Compounds Represented by Formula (1)] The following are specific examples of compounds represented by formula (1) according to the embodiments of the present invention. The compounds represented by formula (1) are not limited to these.

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105] In nonlinear optically active compounds, the dipole moment of the compound is preferably 14D to 37D, more preferably 17D to 34D, and even more preferably 19D to 31D. As described later, the effect of silicone-based surfactants on improving nonlinear optical properties is thought to be obtained by suppressing the association of dipoles in nonlinear optically active compounds. The effect of improving nonlinear optical properties is more likely to be exhibited when applied to nonlinear optically active compounds with a moderately large dipole moment. On the other hand, for nonlinear optically active compounds with a remarkably large dipole moment and strong association forces, the effect of the surfactant on improving nonlinear optical properties may be insufficient.

[0106] [Nonlinear Optically Active Polymer Compounds] The nonlinear optically active material according to the embodiment of the present invention may also be a nonlinear optically active polymer compound. A nonlinear optically active polymer compound refers to a polymer compound having nonlinear optical activity. A nonlinear optically active polymer compound is preferably a nonlinear optically active polymer compound having a side chain, in which a monovalent or multivalent group obtained by removing at least one hydrogen atom from the compound represented by formula (1) is bonded to a repeating unit in the polymer compound (hereinafter also referred to as a "nonlinear optically active polymer compound having a group derived from the compound represented by formula (1)"). A nonlinear optically active polymer compound is more preferably a nonlinear optically active polymer compound in which a monovalent group obtained by removing one hydrogen atom from the compound represented by formula (1) is bonded to a repeating unit in the polymer compound. That is, a nonlinear optically active polymer compound is preferably a nonlinear optically active polymer compound containing a monovalent or multivalent group obtained by removing at least one hydrogen atom from the compound represented by formula (1), and more preferably a nonlinear optically active polymer compound containing a monovalent group obtained by removing one hydrogen atom from the compound represented by formula (1).

[0107] The nonlinear optically active polymer compound preferably has at least one selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimide, polycarbonate, maleimide-styrene copolymers, and copolymers thereof as its main chain; more preferably has at least one selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, and polycarbonate; and even more preferably has at least one selected from the group consisting of poly(meth)acrylic acid esters, polystyrene, polycarbonate, and maleimide-styrene copolymers. Having such a main chain is preferable because it further exhibits the properties of the nonlinear optically active compound in the side chain. In one embodiment, the nonlinear optically active polymer compound can be a compound having a side chain of at least one selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, maleimide-styrene copolymers, polyimide, and polycarbonate.

[0108] If a nonlinear optically active polymer compound contains a monovalent group obtained by removing one hydrogen atom from the compound represented by formula (1), the content of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (1) can be expressed as the ratio of the total mass of the nonlinear optically active polymer compound to the mass of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (1), or as the molar percentage of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (1) relative to the total of each repeating unit of the nonlinear optically active polymer compound.

[0109] When the above content is expressed as a mass ratio, there are no particular restrictions on the range. From the viewpoint of balancing electro-optical effect and solubility, when the total mass of the nonlinear optically active polymer compound is set to 100, the mass of the monovalent group obtained by removing one hydrogen atom from the compound represented by formula (1) 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.

[0110] When the above content is expressed in mole percentage, there are no particular restrictions on the range. From the viewpoint of balancing electro-optical effect and solubility, the mole percentage of the monovalent group obtained by subtracting one hydrogen atom from the compound represented by formula (1) 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.

[0111] In a nonlinear optically active polymer compound, the content of a monovalent group obtained by removing one hydrogen atom from the compound represented by formula (1) is: １ It is calculated by methods such as H-NMR, absorbance measurement, and gel permeation chromatography (GPC), but preferably, １ H-NMR, absorbance measurement, most preferably １ It is calculated using H-NMR.

[0112] １ ​A specific method for calculating the content of a monovalent group (removed from the compound represented by formula (1)) in a nonlinear optically active polymer compound using 1H-NMR is as follows: The spectral integral value derived from a specific hydrogen atom of the monovalent group (removed from the compound represented by formula (1)) is used as a reference, and the ratio of this value to the spectral integral value derived from a specific hydrogen atom of the group in each repeating unit of the nonlinear optically active polymer compound is determined. This allows for the calculation of the molar ratio between the monovalent group (removed from the compound represented by formula (1)) and 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 (removed from the compound represented by formula (1)) in the nonlinear optically active polymer compound can be determined.

[0113] When calculating the content of a monovalent group (a compound with one hydrogen atom removed) in a nonlinear optically active polymer compound by absorbance measurement, the specific method involves dividing the maximum absorbance obtained by dissolving a monovalent group (a compound with one hydrogen atom removed) at a predetermined concentration in a solution by the concentration, and then calculating the content from the ratio of the value obtained by similarly measuring the absorbance of the nonlinear optically active polymer compound. The absorbance at this time is measured using an ultraviolet-visible-near-infrared spectrophotometer.

[0114] The weight-average molecular weight of the nonlinear optically active polymer compound is not particularly limited, but it is preferably 0.5 million or more, more preferably 10,000 or more, and even more preferably 30,000 or more, as this improves durability. Furthermore, it is preferably 500,000 or less, more preferably 400,000 or less, and even more preferably 300,000 or less, as this maintains solubility. The weight-average molecular weight of the nonlinear optically active polymer compound is confirmed by measuring the weight-average molecular weight of polystyrene as a standard using GPC.

[0115] There are no particular restrictions 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. A molecular weight distribution of 3 or less is preferable from the viewpoint of orientation control. The molecular weight distribution of the nonlinear optically active polymer compound can be confirmed by measuring the ratio of the number-average molecular weight to the weight-average molecular weight using polystyrene as a standard, using GPC.

[0116] There are no particular restrictions on the glass transition temperature (Tg) of nonlinear optically active polymer compounds, but it is generally between 40°C and 300°C. A temperature of 45°C or higher is preferred, 50°C or higher is more preferred, and 80°C or higher is even more preferred, as this improves heat resistance. Furthermore, from the viewpoint of the influence on the nonlinear optically active compound during the poling process, a temperature of 280°C or lower is preferred, 250°C or lower is more preferred, and 230°C or lower is even more preferred. The Tg of a nonlinear optically active polymer compound is confirmed by measuring the temperature corresponding to the intersection of the gradient of the endothermic rising portion of the baseline shift of the DSC curve associated with the glass transition and the baseline, using a differential scanning calorimeter (DSC).

[0117] There are no particular restrictions on the decomposition temperature (Td) of the nonlinear optically active polymer compound, but it is preferably 0°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. Furthermore, it is 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 can be confirmed by measuring the temperature at which the mass decreases by 5% using a thermogravimetric differential thermal analyzer (TG-DTA).

[0118] [Specific Examples of Nonlinear Optically Active Polymer Compounds] The following are specific examples of nonlinear optically active polymer compounds according to the embodiment of the present invention. The nonlinear optically active polymer compounds are not limited to these. In the following formula, v, w, x, y, and z represent the molar ratio of each repeating unit constituting the nonlinear optically active compound.

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163] <Composition> The composition according to the embodiment of the present invention comprises a nonlinear optically active material, a surfactant, and a solvent, wherein the surfactant comprises a silicone-based surfactant, and the nonlinear optically active material comprises at least one selected from the group consisting of a compound represented by formula (1) and a nonlinear optically active polymer compound containing a monovalent or multivalent group obtained by removing at least one hydrogen atom from the compound represented by formula (1), and the content of the silicone-based surfactant with respect to the total solid content in the composition is 3% by mass or less. Unless otherwise specified in this specification, the content of each component in the composition refers to the content relative to the total mass of the composition.

