Composition, film, and display device

Abstract

The present invention provides a composition containing a quantum dot (A) and a vinyl copolymer (B); the vinyl copolymer (B) has a structural unit derived from a (meth) acrylic acid, a structural unit derived from a (meth) acrylic acid ester having a carboxyl group, and a structural unit derived from a (meth) acrylic acid ester having no carboxyl group, contains a tellurium compound, has a molecular weight distribution of 2.0 or less, and has an acid value of 100-150 mgKOH / g.

Description

Technical Field

[0001] The present invention relates to a composition, a film formed therefrom, and a display device comprising the film. Background Art

[0002] As a curable resin composition for forming a cured film such as a wavelength conversion film included in a display device, a composition containing quantum dots is known (Patent Document 1). Prior art literature Patent Literature

[0003] Patent Document 1: Japanese Patent Application Publication No. 2016-71362 Summary of the invention Problem that the invention aims to solve

[0004] One object of the present invention is to provide a quantum dot-containing composition capable of forming a film having good pattern forming properties and light emitting properties. Another object of the present invention is to provide a film formed from the composition and a display device including the film. Technical means of solving problems

[0005] The present invention provides the composition, film, and display device shown below. [1] A composition comprising quantum dots (A) and a vinyl copolymer (B); the vinyl copolymer (B) having structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate having a carboxyl group, and structural units derived from (meth)acrylate not having a carboxyl group, and containing a tellurium compound, having a molecular weight distribution of less than 2.0, and an acid value of 100 mgKOH / g to 150 mgKOH / g. [2] The composition according to [1], wherein the vinyl copolymer (B) has structural units derived from monomers represented by formula (I), formula (II) and formula (III); [Chemistry 1] [In formula (I), X1 represents a hydrogen atom or a methyl group.] [Chemistry 2] [In formula (II), X2 represents a hydrogen atom or a methyl group. Y1 represents a linear, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms. Y2 represents a linear, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms.] [Chemistry 3] [In formula (III), X3 represents a hydrogen atom or a methyl group. R1 represents a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms.] [3] The composition according to [1] or [2], wherein the vinyl copolymer (B) further contains a structural unit having an ultraviolet curable functional group. [4] The composition according to any one of [1] to [3], wherein the weight average molecular weight per mol of ethylenically unsaturated bonds in the vinyl copolymer (B), i.e., the ethylenically unsaturated bond equivalent, is more than 1,000 and not more than 8,000. [5] The composition according to any one of [1] to [4], wherein the content of the tellurium compound in the vinyl copolymer (B) is more than 0 ppm and less than 350 ppm in terms of metal tellurium. [6] The composition according to any one of [1] to [5], further comprising a polymerizable compound (C) and a polymerization initiator (D). [7] The composition according to any one of [1] to [6], further comprising a solvent (E). [8] According to the composition described in any one of [1] to [7], the quantum dot (A) is at least one selected from the group consisting of compounds of Group 12 elements and Group 16 elements, compounds of Group 13 elements and Group 15 elements, compounds of Group 13 elements and Group 16 elements, and compounds of Group 14 elements and Group 16 elements. [9] The composition according to any one of [1] to [8], wherein the content of the quantum dots (A) is 50 to 350 parts by mass based on 100 parts by mass of the vinyl copolymer (B).

[10] A film formed from the composition according to any one of [1] to [9].

[11] A display device comprising the film described in

[10] . Effects of the Invention

[0006] The present invention can provide a composition containing quantum dots capable of forming a film having good pattern forming properties and light emitting properties, a film formed from the composition, and a display device including the film. DETAILED DESCRIPTION

[0007] <Composition> The composition related to the present invention (hereinafter also referred to as "composition") contains quantum dots (A) and a specific vinyl copolymer (B) described later. The composition may further contain other components such as a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). The composition may also be a curable composition that is cured by light irradiation or heat.