[0164] Examples of combinations of nonlinear optically active materials, silicone surfactants, and solvents contained in the composition include the following: • Nonlinear optically active compound / silicone surfactant / solvent • Nonlinear optically active polymer compound / silicone surfactant / solvent • Nonlinear optically active compound / nonlinear optically active polymer compound / silicone surfactant / solvent • Nonlinear optically active compound / polymer material / silicone surfactant / solvent Note that the composition may contain one or more of the above-mentioned nonlinear optically active compounds, nonlinear optically active polymer compounds, silicone surfactants, and solvents.

[0165] The content of the silicone-based surfactant in the composition is 3% by mass or less relative to the total solid content in the composition. If the content exceeds 3% by mass, the electro-optic coefficient may deteriorate. The content of the silicone-based surfactant relative to the total solid content in the composition is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less. The lower limit of the content is not particularly limited as long as it is greater than 0% by mass, but is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, particularly preferably 0.05% by mass or more, even more particularly preferably 0.1% by mass or more, and most preferably 0.5% by mass or more. As described above, in the present invention, there is a suitable range for the concentration of the surfactant, and it has been found that if the concentration of the surfactant exceeds the suitable concentration, the nonlinear optical properties deteriorate. As the concentration of surfactant increases, the concentration of nonlinear optically active compounds in the material decreases. However, since surfactants themselves do not have nonlinear optical activity, if the concentration of surfactant becomes excessive, the decrease in nonlinear optical properties due to the decrease in the concentration of nonlinear optically active compounds will outweigh the effect of the surfactant on improving nonlinear optical properties, resulting in an overall decrease in nonlinear optical properties.

[0166] In one embodiment, the content of the silicone-based surfactant relative to the total solid content in the composition can be 0.001 to 3% by mass, 0.005 to 1% by mass, 0.01 to 0.5% by mass, or 0.01 to 0.2% by mass, relative to the total solid content in the composition.

[0167] The content of silicone-based surfactants relative to the total amount of surfactants in the composition is preferably 40% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass, i.e., containing only silicone-based surfactants as the surfactant.

[0168] The content of the silicone-based surfactant relative to the total mass of the composition is preferably 0.0001 parts by mass (content: 1 ppm by mass) or more, more preferably 0.001 parts by mass (content: 10 ppm by mass) or more, even more preferably 0.005 parts by mass (content: 50 ppm by mass) or more, and particularly preferably 0.01 parts by mass (content: 100 ppm by mass) or more per 100 parts by mass of the composition. A content of 0.0001 parts by mass (content: 1 ppm by mass) or more per 100 parts by mass of the composition is preferable because it results in good coatability. On the other hand, the content of the silicone-based surfactant in the composition is preferably 1 part by mass (content: 10,000 ppm by mass) or less per 100 parts by mass of the composition, more preferably 0.5 parts by mass (content: 5,000 ppm by mass) or less, and even more preferably 0.3 parts by mass (content: 3,000 ppm by mass) or less.

[0169] In one embodiment, the content of the silicone-based surfactant in the composition may be 0.0001 to 3 parts by mass (content: 1 ppm to 30,000 ppm), 0.001 to 1 part by mass (content: 10 to 10,000 ppm), 0.005 to 0.5 parts by mass (content: 50 to 5,000 ppm), or 0.01 to 0.3 parts by mass (content: 100 to 3,000 ppm) per 100 parts by mass of the composition.

[0170] The content of the silicone-based surfactant in the composition is preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, and even more preferably 1.0 part by mass or less, per 100 parts by mass of the nonlinear optically active material. The lower limit of the content is not particularly limited as long as it is greater than 0 parts by mass, but is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more.

[0171] However, when the composition contains a nonlinear optically active compound as a nonlinear optically active material, the content of the silicone-based surfactant in the composition is preferably 15 parts by mass or less, more preferably 2.5 parts by mass or less, and even more preferably 1.0 part by mass or less, per 100 parts by mass of the nonlinear optically active compound. The lower limit of the content is not particularly limited as long as it is greater than 0 parts by mass, but is preferably 0.005 parts by mass or more, more preferably 0.025 parts by mass or more, and even more preferably 0.05 parts by mass or more.

[0172] When the composition contains a nonlinear optically active polymer compound as the nonlinear optically active material, the content of the silicone-based surfactant in the composition is preferably 3 parts by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.2 parts by mass or less, per 100 parts by mass of the nonlinear optically active polymer compound. The lower limit of the content is not particularly limited as long as it is greater than 0 parts by mass, but is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more.

[0173] There are no particular restrictions on the content of the nonlinear optically active compound in the composition, but it is preferable to have a higher content of the component exhibiting nonlinear optical activity. For example, it is preferable to have 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, even more preferably 1 part by mass or more, and particularly preferable to have 2 parts by mass or more, per 100 parts by mass of the composition. It is also preferable to have 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, and particularly preferable to have 20 parts by mass or less, per 100 parts by mass of the composition. It is preferable to have a content of 0.1 parts by mass or more of the nonlinear optically active compound per 100 parts by mass of the composition because it enables the composition to exhibit nonlinear optical activity. It is also preferable to have a content of 50 parts by mass or less because it is possible to suppress the deterioration of properties due to the association of the nonlinear optically active compound and ensure solubility in the solvent.

[0174] There are no particular restrictions on the content of the nonlinear optically active polymer compound in the composition, but it 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. Furthermore, 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. An content of 1 part by mass or more of the nonlinear optically active polymer compound per 100 parts by mass of the composition is preferable from the viewpoint of ensuring film thickness. Furthermore, an content of 50 parts by mass or less is preferable because it provides good coatability.

[0175] [Silicone-based surfactants] The silicone-based surfactants used in the embodiments of the present invention have the function of improving the affinity between components in a composition by adjusting their polarity, and the function of lowering the surface tension of the solvent. As a result, they are used in a wide range of improvement applications such as dispersants, foaming agents, defoaming agents, emulsifiers, food additives, humectants, antistatic agents, wettability enhancers, lubricants, and rust inhibitors.

[0176] Specific examples of silicone-based surfactants include polysiloxanes; compounds obtained by partially modifying polysiloxanes with ethers, esters, or aralkyl compounds; compounds obtained by substituted polysiloxanes with alkyl groups; and reactive polysiloxanes obtained by adding reactive groups to polysiloxanes. From the viewpoint of heat resistance and compatibility with nonlinear optically active compounds, at least one silicone-based surfactant selected from the group consisting of polyether-modified silicone-based surfactants and aralkyl-modified silicone-based surfactants is preferred, and aralkyl-modified silicone-based surfactants are more preferred. The range of such preferred silicone-based surfactants does not depend on the type of nonlinear optically active material used. For example, even when the nonlinear optically active material is a nonlinear optically active polymer compound, the preferred range of the silicone-based surfactant remains as described above.

[0177] More specific examples of silicone-based surfactants include the KF series, X-22 series, and KP series from Shin-Etsu Chemical Co., Ltd., the BYK series from BYK Corporation, the SH series, BY series, OFX series, SF series, FZ series, and L series from Dow Toray Industries, Inc., and the Polyflow KL series from Kyoeisha Chemical Co., Ltd.While there are no particular limitations on the materials listed in the catalogs provided by each company, in terms of solubility in organic solvents and heat resistance, we especially recommend KF-351A, KF-945, KF-96, KF-6015, KF-6017, KF-410, KF-414, KF-4917, X-22-7322, X-22-1877, KF-50, KF-6004, KF-889, KF-53, X-22-163, X-22-164, KP-124, KP-106, KP-623, KP-323, KP-327, KP-341, KP-624. KP-310, KP-301, KP-105, KF-352A, KF-353, KF-354L, KF-355A, KF-615 A, KF-945, KF-640, KF-642, KF-643, KF-644, KF-6020, KF-6204, X-22- 4515, KF-6011, KF-6012, X-22-2516, KF-412, KF-413, KF-415, KF-4003, KF-4701, KF-4917, KF-7235B, BYK-361N, BYK-300, BYK-302, BYK-330, BYK-331, BYK-310, BYK-313, BYK-315N, BYK-370, BYK-320, BYK-322, BYK-323, BYK-3440, BYK-3 45, BYK-3560, BYK-306, BYK-325, BYK-333, BYK-342, BYK-346, BYK-34 7, BYK-348, BYK-349, BYK-377, BYK-378, BYK-3455, BYK-UV3576 (manufactured by BYK) ), SH200, 580, BY16-606, BY16-846, OFX-0203, OFX-0230, SF8416, SF8419, 501W, FZ-2110, FZ-2123, L-7001, OFX-0309, OFX-5211, SF8410, SH3746, SH8400, SH8700, SH510, SH550, SH710 (manufactured by Dow Toray Industries, Inc.), Polyflow KL-400HF, Polyflow KL-401, Polyflow KL-402, Polyflow KL-406 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. are preferred.

[0178] Surfactants are commonly used as additives in film formation processes to improve film flatness due to their function of reducing the surface tension of the solvent, as described above. In this embodiment, by including a specific type of surfactant at an appropriate concentration, it is possible to improve not only the flatness of the film but also the nonlinear optical properties of the nonlinear optically active material.

[0179] The reason why surfactants improve the nonlinear optical properties of nonlinear optically active materials can be explained as follows. As mentioned above, in compositions used to form nonlinear optically active materials, the nonlinear optically active compounds undergo dipole association, which tends to result in insufficient expression of nonlinear optical properties in the resulting nonlinear optically active material. In contrast, when a surfactant is included in the composition, the surfactant is adsorbed onto the nonlinear optically active compound, reducing the interaction between dipoles and suppressing dipole association. As a result, the nonlinear optical properties of the resulting nonlinear optically active material are improved. In particular, this effect is considered to be greater when the dipole of the nonlinear optically active compound is large. Nonlinear optically active compounds represented by equation (1) are known to have relatively large dipoles, and are therefore considered to be more effective.

[0180] Furthermore, in this embodiment, it was found that silicone-based surfactants, in particular, were highly effective in improving nonlinear optical properties. The reason for this can be explained as follows. While fluorine-based surfactants are also representative surfactants, alongside silicone-based surfactants, fluorine-based surfactants are more strongly adsorbed to the gas-liquid interface (composition surface) than silicone-based surfactants, and therefore their adsorption to nonlinear optically active compounds dissolved in the composition is considered to be smaller. Consequently, silicone-based surfactants are preferred for suppressing association between dipoles and improving nonlinear optical properties.

[0181] Furthermore, in this embodiment, it was found that there is a suitable range for the concentration of the silicone-based surfactant in the composition, and that exceeding this suitable concentration reduces the nonlinear optical properties of the resulting nonlinear optically active material. The reason for this can be explained as follows. It is thought that nonlinear optically active materials exhibit nonlinear optical properties when orientation is imparted to the nonlinear optically active compounds contained therein by poling, and when this orientation is maintained. This maintenance of orientation is largely due to the interaction between the nonlinear optically active compounds and surrounding compounds. Therefore, it is thought that when the concentration of the silicone-based surfactant exceeds the suitable range, the excess silicone-based surfactant is adsorbed onto the nonlinear optically active compounds, weakening the interaction between the nonlinear optically active compounds and surrounding compounds, and relaxing the orientation, thereby reducing the nonlinear optical properties of the nonlinear optically active material.

[0182] The compositions according to embodiments of the present invention may contain a surfactant containing fluorine as a surfactant, as long as the effects of the present invention are not impaired. Examples of surfactants containing fluorine include fluorine-containing oligomers; perfluoroalkyl group-containing oligomers; the above oligomers having UV reactive groups; and the like. Specifically, examples include the Florard series manufactured by 3M; the Megafac® F series and Megafac® R series manufactured by DIC Corporation; the Surflon® S series manufactured by AGC Seimi Chemical Co., Ltd.; the Unidyne® series and Demnam® series manufactured by Daikin Industries, Ltd.; the F-Top EF series manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; the Polyflow series manufactured by Kyoeisha Chemical Co., Ltd.; the Troisol S series manufactured by Troy Chemicals Inc.; the PolyFox series manufactured by OMNOVA Inc.; and the Capstone® series manufactured by DuPont Inc. While there are no particular limitations on the materials listed in the catalogs provided by each company, in particular, from the perspective of solubility in organic solvents, FC-4430, FC-4432 (manufactured by 3M), F-444, F-477, F-554, F-556, F-565, F-568, F-557, F-559, F-560, F-561, F-562, F-552, RS-75, RS-78, RS-56, F-410, F-510, F-553, F-430, F-555 (manufactured by DIC Corporation), S-242, S-243, S-420, S-611, S-651, S-386, S-680, S-685, S-693 (manufactured by AGC Seimi Chemical Co., Ltd.), No. 7, No. Preferred varieties include 50, No. 54, No. 75, No. 77, No. 85, No. 90, No. 95, No. 99 (manufactured by Kyoeisha Chemical Co., Ltd.), TG-5502, S-20, S-65, S-200 (manufactured by Daikin Industries, Ltd.), EF-PP31, EF-PP33, EF-PP32, EF-L174 (manufactured by Mitsubishi Materials Electronic Chemicals Corporation), S-366 (manufactured by Troy Chemicals Corporation), PF-6320, PF-154, PF-159, PF-3320, PF-151, PF-652, PF-636 (manufactured by OMNOVA Corporation), FS-22, FS-66, FS-83 (manufactured by DuPont).

[0183] [Solvent] The solvent that can be used in the composition according to the embodiment of the present invention is not particularly limited as long as it dissolves the nonlinear optically active material and the silicone-based surfactant. Preferably, the solvent is 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; acetone, ethyl methyl ketone, isopropyl methyl ketone, isopropyl Ketones such as methyl ketone, butyl methyl ketone, diacetone alcohol, diethyl ketone, cyclopentanone, cyclohexanone; esters such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, phenyl acetate, 2-methoxyethyl acetate, ethyl lactate, γ-butyrolactone, ethyl benzoate, methyl benzoate, benzoyl benzoate, 2-ethylhexyl benzoate, 4-methylbenzoate ethyl; N,N-dimethylformamide, N,N-dimethylacetamide, N Amides such as -methyl-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 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, anisole, etc. These organic solvents may be used individually or in combination of two or more.

[0184] Of the above solvents, chlorobenzene, orthodichlorobenzene, 1,2-dichloroethane, trifluoromethylbenzene, 3-methoxybenzotrifluoride, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are more preferred from the viewpoint of coating properties, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are even more preferred, and cyclopentanone, cyclohexanone, toluene, anisole, and dibromomethane are particularly preferred.

[0185] There are no particular restrictions on the solvent content in the composition, but it 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, per 100 parts by mass of the composition. Furthermore, 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, per 100 parts by mass of the composition. A solvent content of 50 parts by mass or more per 100 parts by mass of the composition is preferable because it provides good coatability. Furthermore, a solvent content of 99 parts by mass or less is preferable because it ensures a sufficient film thickness.

[0186] [Polymer Materials] The composition may contain polymer materials. The inclusion of polymer materials in the composition is preferable because it improves the coatability and helps maintain the orientation of the nonlinear optically active compound.

[0187] There are no particular restrictions on the content of polymer materials, but from the viewpoint of coatability and solubility, it is preferably 0 to 99 parts by mass, more preferably 0 to 95 parts by mass, and even more preferably 0 to 90 parts by mass per 100 parts by mass of the composition.

[0188] [Other components] In addition to nonlinear optically active materials, silicone-based surfactants and solvents, and polymer materials, other components may be used in the composition.

[0189] Other components are not particularly limited as long as they do not hinder the purpose for which the composition is used. However, as long as they do not impair the effects of the present invention, surfactants other than silicone-based surfactants, antioxidants such as hydroquinone, ultraviolet absorbers such as benzophenone, adhesion aids such as silane coupling agents, polymer materials having crosslinking groups, compatibilizers, curing agents, pigments, preservatives, and the like may be included as needed.