[0008] According to the composition related to the present invention, a film with good pattern formation and luminescent properties can be formed. The composition is preferably capable of forming a film with a line and space pattern (line and space pattern) with a width of 20 μm. The composition is preferably capable of forming a film with good quantum yield QY and / or external quantum efficiency EQE, and more preferably capable of forming a film with good quantum yield QY and external quantum efficiency EQE. Further, according to the composition related to the present invention, a film with good pattern formation and luminescent properties and good appearance can be formed. Good appearance refers to a state in which there are no aggregates in the coating film or the aggregates are sufficiently reduced, specifically referring to no foreign matter is confirmed when the appearance is evaluated according to the method described in the embodiments described later.

[0009] In this specification, the following terms have the following meanings. “(Meth)acrylic acid” refers to at least one of acrylic acid and methacrylic acid. Similarly, “(meth)acryloyloxy” refers to at least one of acryloyloxy and methacryloyloxy, and “(meth)acryloyl” refers to at least one of acryloyl and methacryloyl. The "(meth)acrylate" refers to an ester compound in which the hydrogen atom of the carboxyl group of (meth)acrylic acid is substituted with a hydrocarbon group.

[0010] The "vinyl copolymer" refers to a copolymer of two or more vinyl monomers. The "vinyl monomer" refers to a monomer having a polymerizable vinyl group (ethylenically unsaturated double bond), and includes a monomer having a (meth)acryloyl group and a monomer having an allyl group.

[0011] “Blue” refers to all light that is visually perceived as blue (the wavelength range of blue, for example, all light having intensity between 380 nm and 495 nm), and is not limited to light of a single wavelength. “Green” refers to all light that is visually perceived as green (the wavelength range of green, for example, all light having intensity between 495 nm and 585 nm), and is not limited to light of a single wavelength. “Red” refers to all light that is visually perceived as red (the wavelength range of red, for example, all light having intensity between 585 nm and 780 nm), and is not limited to light of a single wavelength. “Yellow” refers to all light that is visually perceived as yellow (the wavelength range of yellow, for example, all light having intensity between 560 nm and 610 nm), and is not limited to light of a single wavelength.

[0012] The components contained or may be contained in the composition are described below. It should be noted that, in the present specification, the compounds exemplified as the components contained or may be contained in the composition may be used alone or in combination of two or more unless otherwise specified.

[0013] [1]Quantum dot(A) Quantum dots (A) are luminescent semiconductor particles with a particle size of 1 nm or more and 100 nm or less, which can utilize the band gap of the semiconductor to absorb ultraviolet light or visible light (e.g., blue light) and then emit light. Quantum dots (A) preferably emit green or red light, and more preferably absorb blue light and emit green or red light.

[0014] The luminescent spectrum of the quantum dot (A) emitting green light preferably includes a peak having a maximum value in a wavelength range of 500 nm to 560 nm, more preferably includes a peak having a maximum value in a wavelength range of 520 nm to 545 nm, and further preferably includes a peak having a maximum value in a wavelength range of 525 nm to 535 nm. This can further improve the green light-emitting characteristics of the display device. The half width (full width at half-maximum) of the peak is preferably 15 nm to 80 nm, more preferably 15 nm to 60 nm, further preferably 15 nm to 50 nm, and particularly preferably 15 nm to 45 nm. This can further improve the green light-emitting characteristics of the display device.

[0015] The luminescent spectrum of the quantum dots (A) emitting red light preferably includes a peak having a maximum value in a wavelength range of 610 nm to 750 nm, more preferably includes a peak having a maximum value in a wavelength range of 620 nm to 650 nm, and further preferably includes a peak having a maximum value in a wavelength range of 625 nm to 645 nm. This can further improve the red light-emitting characteristics of the display device. The half width of the peak is preferably 15 nm to 80 nm, more preferably 15 nm to 60 nm, further preferably 15 nm to 50 nm, and particularly preferably 15 nm to 45 nm. This can further improve the red light-emitting characteristics of the display device. The emission spectrum of the quantum dot (A) can be measured by the method described in the Examples section below.