[0190] There are no particular restrictions on the content of other components in the composition, but from the viewpoint of uniformity of film thickness, it 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 per 100 parts by mass of the composition.

[0191] [Method for Manufacturing the Composition] A method for manufacturing the composition according to the embodiment of the present invention may include the step of dissolving the above-mentioned nonlinear optically active material and the above-mentioned silicone-based surfactant in the above-mentioned solvent. In one embodiment, a method for manufacturing the composition is provided that includes the steps of mixing and heating and stirring the above-mentioned nonlinear optically active material and silicone-based surfactant with the above-mentioned solvent to dissolve them, and filtering this solution. When using a combination of a nonlinear optically active material and a polymer material, the polymer material can be further mixed and dissolved when mixing the nonlinear optically active material and the solvent. In another embodiment, a method for manufacturing the composition is provided that includes the steps of mixing and heating and stirring a mixture of the above-mentioned nonlinear optically active compound and a silicone-based surfactant with the above-mentioned solvent to dissolve it, and filtering this solution.

[0192] [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 material into a film or thin film. The nonlinear optically active material, in the form of 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.

[0193] <Nonlinear Optical Film> The nonlinear optical film according to the embodiment of the present invention is a nonlinear optical film formed from the above-described composition.

[0194] The components and preferred ranges of the nonlinear optical film are as described above for the composition. However, the nonlinear optical film generally does not contain a solvent.

[0195] It is preferable that the silicone-based surfactant contained in the above-mentioned nonlinear optical film is distributed along the film thickness direction. Methods for determining the distribution of silicone-based surfactant in the film include comparing the peak intensities originating from silicon atoms using energy-dispersive X-ray spectroscopy (SEM-EDX) on a film that has been cut at an angle, and comparing the peak intensities originating from silicone-based surfactants using time-of-flight secondary ion mass spectrometry (TOF-SIMS) while etching the surface from the film surface using a sputter ion gun.

[0196] In one embodiment, a nonlinear optical film according to the present invention comprises at least one selected from the group consisting of a compound represented by formula (1) and a nonlinear optically active polymer compound containing a monovalent or multivalent group obtained by removing at least one hydrogen atom from the compound represented by formula (1), and a silicone-based surfactant, and the silicon atom concentration measured by X-ray photoelectron spectroscopy (XPS) can be 3 at% or less. In another embodiment, a nonlinear optical film according to the present invention may also include at least one selected from the group consisting of a compound represented by formula (1) and a nonlinear optically active polymer compound containing a monovalent or multivalent group obtained by removing at least one hydrogen atom from the compound represented by formula (1), and a silicone-based surfactant. The preferred embodiment of formula (1) in the compound represented by formula (1) or the nonlinear optically active polymer compound containing a monovalent or multivalent group obtained by removing at least one hydrogen atom from the compound represented by formula (1) is as described above for the compositions.

[0197] To obtain a good electro-optic coefficient, the silicon atom concentration of the nonlinear optical film, as measured by X-ray photoelectron spectroscopy (XPS), is preferably 3 at% or less, more preferably 1.8 at% or less, even more preferably 1.1 at% or less, and particularly preferably 0.5 at% or less. There is no particular lower limit to the silicon atom concentration of the nonlinear optical film; for example, it can be 0.003 at% or more, 0.01 at% or more, or 0.03 at% or more. The silicon atom concentration of the nonlinear optical film, as measured by X-ray photoelectron spectroscopy (XPS), can be, for example, 0.03 to 3 at%.

[0198] To obtain good nonlinear optical activity, the nonlinear optically active polymer compound that may be included in the nonlinear optical film according to the embodiment of the present invention is preferably a nonlinear optically active polymer compound that contains a monovalent or multivalent group obtained by removing at least one hydrogen atom from the compound represented by formula (1).

[0199] [Method for Forming Nonlinear Optical Films] There are no particular limitations on the method for forming a nonlinear optical film or nonlinear optical thin film (hereinafter, both are collectively referred to as "nonlinear optical film" in this specification) from the composition according to the embodiment of the present invention. For example, known methods such as injection molding, press molding, soft lithography, and wet coating methods can be used. Among these, wet coating methods such as spin coating, blade coating, immersion coating, and inkjet coating can be used, from the viewpoint of simplicity of manufacturing equipment, mass production capability, and film quality (uniformity of film thickness, low number of defects such as bubbles, etc.).

[0200] One embodiment involves coating a substrate with a composition obtained by dissolving the above-mentioned nonlinear optically active material and a silicone-based surfactant in the above-mentioned solvent, and then drying it. Drying here refers to, for example, a step of drying by placing the substrate on a heating device such as a hot plate and heating it, or a step of drying by placing the coated substrate in a chamber and creating a vacuum, or a step of combining both. A preferred method for forming a nonlinear optical film may include, in this order, a step of coating the above-mentioned composition onto a substrate, a step of drying the coated composition, and a step of firing the dried composition at 100 to 200°C.

[0201] <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 nonlinear optical effects, but examples include wavelength conversion elements, photorefractive elements, and electro-optic elements. Among these, nonlinear optical elements that operate based on electro-optic effects are preferred, and more specifically, electro-optic elements such as optical switches, optical modulators, and phase shifters are preferred. In one embodiment, an optical modulator comprising the nonlinear optical film described above can be provided.

[0202] As an electro-optic element, it is preferable to use an element having a structure in which a nonlinear optical film is formed on a substrate and sandwiched between electrode pairs for input electrical signals.

[0203] Materials that can be used to construct such a substrate include, for example, 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, polyetherketone, and polyimide.

[0204] 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, poly(p-phenylenevinylene), and polyacetylene. The conductive film is formed using known dry deposition methods such as vapor deposition and sputtering, or known wet deposition methods such as immersion coating and electrolytic deposition, and a pattern may be formed 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" in this specification) during poling and operation as an element.

[0205] The substrate surface may further have an adhesive layer to improve the adhesion between the film formed thereon and the substrate, a leveling layer to smooth out surface irregularities, or some intermediate layer that provides these functions together, as needed. There are no particular restrictions on the material used to form such a film, but known materials such as acrylic resins, methacrylic resins, amide resins, vinyl chloride resins, vinyl acetate resins, phenolic resins, urethane resins, vinyl alcohol resins, acetal resins, etc. and copolymers thereof; crosslinked materials such as zirconium chelate compounds, titanium chelate compounds, silane coupling agents, etc., and co-crosslinked materials thereof can be used.

[0206] The electro-optic element is preferably formed to include a waveguide structure, and it is particularly preferable to incorporate the above-mentioned nonlinear optical film into the core layer of the waveguide.

[0207] A cladding layer (hereinafter also referred to as the "lower cladding layer" in this specification) may be formed between the core layer containing the aforementioned nonlinear optical film and the substrate. This lower cladding layer can be any material that has a lower refractive index than the core layer and is not affected during the formation of the core layer. Preferred materials for forming the lower cladding layer include, for example, UV-curable or thermosetting resins such as acrylic, epoxy, oxetane, thiirane, and silicone; polyimide; and glass.

[0208] After forming the core layer with the nonlinear optical film described above, a cladding layer (hereinafter also referred to as the "upper cladding layer" in this specification) may be formed on top of it in the same manner as the lower cladding layer. This forms a slab-type waveguide with the configuration of substrate / lower cladding layer / core layer / upper cladding layer.

[0209] After forming the core layer, the core layer can be patterned using known methods employing semiconductor process technologies such as reactive ion etching (RIE), photolithography, and electron beam lithography to form channel-type waveguides or ridge-type waveguides. Alternatively, a channel-type waveguide can be formed by patterning and irradiating a portion of the core layer with UV light, an electron beam, or the like, thereby changing the refractive index of the irradiated area.

[0210] A basic electro-optic element can be formed by forming electrodes (hereinafter also referred to as "upper electrodes" in this specification) for applying an input electrical signal on the surface of the upper cladding layer in a desired region of the upper cladding layer.

[0211] When forming channel-type waveguides or ridge-type waveguides as described above, known device structures such as straight, Y-branch, directional coupler, and Mach-Zehender types can be configured as the core layer pattern, and these can be applied to known optical information communication devices such as optical switches, optical modulators, and phase shifters. One example of application to optical information communication devices is the application to an optical modulator equipped with a nonlinear optical element that operates based on the electro-optic effect described above.

[0212] 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 can be modified and implemented as such without departing from its essence.

[0213] <Synthesis of Nonlinear Optically Active Polymer Compound 2>

[0214] [Synthesis of Compound 1]

[0215]

[0216] In a 1 L flask, a solution of 4-bromosalicylaldehyde (20.1 g, 0.1 mol) and potassium carbonate (27.6 g, 0.2 mol) in N,N-dimethylformamide (DMF) (200 mL) was cooled to 0°C. While stirring, benzyl bromide (22.2 g, 0.13 mol) was slowly added. After the addition, the temperature was raised to room temperature and the mixture was stirred for 3 hours. After the reaction was complete, water (200 mL) was added and the mixture was extracted with DCM (300 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 1 (17.8 g, yield 61.1%).

[0217] [Synthesis of Compound 2]

[0218]

[0219] In a 500 mL flask, a solution of compound 1 (16.3 g, 56.1 mmol) and diethyl (thiophene-2-ylmethyl) phosphonate (15.8 g, 67.3 mmol) in tetrahydrofuran (THF) (163 mL) was cooled to 0°C. While stirring, tert-butoxy potassium (6.92 g, 61.7 mmol) was slowly added. After the addition, the temperature was raised to room temperature and stirred for 4 hours. After the reaction was complete, water (100 mL) was added and the mixture was extracted with DCM (200 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 2 (17.4 g, yield 83.7%).

[0220] [Synthesis of Compound 3]

[0221]

[0222] In a 500 mL flask, under a nitrogen stream, imidazole (28.2 g, 414 mmol) was added to a solution of diethanolamine (10.9 g, 104 mmol) in N,N-dimethylformamide (DMF) (163 mL). After cooling to 0°C, tert-butyldimethylchlorosilane (32.8 g, 217 mmol) was slowly added while stirring. After the addition, the temperature was raised to room temperature and stirred for 4 hours. After the reaction was complete, water (100 mL) was added and the mixture was extracted with DCM (300 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 3 (32.0 g, yield 92.7%).

[0223] [Synthesis of Compound 4]

[0224]

[0225] Compound 3 (15.8 g, 47.5 mmol) was added to a toluene solution (147 mL) of compound 2 (14.7 g, 39.6 mmol) in a 500 mL flask. After bubbling the reaction solution with nitrogen for 20 minutes, tert-butoxysodium (5.32 g, 55.4 mmol) and separately prepared Pd were added under a nitrogen stream. ２ (dba) ３ A solution of (362 mg, 0.40 mmol) and XPhos (754 mg, 1.6 mmol) in toluene (11 mL) was added. After addition, the reaction solution was heated to 95°C and stirred at 95°C for 3.5 hours. After the reaction was complete, water (100 mL) was added and extracted with DCM (300 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 4 (18.3 g, yield 74.1%).

[0226] [Synthesis of Compound 5]

[0227]

[0228] In a 500 mL flask, under a nitrogen stream, a solution of compound 4 (17.2 g, 27.5 mmol) in tetrahydrofuran (THF) (172 mL) was cooled to -78°C. Then, a hexane solution of n-butyllithium (1.6 M, 18.9 mL, 30.3 mmol) was added, and the mixture was stirred for 30 minutes. Subsequently, tetrahydrofuran (8.5 mL) of N,N-dimethylformamide (8.5 mL, 110 mL) was added, and the mixture was heated to 0°C and stirred for 1.5 hours. After the reaction was complete, water (100 mL) was added, and the mixture was extracted with DCM (300 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 5 (13.3 g, yield 74.3%).

[0229] [Synthesis of Compound 6]

[0230]

[0231] In a 500 mL flask, a solution of compound 5 (7.6 g, 11.7 mmol) in tetrahydrofuran (146 mL) was cooled to 0°C, and 4 M hydrochloric acid (87.4 mL, 351 mmol) was added dropwise. After addition, the mixture was heated to room temperature and stirred for 2 hours. After the reaction was complete, water (100 mL) was added, neutralized with sodium bicarbonate, and then extracted with DCM (300 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 6 (4.5 g, yield 90.9%). The results of the NMR measurement of compound 6 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ9.80 (s, 1H), 7.61 (d, 1H), 7.26-7.48 (m, 7H), 7.14 (d, 1H), 7.01 (d, 1H), 6. 31 (dd, 1H), 6.20 (d, 1H), 5.20 (s, 2H) 3.80 (dd, 4H), 3.58 (dd, 4H), 2.85 (s, 2H)

[0232] [Synthesis of Nonlinear Optically Active Compound 3]

[0233]

[0234] In a 100 mL three-necked flask, under a nitrogen stream, a solution of compound 6 (200 mg, 0.51 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (168 mg, 0.53 mmol) in THF (10 mL) was added, and ethanol (10 mL) was stirred at room temperature for 18 hours. The solution was then concentrated under reduced pressure and purified by silica gel chromatography to obtain nonlinear optically active compound 3 (250 mg, yield 71.2%). The results of the NMR measurement of nonlinear optically active compound 3 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.77 (d, 1H), 7.33-7.57 (m, 13H), 7.28 (d, 1H), 7.16 (d, 1H), 6.95 (d, 1H), 5.19 (s, 2H), 3.80 (t, 4H), 3.61 (t, 4H), 2.72 (s, 2H)

[0235] [Synthesis of base polymer 1]

[0236]

[0237] Styrene (10.2 g, 97.8 mmol), N-ethylmaleimide (7.34 g, 58.7 mmol), and N-succinimidyl 3-maleimidopropionic acid (10.4 g, 39.1 mmol) were added to a flask, purged with nitrogen, dissolved in deoxygenated DMF (1882 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (194 mg, 0.78 mmol) were added. The reaction solution was heated to 60°C and stirred for 6 hours. Then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was cooled to room temperature. After cooling, it was added dropwise to methanol (8.8 L), and the resulting solid was filtered. The filtered solid was rinsed with methanol (2.2 L) and vacuum dried. The dried solid was redissolved in THF (360 mL) and filtered. The filtrate was added dropwise to methanol (3.4 L), and the resulting solid was filtered off. The filtered solid was rinsed with methanol (1.5 L) and vacuum dried to obtain base polymer 1 (20.2 g, yield 72.3%). The molecular weight of the obtained base polymer 1 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (column: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: LiBr (0.5 wt%) in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 27,000, and the number-average molecular weight Mn was 12,000.

[0238] [Synthesis of nonlinear optically active polymer compound 2']

[0239]

[0240] Under a nitrogen atmosphere, base polymer 1 (600 mg) and compound 6 (77 mg, 0.18 mmol) were dissolved in anhydrous chloroform (21.9 mL). 4-dimethylaminopyridine (DMAP) (223 mg, 1.82 mmol) and N-N'-dicyclohexylcarbodiimide (DCC) (260 mg, 1.26 mmol) were added, and the mixture was stirred in an oil bath at 60°C for 6 hours. Anhydrous methanol (2.0 mL) was then added, and the mixture was stirred in an oil bath at 60°C for 6 hours. After cooling to room temperature, the reaction solution was added dropwise to methanol (150 mL). The resulting solid was filtered and rinsed with methanol (50 mL). The filtered material was dissolved in dichloromethane (10 mL) and added dropwise to methanol (150 mL). The resulting solid was filtered and rinsed with methanol (50 mL). The filtered material was redissolved in dichloromethane (10 mL) and added dropwise to hexane (150 mL). The resulting solid was filtered, rinsed with hexane (50 mL), and then vacuum-dried to obtain nonlinear optically active polymer compound 2' (550 mg).