[0016] As a quantum dot (A), for example, it can be composed of a semiconductor material containing one or more elements selected from the group consisting of Group 2 elements, Group 11 elements, Group 12 elements, Group 13 elements, Group 14 elements, Group 15 elements and Group 16 elements of the periodic table.

[0017] Specific examples of semiconductor materials that can constitute quantum dots include: Compounds of Group 14 elements and Group 16 elements such as SnS2, SnS, SnSe, SnTe, PbS, PbSe, PbTe; Compounds of Group 13 elements and Group 15 elements such as GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, InGaN, InGaP; Compounds of Group 13 elements and Group 16 elements such as Ga2O3, Ga2S3, Ga2Se3, Ga2Te3, In2O3, In2S3, In2Se3, In2Te3, AgInGaS; Compounds of Group 12 elements and Group 16 elements such as ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe, ZnSTe, ZnSeS, ZnSeTe, CdSTe, CdSeTe, HgSTe, HgSeS, HgSeTe; Compounds of Group 15 elements and Group 16 elements such as As2O3, As2S3, As2Se3, As2Te3, Sb2O3, Sb2S3, Sb2Se3, Sb2Te3, Bi2O3, Bi2S3, Bi2Se3, Bi2Te3; Compounds of Group 2 elements and Group 16 elements such as MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe; A single substance of a Group 14 element, a Group 15 element, or a Group 16 element such as Si or Ge.

[0018] Among them, from the perspective of tending to improve the luminescence characteristics, the quantum dots (A) are preferably at least one selected from the group consisting of compounds of Group 12 elements and Group 16 elements, compounds of Group 13 elements and Group 15 elements, compounds of Group 13 elements and Group 16 elements, and compounds of Group 14 elements and Group 16 elements.

[0019] When the quantum dots (A) contain S or Se, the surface of the quantum dots modified with metal oxides or organic substances can be used. By using the surface-modified quantum dots, the precipitation of S or Se caused by the reactive components contained or may be contained in the composition can be prevented. Furthermore, the quantum dots (A) may also be combined with the above compounds to form a core-shell structure. Examples of such a combination include fine particles having a CdSe core and a ZnS shell, and fine particles having an InP core and a ZnSeS shell.

[0020] Since the energy state of quantum dots (A) depends on their size, the emission wavelength can be freely selected by changing the particle size. In addition, since the spectrum width of the light emitted by quantum dots (A) is narrow, it is beneficial to the wide color gamut of the display device. Furthermore, since the responsiveness of quantum dots (A) is high, it is also beneficial in terms of the utilization efficiency of primary light.

[0021] The composition may also contain two or more quantum dots (A). For example, the composition may contain only one quantum dot (A) that absorbs light once and emits green light, or a combination of two or more quantum dots (A). The composition may contain only one quantum dot (A) that absorbs light once and emits red light, or a combination of two or more quantum dots (A).

[0022] The content of quantum dots (A) in the composition, relative to the total amount of solid components of the composition, is, for example, 1% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, for example, 60% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less.

[0023] The total amount of solid content of the composition refers to the total amount of components other than the solvent (E) among the components contained in the composition. The content of the solid content of the composition can be measured by a known analytical method such as liquid chromatography or gas chromatography. The content of each component in the solid content of the composition can be calculated based on the mixing when the composition is prepared.

[0024] The content of quantum dots (A) in the composition, relative to 100 parts by mass of the vinyl copolymer (B), is, for example, 50 parts by mass or more, preferably 55 parts by mass or more, more preferably 60 parts by mass or more, and further preferably 70 parts by mass or more, and is, for example, 350 parts by mass or less, preferably 250 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 150 parts by mass or less.

[0025] When the composition contains two or more quantum dots (A), the content or content of the quantum dots (A) refers to the total content or content of the two or more quantum dots (A). The same applies to components other than the quantum dots (A) that the composition contains or may contain.

[0026] [2] Organic ligand (G) The composition may further contain an organic ligand (G), and the quantum dot (A) may also be present in the composition in a state of being coordinated with the organic ligand (G). The organic ligand (G) is, for example, an organic compound having a polar group that exhibits coordination ability to the quantum dot (A). The organic ligand (G) may, for example, be coordinated on the surface of the quantum dot (A). The composition may also contain one or more organic ligands (G).

[0027] In the composition, it is preferred that at least a portion of the organic ligand (G) molecules are coordinated with the quantum dots (A), or all or substantially all of the molecules are coordinated with the quantum dots (A). From the viewpoint of improving the stability and dispersibility of the quantum dots (A) and the luminescent properties of the film, it is advantageous to contain an organic ligand (G) coordinated with the quantum dots (A).

[0028] The above-mentioned polar group of the organic ligand (G) is, for example, at least one group selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH) and an amino group (-NH2). The polar group selected from this group is advantageous in improving the coordination to the quantum dots (A). High coordination can help improve the stability and dispersibility of the quantum dots (A) in the composition and improve the luminescent properties of the film. Among them, the polar group is more preferably at least one group selected from the group consisting of a thiol group and a carboxyl group. The organic ligand (G) may have one or more polar groups.

[0029] The organic ligand (G) may be, for example, an organic compound represented by the following formula. X A -R X (x) Where, X A is the polar group mentioned above, R X It is a monovalent hydrocarbon group that may contain heteroatoms (N, O, S, halogen atoms, etc.). The hydrocarbon group may also have one or more unsaturated bonds such as carbon-carbon double bonds. The hydrocarbon group may also have a straight chain, branched chain or cyclic structure. The number of carbon atoms in the hydrocarbon group is, for example, greater than 1 and less than 40, or may be greater than 1 and less than 30. The methylene group contained in the hydrocarbon group may also be replaced by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc.

[0030] Group R X It may also contain a polar group. As a specific example of the polar group, the polar group X A The relevant records above.

[0031] As having carboxyl group as polar group X ASpecific examples of the organic ligand include, in addition to formic acid, acetic acid, and propionic acid, saturated or unsaturated fatty acids. Specific examples of saturated or unsaturated fatty acids include saturated fatty acids such as butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid, behenic acid, and tetradecanoic acid; monovalent unsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, eicosenoic acid, erucic acid, and nervonic acid; polyvalent unsaturated fatty acids such as linoleic acid, α-linolenic acid, γ-linolenic acid, stearatetraenoic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosatetraenoic acid, docosadienoic acid, and adrenic acid (docosatetraenoic acid).

[0032] Having a thiol group or an amino group as the polar group X A Specific examples of the organic ligand include the above-mentioned organic ligand having a carboxyl group as a polar group X A The carboxyl group of the organic ligand is replaced by a thiol group or an amino group of the organic ligand.

[0033] In addition to the above, examples of the organic ligand represented by the above formula (x) include compounds (G-1) and compounds (G-2).

[0034] [Compound (G-1)] Compound (G-1) is a compound having a first functional group and a second functional group. The first functional group is a carboxyl group (-COOH), and the second functional group is a carboxyl group or a thiol group (-SH). Since compound (G-1) has a carboxyl group and / or a thiol group, it can become a ligand coordinated with quantum dots (A). The composition may contain only one compound (G-1) or may contain two or more.

[0035] One example of compound (G-1) is a compound represented by the following formula (G-1a). Compound (G-1) may be an acid anhydride of the compound represented by formula (G-1a).

[0036] [Chemistry 4] [Where R B represents a divalent hydrocarbon group. B When there are multiple substituents, these may be the same or different. The above hydrocarbon group may have more than one substituent. When there are multiple substituents, these may be the same or different, and these may also be combined with each other to form a ring together with the atoms to which they are combined. The -CH2- contained in the above hydrocarbon group may also be replaced by at least one of -O-, -S-, -SO2-, -CO- and -NH-. P represents an integer greater than or equal to 1 and less than or equal to 10.]