[0241] Here, there are two possible configurations for compound 6: one in which only one of the two hydroxyl groups reacts and links to base polymer 1 at one site, and another in which both react and links to base polymer 1 at two sites. In the case of two-site linkage to the base polymer, there are two-site linkages within a single base polymer molecule, and two-site linkages between the molecules of two base polymers. Therefore, (x + 2y) is greater than 0.02 and less than 0.044.

[0242] [Synthesis of Nonlinear Optically Active Polymer Compound 2]

[0243]

[0244] Under a nitrogen atmosphere, 500 mg of nonlinear optically active polymer compound 2' and 131 mg, 0.42 mmol of 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile were dissolved in 25 mL of deoxygenated THF. Then, 12.5 mL of dehydrated ethanol was added, and the mixture was stirred at 60°C for 8 hours. After cooling to room temperature, the reaction solution was concentrated using an evaporator. The concentrate was redissolved in 10 mL of dichloromethane and added dropwise to 150 mL of methanol. The resulting solid was filtered and rinsed with 50 mL of methanol. The filtered material was dissolved in 10 mL of dichloromethane and added dropwise to 150 mL of methanol. The resulting solid was filtered and rinsed with 50 mL of methanol. The filtered material was redissolved in dichloromethane (10 mL) and added dropwise to hexane (150 mL). The resulting solid was filtered, rinsed with hexane (50 mL), and then vacuum-dried to obtain nonlinear optically active polymer compound 2 (420 mg). The content of groups obtained by removing one or two hydrogen atoms from nonlinear optically active compound 3 in nonlinear optically active polymer compound 2 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content of groups obtained by removing one or two hydrogen atoms from nonlinear optically active compound 3 was found to be 19.3% by mass. The molecular weight of the obtained nonlinear optically active polymer compound 2 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: LiBr (0.5 wt%) in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 44,000 and the number-average molecular weight Mn was 17,000.

[0245] [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 for coating the composition. Here, the glass plate contained in the ITO substrate corresponds to the carrier, and the ITO film corresponds to the electrode.

[0246] (Preparation of film 1) Polymethyl methacrylate (PMMA, molecular weight 82000) and nonlinear optically active compound 1 (Tokyo Chemical Industries, Ltd., NEO-823, dipole moment: 20.5D) were dissolved in cyclohexanone in a ratio of 80:20 to obtain a mixed solution 1 with a total solid content concentration of 13.0% by mass. BYK-331 (polyether-modified dimethylsiloxane, manufactured by BYK) was added to the mixed solution 1 so that the content of the silicone-based surfactant relative to the total solid content in the composition was 0.01% by mass. The solution after addition was filtered through a PTFE (polytetrafluoroethylene) filter with a pore size of 0.22 μm to obtain composition 1. Composition 1 was coated onto the side of the ITO substrate on which the ITO film was provided using a spin coater (Mikasa Corporation, MS-A150).

[0247]

[0248] The dipole moment of nonlinear optically active compound 1 was determined by density functional theory (DFT) calculation. Using the Gaussian 16 package, the molecular shape in chloroform was optimized at calculation level CAM-B3LYP / 6-311+G(d,p) and the dipole moment was calculated. The effect of the solvent, chloroform, was incorporated by applying a continuous dielectric model (PCM). The dipole moments of nonlinear optically active compounds 2 and 4, described later, were determined in the same manner.

[0249] An ITO substrate coated with composition 1 was pre-baked on a hot plate (AS ONE Corporation, HP-1SA) at 60°C for 1 minute. After pre-baking, the ITO substrate was subjected to a vacuum constant-temperature drying treatment at 85°C for 15 hours to remove the solvent and obtain the film-coated substrate (substrate 1) of Example 1. Substrate 1 is a substrate on which a film (film 1) containing a nonlinear optically active compound and a silicone-based surfactant is formed on an ITO substrate.

[0250] (Preparation of electrode-attached substrate) On a portion of the surface of the film 1 side of the prepared substrate 1, a film thickness of 50 nm and an area of ​​30 mm² were applied. ２ Gold electrodes were formed by depositing gold using a vacuum deposition apparatus (ULVAC, Inc., EX-400-C08) to obtain an electrode-equipped substrate 1. The surface of the electrode-equipped substrate 1 on the film 1 side has a gold electrode-forming area where gold electrodes are formed and a non-electrode-forming area where gold electrodes are not formed. The electrode-equipped substrate 1 has the following layer structure and was used to evaluate the electro-optic coefficient. Layer structure: ITO substrate (glass plate carrier + ITO film) / film 1 / gold electrode

[0251] [Polling Process] The electrode-equipped substrate 1 was heated to 115°C using a temperature controller (Lake Shore Cryotronics, Model 3060), and then cooled to room temperature with liquid nitrogen while applying a voltage of 75 V / μm using a voltage application device (Keithley, 2470 SourceMeter). This process resulted in a polled substrate 1 in which the nonlinear optically active compound on the electrode-equipped substrate 1 was field-oriented. The arithmetic roughness (Ra) of the polled substrate 1 was measured using an optical interferometer (Hitachi High-Tech Corporation, VertScan optical interferometer). The results are shown in Table 1.

[0252] [Electro-optic coefficient] The electro-optic coefficient (hereinafter also referred to as "electro-optic coefficient" in this specification) was measured at a wavelength of 1.31 μm (laser light source: Santec Corporation, TSL-570) using a method similar to that disclosed in C. C. Teng et al., Apple Phys. Lett., 56, p1734 (1990), and Y. Shuto et al., J. Apple Phys., 77, p4632 (1995). A function generator (Teledyne LeCroy, T3AFG10) was used to apply the AC voltage, and a lock-in amplifier (NF Circuit Design Block Co., Ltd., digital lock-in amplifier LI5600) was used to evaluate the intensity. For Example 1, Examples 2-3 (described later), and Comparative Examples 2-4, the measured electro-optic coefficients were evaluated using the relative electro-optic coefficient, which is the ratio of the electro-optic coefficient without surfactant (the electro-optic coefficient of Comparative Example 1) to 1. The results are shown in Table 1.

[0253] [X-ray photoelectron spectroscopy (XPS) measurement] X-ray photoelectron spectroscopy (XPS) analysis was performed on the non-electrode formation area of ​​film 1 on the polled substrate 1 under the following conditions, and the atomic concentration of silicon was measured from the Si2p spectrum. A substrate sample formed from a composition without added silicone-based surfactant was used as a blank, and the value obtained by subtracting the measurement value of the blank was taken as the atomic concentration of silicon of the polled substrate 1 (silicon concentration by XPS). Equipment used: KRATOS ULTRA2 (Shimadzu Corporation) X-ray source: Monochromatic Al-Kα Output: 15kV / 300W Charge neutralization: Low-speed electron beam irradiation Measurement area: 700μm × 300μm Extraction angle (from surface): 90° The results are shown in Table 1.

[0254] [Example 2] A substrate was prepared and evaluated in the same manner as in Example 1, except that BYK-331 was added to the composition at a concentration of 0.1% by mass relative to the total solid content. The results are shown in Table 1.

[0255] [Example 3] A substrate was prepared and evaluated in the same manner as in Example 1, except that BYK-331 was added to the composition at a concentration of 1% by mass relative to the total solid content. The results are shown in Table 1.

[0256] [Comparative Example 1] A substrate was prepared and evaluated using the same procedure as in Example 1, except that BYK-331 was not added. The results are shown in Table 1.

[0257] [Comparative Example 2] A substrate was prepared and evaluated using the same procedure as in Example 1, except that BYK-331 was added to the composition at a concentration of 5% by mass relative to the total solid content. The results are shown in Table 1.

[0258] [Comparative Example 3] The substrate was prepared and evaluated using the same procedure as in Example 1, except that S-693 (fluorine-based surfactant manufactured by AGC Seimi Chemical Co., Ltd.) was added instead of BYK-331, and silicon concentration was not measured by XPS. The results are shown in Table 1.

[0259] [Comparative Example 4] The substrate was prepared and evaluated using the same procedure as in Comparative Example 3, except that S-693 was added to the composition at a concentration of 0.1% by mass relative to the total solid content, and the silicon concentration was not measured by XPS. The results are shown in Table 1.

[0260]

[0261] As shown in Table 1, in the composition according to the embodiment of the present invention, a specific amount of silicone-based surfactant was observed to improve both flatness and the electro-optic coefficient.

[0262] [Example 4] Except for setting the polling voltage to 100 V / μm, the substrate was prepared and evaluated in the same procedure as in Example 2. For Example 4 and Examples 5 to 8 described later, the measured electro-optic coefficient was evaluated using the relative electro-optic coefficient, which is the ratio of the electro-optic coefficient without surfactant (electro-optic coefficient of Comparative Example 5) to 1. The evaluation of Ra was performed in the same manner as in Example 1. The results are shown in Table 2.

[0263] [Example 5] A substrate was prepared and evaluated in the same procedure as in Example 4, except that BYK-323 (aralkyl-modified polymethylalkylsiloxane, manufactured by BYK) was added instead of BYK-331 (polyether-modified dimethylsiloxane, manufactured by BYK). The results are shown in Table 2.

[0264] [Example 6] A substrate was prepared and evaluated using the same procedure as in Example 4, except that BYK-320 (polyether-modified methylalkylsiloxane, manufactured by BYK) was added instead of BYK-331. The results are shown in Table 2.

[0265] [Example 7] A substrate was prepared and evaluated using the same procedure as in Example 4, except that BYK-UV3576 (modified dimethylsiloxane containing acrylic functional groups, manufactured by BYK) was added instead of BYK-331. The results are shown in Table 2.

[0266] [Example 8] A substrate was prepared and evaluated using the same procedure as in Example 4, except that BYK-315N (polyester-modified methylalkylsiloxane, manufactured by BYK) was added instead of BYK-331. The results are shown in Table 2.

[0267] [Comparative Example 5] The substrate was prepared and evaluated using the same procedure as in Comparative Example 1, except that the polling voltage was set to 100 V / μm. The results are shown in Table 2.

[0268]

[0269] As shown in Table 2, in the compositions according to the embodiments of the present invention, an improvement in flatness was confirmed regardless of the type of silicone surfactant, and at the same time, an improvement in the electro-optic coefficient was also confirmed. Among these, polyether-modified silicone surfactants and aralkyl-modified silicone surfactants were particularly effective in improving performance, and it was confirmed that aralkyl-modified silicone surfactants significantly improved performance.

[0270] [Comparative Example 6] A nonlinear optically active compound 2 (Sigma-Aldrich Dispersed 1, dipole moment: 12.2D) was used instead of nonlinear optically active compound 1, and the polling voltage was set to 50 V / μm. Except for this, the substrate was prepared and evaluated in the same procedure as in Example 2. For Comparative Example 6, the measured electro-optic coefficient was evaluated using the relative electro-optic coefficient, which is the ratio of the electro-optic coefficient without surfactant (electro-optic coefficient of Comparative Example 7) to 1. The evaluation of Ra was performed in the same manner as in Example 1. The results are shown in Table 3.

[0271]

[0272] [Comparative Example 7] A substrate was prepared and evaluated using the same procedure as in Comparative Example 1, except that nonlinear optically active compound 2 was used instead of nonlinear optically active compound 1, and the polling voltage was set to 50 V / μm. The results are shown in Table 3.

[0273]

[0274] [Example 9] A substrate was prepared and evaluated in the same procedure as in Example 2, except that a nonlinear optically active compound 4 (compound described in International Publication No. 2025 / 182877 (EOD-005), dipole moment: 34.4D) was used instead of nonlinear optically active compound 1, and the polling voltage was set to 50 V / μm.

[0275]

[0276] For Example 9, the measured electro-optic coefficient was evaluated using the relative electro-optic coefficient, which is the ratio of the electro-optic coefficient without surfactant (the electro-optic coefficient of Comparative Example 8) to 1. The evaluation of Ra was performed in the same manner as in Example 1. The results are shown in Table 4.

[0277] [Comparative Example 8] A substrate was prepared and evaluated using the same procedure as in Comparative Example 1, except that nonlinear optically active compound 4 was used instead of nonlinear optically active compound 1, and the polling voltage was set to 50 V / μm. The results are shown in Table 4.

[0278]

[0279] As shown in Tables 3 and 4, an improvement in flatness was confirmed in the compositions according to the embodiments of the present invention, and in particular, an improvement in the electro-optic coefficient was confirmed when a nonlinear optically active compound represented by formula (1) was used.

[0280] [Example 10] Using a composition obtained by adding 0.01% by mass of the fluorine-based surfactant S-693 (fluorine-based surfactant manufactured by AGC Seimi Chemical Co., Ltd.) to the composition used in Example 1, a substrate was prepared and evaluated in the same procedure as in Example 1.

[0281] For Example 10, the measured electro-optic coefficient was evaluated using the relative electro-optic coefficient, which is the ratio of the electro-optic coefficient without surfactant (the electro-optic coefficient of Comparative Example 1) to 1. The evaluation of Ra was performed in the same manner as in Example 1. The results are shown in Table 5.

[0282]

[0283] As shown in Table 5, in the compositions according to the embodiments of the present invention, even when specific amounts of silicone-based surfactants and fluorine-based surfactants were mixed, an improvement in flatness and an improvement in the electro-optic coefficient were confirmed. However, as can be seen from the comparison between Table 1 and Table 5, the improvement in the electro-optic coefficient was smaller compared to when only silicone-based surfactants were used, and it was confirmed that using only silicone-based surfactants contributed more to the improvement in the electro-optic coefficient.

[0284] [Example 11] A mixed solution 2 was prepared by dissolving the nonlinear optically active polymer compound 1 in cyclohexanone to a total solid content concentration of 12% by mass. BYK-323 (aralkyl-modified polymethylalkylsiloxane, manufactured by BYK) was added to this mixed solution 2 so that the content of the silicone-based surfactant relative to the total solid content of the composition was 0.01% by mass. Using this composition 2, a substrate was prepared and evaluated in the same procedure as in Example 1, except that the polling voltage was set to 50 V / μm. The nonlinear optically active polymer compound 1 was prepared by the method described in Japanese Patent Application No. 2024-057420.

[0285]

[0286] For Example 11 and Example 12 (described later), the measured electro-optic coefficient was evaluated using the relative electro-optic coefficient, which is the ratio of the electro-optic coefficient without surfactant (the electro-optic coefficient of Comparative Example 10) to 1. The evaluation of Ra was performed in the same manner as in Example 1. The results are shown in Table 6.

[0287] [Example 12] A substrate was prepared and evaluated in the same manner as in Example 11, except that BYK-323 was added to the composition at a concentration of 0.1% by mass relative to the total solid content. The results are shown in Table 6.

[0288] [Comparative Example 9] A substrate was prepared and evaluated in the same manner as in Example 11, except that BYK-323 was added to the composition at a concentration of 5.12% by mass relative to the total solid content. During the polling process, an excessive current flowed, preventing the application of the predetermined voltage to the nonlinear optically active polymer compound 1, and thus making it impossible to measure the electro-optic coefficient. The results are shown in Table 6.