[0037] As R BExamples of the divalent hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

[0038] Examples of the chain hydrocarbon group include a linear or branched alkanediyl group, which usually has a carbon number of 1 or more and 50 or less, preferably 1 or more and 20 or less, and more preferably 1 or more and 10 or less. Examples of the alicyclic hydrocarbon group include a monocyclic or polycyclic cycloalkanediyl group, which usually has a carbon number of 3 or more and 50 or less, preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less. Examples of the aromatic hydrocarbon group include a monocyclic or polycyclic arenediyl group, which usually has a carbon number of 6 or more and 20 or less.

[0039] Examples of the substituent that the hydrocarbon group may have include an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 3 to 50 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carboxyl group, an amino group, a halogen atom, etc. The substituent that the hydrocarbon group may have is preferably a carboxyl group, an amino group or a halogen atom.

[0040] When -CH2- contained in the above hydrocarbon group is replaced by at least one of -O-, -CO- and -NH-, at least one of -CO- and -NH- is preferably replaced by -CH2-, more preferably -NH-. p is preferably 1 or 2.

[0041] Examples of the compound represented by formula (G-1a) include compounds represented by the following formulae (1-1) to (1-9).

[0042] [Chemistry 5]

[0043] Specific examples of the compound represented by the chemical formula (G-1a) include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, 4-mercaptobutyric acid, mercaptosuccinic acid, mercaptostearic acid, mercaptooctanoic acid, 4-mercaptobenzoic acid, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid, L-cysteine, N-acetyl-L-cysteine, 3-methoxybutyl 3-mercaptopropionate, 3-mercapto-2-methylpropionic acid, etc. Among them, 3-mercaptopropionic acid and mercaptosuccinic acid are preferred.

[0044] Another example of compound (G-1) is a polycarboxylic acid compound, and preferably a compound (G-1b) represented by formula (G-1a) in which -SH in formula (G-1a) is replaced by a carboxyl group (-COOH).

[0045] Examples of the compound (G-1b) include the following compounds. Succinic acid, glutaric acid, adipic acid, octafluoroadipic acid, azelaic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, dodecanedioic acid, 3-ethyl-3-methylglutaric acid, hexafluoroglutaric acid, trans-3-hexenedioic acid, sebacic acid, hexadecanoic acid, butynedioic acid, trans-aconitic acid, 1,3-adamantanedicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, 1,1-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, cis- or trans-1,3-cyclohexanedicarboxylic acid, cis- or trans-1,4 -cyclohexanedicarboxylic acid, 1,1-cyclopentanediacetic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, decahydro-1,4-naphthalene dicarboxylic acid, 2,3-norbornene dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, phthalic acid, 3-fluorophthalic acid, isophthalic acid, tetrafluoroisophthalic acid, terephthalic acid, tetrafluoroterephthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,1'-ferrocene dicarboxylic acid, 2,2'-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 2,5-furan dicarboxylic acid, benzophenone-2,4'-dicarboxylic acid hydrate, benzophenone-4,4'-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, pyrazole-3,5-dicarboxylic acid monohydrate, 4,4'-stilbene dicarboxylic acid, anthraquinone-2,3-dicarboxylic acid, 4-(carboxymethyl)benzoic acid, chelidonic acid monohydrate, azobenzene-4,4'-dicarboxylic acid, azobenzene-3,3'-dicarboxylic acid, chlorendic acid, 1H-imidazole-4,5-dicarboxylic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 1,1 0-bis(4-carboxyphenoxy)decane, dipropylmalonic acid, dithiodiglycolic acid, 3,3'-dithiodipropionic acid, 4,4'-dithiodibutyric acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfone, ethylene glycol bis(4-carboxyphenyl) ether, 3,4-ethylenedioxythiophene-2,5-dicarboxylic acid, 4,4'-isopropyldiphenoxyacetic acid, 1,3-acetonedicarboxylic acid, methylenedisalicylic acid, 5,5'-thiodisalicylic acid, tris(2-carboxyethyl)isocyanurate, tetrafluorosuccinic acid, α,α,α',α'-tetramethyl-1,3-benzenedipropionic acid, 1,3,5-benzenetricarboxylic acid, etc.