[0289] [Comparative Example 10] A substrate was prepared and evaluated using the same procedure as in Example 11, except that BYK-323 was not added. The results are shown in Table 6.

[0290]

[0291] [Example 13] A mixed solution 3 was prepared by dissolving a nonlinear optically active polymer compound 2 in cyclohexanone to a total solid content concentration of 14% by mass. BYK-323 (aralkyl-modified polymethylalkylsiloxane, manufactured by BYK) was added to this mixed solution 3 so that the content of the silicone-based surfactant relative to the total solid content of the composition was 0.1% by mass. Using this composition 3, a substrate was prepared and evaluated in the same procedure as in Example 1, except that the poling temperature was 160°C and the voltage was 50V / μm.

[0292] For Example 13 and Example 14 (described later), the measured electro-optic coefficient was evaluated using the relative electro-optic coefficient, which is the ratio of the electro-optic coefficient without surfactant (the electro-optic coefficient of Comparative Example 11) to 1. The evaluation of Ra was performed in the same manner as in Example 1. The results are shown in Table 7.

[0293] [Example 14] A substrate was prepared and evaluated using the same procedure as in Example 13, except that BYK-331 (polyether-modified dimethylsiloxane, manufactured by BYK) was added instead of BYK-323. The results are shown in Table 7.

[0294] [Comparative Example 11] A substrate was prepared and evaluated using the same procedure as in Example 13, except that BYK-323 was not added. The results are shown in Table 7.

[0295]

[0296] As shown in Tables 6 and 7, in the compositions according to the embodiments of the present invention, even when a nonlinear optically active polymer compound having a group derived from the compound represented by formula (1) is used, it was confirmed that a specific amount of silicone-based surfactant improves flatness, and an improvement in the electro-optic coefficient was also confirmed.

[0297] Although various embodiments have been described above, it goes without saying that the present invention is not limited to these examples. It is clear to those skilled in the art that various modifications or alterations can be conceived within the scope of the claims, and these will naturally also fall within the technical scope of the present invention. Furthermore, the components in the above embodiments may be combined in any way without departing from the spirit of the invention.

[0298] This application is based on the Japanese Patent Application No. 2024-196198 filed on November 8, 2024, the contents of which are incorporated by reference within this application.

[0299] 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 non-linear optical active material, a surfactant, and a solvent, wherein the surfactant contains a silicone-based surfactant, and the non-linear optical active material includes at least one selected from the group consisting of a compound represented by the following formula (1) and a non-linear optical active polymer compound containing a monovalent or polyvalent group obtained by removing at least one hydrogen atom from the compound represented by the following formula (1), and the content of the silicone-based surfactant with respect to the total solid content in the composition is 3% by mass or less. [In formula (1), Ar ３１ is 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, R ３１ and R ３３ are each independently a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, and a part of the carbon atoms thereof may be substituted with an oxygen atom, a sulfur atom, and / or a silicon atom, a divalent group selected from 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 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, and a part of the carbon atoms thereof may be substituted with an oxygen atom, a sulfur atom, and / or a silicon atom, 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, Y ３１ is each independently a divalent π-conjugated linking group which may have a substituent, Z ３１ is a group represented by the following formula (2), m ３１ is an integer of 0 to 5, m ３２ is an integer of 1 to 5, m ３３ is an integer of 0 to 5, n ３１ is an integer of 1 to 15. ] [In formula (2), *J ４１ Y ３１ This is the bonding position with R ４１ and R ４２ Each is independently a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, which may have substituents, and some of the carbon atoms 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 substituents; or an aromatic heterocyclic group having 3 to 50 carbon atoms, which may have substituents. ４１ and R ４２ They may be bonded together to form a ring, or R ４１ and R ４２ R ４１ and R ４２ These may also form a carbonyl group together with the carbon atom to which they are bonded, R ４３ and R ４４ Each of these is independently a cyano group, a C1-C10 alkyloxycarbonyl group which may have substituents, or a C1-C10 alkylsulfonyl group which may have substituents, X ４１ is O, S, or N-Q ４１ Q ４１ This refers to a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, which may have substituents, and in which some carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have substituents.

2. The composition according to claim 1, wherein the silicone-based surfactant is at least one selected from the group consisting of polyether-modified silicone-based surfactants and aralkyl-modified silicone-based surfactants.

3. The composition according to claim 1, wherein the silicone-based surfactant is an aralkyl-modified silicone-based surfactant.

4. The composition according to claim 1, comprising a nonlinear optically active polymer compound containing a monovalent group obtained by removing one hydrogen atom from the compound represented by formula (1).

5. The composition according to claim 4, wherein the silicone-based surfactant is at least one selected from the group consisting of polyether-modified silicone-based surfactants and aralkyl-modified silicone-based surfactants.

6. The composition according to claim 4, wherein the silicone-based surfactant is an aralkyl-modified silicone-based surfactant.

7. A nonlinear optical film formed from the composition according to any one of claims 1 to 6.

8. An optical modulator comprising the nonlinear optical film described in claim 7.

9. A method for forming a nonlinear optical film, comprising the steps of: applying a composition according to any one of claims 1 to 6 onto a substrate; drying the applied composition; and firing the dried composition at 100 to 200°C, in this order.

10. A nonlinear optical film comprising at least one selected from the group consisting of a compound represented by the following formula (1) and a nonlinear optically active polymer compound containing a monovalent or multivalent group obtained by removing at least one hydrogen atom from the compound represented by the following formula (1), and a silicone-based surfactant, wherein the silicon atom concentration measured by X-ray photoelectron spectroscopy (XPS) is 3 at% or less. [In formula (1), Ar ３１ Each of these is independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have substituents, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have substituents, and R ３１ and R ３３ Each is 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 substituents, in which some carbon atoms 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 substituents; or an aromatic heterocyclic group having 3 to 50 carbon atoms, which may have substituents. ３２ and R ３４ Each is independently a hydrogen atom, a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have substituents, a group which may have some carbon atoms substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have substituents, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom, Y ３１ Each is independently a divalent π-conjugated linkage group which may have substituents, and Z ３１ This is a group represented by the following formula (2), m ３１ m is an integer between 0 and 5. ３２ m is an integer between 1 and 5. ３３ n is an integer between 0 and 5. ３１ [This is an integer between 1 and 15.] [In formula (2), *J ４１ Y ３１ This is the bonding position with R ４１ and R ４２ Each is independently a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, which may have substituents, and some of the carbon atoms 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 substituents; or an aromatic heterocyclic group having 3 to 50 carbon atoms, which may have substituents. ４１ and R ４２ They may be bonded together to form a ring, or R ４１ and R ４２ R ４１ and R ４２ These may also form a carbonyl group together with the carbon atom to which they are bonded, R ４３ and R ４４ Each of these is independently a cyano group, a C1-C10 alkyloxycarbonyl group which may have substituents, or a C1-C10 alkylsulfonyl group which may have substituents, X ４１ is O, S, or N-Q ４１ Q ４１ This refers to a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, which may have substituents, and in which some carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have substituents.

11. The nonlinear optical film according to claim 10, wherein the silicone-based surfactant is at least one selected from the group consisting of polyether-modified silicone-based surfactants and aralkyl-modified silicone-based surfactants.

12. The nonlinear optical film according to claim 10, wherein the silicone-based surfactant is an aralkyl-modified silicone-based surfactant.

13. The nonlinear optical film according to claim 10, comprising a nonlinear optically active polymer compound containing a monovalent group obtained by removing one hydrogen atom from the compound represented by formula (1).

14. The nonlinear optical film according to claim 13, wherein the silicone-based surfactant is at least one selected from the group consisting of polyether-modified silicone-based surfactants and aralkyl-modified silicone-based surfactants.

15. The nonlinear optical film according to claim 13, wherein the silicone-based surfactant is an aralkyl-modified silicone-based surfactant.

16. An optical modulator comprising a nonlinear optical film according to any one of claims 10 to 15.

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