[0046] From the viewpoint of improving the stability and dispersibility of quantum dots (A) and the luminescent properties of the film, the molecular weight of compound (G-1) is preferably 3000 or less, more preferably 2500 or less, further preferably 2000 or less, among which, further preferably 1000 or less, particularly preferably 800 or less, and most preferably 500 or less. The molecular weight of compound (G-1) is usually 100 or more.

[0047] The molecular weight may be a number average molecular weight or a weight average molecular weight. In this case, the number average molecular weight and the weight average molecular weight are respectively the number average molecular weight and the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

[0048] When the composition contains compound (G-1), the content ratio of compound (G-1) in the composition to quantum dots (A) is preferably 0.001 or more, more preferably 0.01 or more, further preferably 0.02 or more, preferably 1 or less, more preferably 0.5 or less, further preferably 0.45 or less, in terms of mass ratio. From the viewpoint of improving the stability and dispersibility of quantum dots (A) and the luminescent properties of the film, it is advantageous when the content ratio is within this range.

[0049] When the composition contains compound (G-1), from the viewpoint of improving the stability and dispersibility of quantum dots (A) and the luminescent properties of the film, the content of compound (G-1) in the composition relative to the total solid content of the composition is preferably 0.1 mass % or more, more preferably 0.2 mass % or more, further preferably 0.5 mass % or more, preferably 20 mass % or less, more preferably 10 mass % or less, further preferably 8 mass % or less.

[0050] [Compound (G-2)] Compound (G-2) is a compound different from compound (G-1), which contains a polyalkylene glycol structure and has a polar group at the molecular end. The molecular end is preferably the end of the longest carbon chain (the carbon atoms in the carbon chain may also be replaced by other atoms such as oxygen atoms) in compound (G-2).

[0051] The composition may contain only one compound (G-2) or two or more. The composition may contain compound (G-1) or compound (G-2), or may contain compound (G-1) and compound (G-2). It should be noted that the compound containing a polyalkylene glycol structure and having the above-mentioned first functional group and second functional group belongs to compound (G-1).

[0052] The polyalkylene glycol structure refers to a structure represented by the following formula (n is an integer greater than or equal to 2):

[0053] [Chemistry 6] In the formula, R C The alkylene group includes, for example, an ethylene group and a propylene group.

[0054] Specific examples of the compound (G-2) include polyalkylene glycol compounds represented by the following formula (G-2a).

[0055] [Chemistry 7]

[0056] In formula (G-2a), X is a polar group, Y is a monovalent group, and Z is C is a divalent or trivalent group. n is an integer greater than 2. m is 1 or 2. C It is an alkylene group.

[0057] The polar group X is preferably at least one group selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH) and an amino group (-NH2). The polar group selected from this group is advantageous in terms of improving the coordination to the quantum dot (A). Among them, from the viewpoint of improving the stability and dispersibility of the quantum dot (A) and the luminescent properties of the film, the polar group X is more preferably at least one group selected from the group consisting of a thiol group and a carboxyl group.

[0058] The group Y is a monovalent group. There is no particular limitation on the group Y, and examples thereof include monovalent hydrocarbon groups which may have substituents (N, O, S, halogen atoms, etc.). -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc. The number of carbon atoms in the above hydrocarbon group is, for example, not less than 1 and not more than 12. The hydrocarbon group may contain an unsaturated bond.

[0059] As group Y, there can be mentioned: an alkyl group having a carbon number of 1 or more and 12 or less in a straight chain, branched chain or cyclic structure; an alkoxy group having a carbon number of 1 or more and 12 or less in a straight chain, branched chain or cyclic structure. The carbon number of the alkyl group and the alkoxy group is preferably 1 or more and 8 or less, more preferably 1 or more and 6 or less, and further preferably 1 or more and 4 or less. -CH2- contained in the alkyl group and the alkoxy group can be replaced by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc. Among them, group Y is preferably a straight chain or branched chain alkoxy group having a carbon number of 1 or more and 4 or less, and more preferably a straight chain alkoxy group having a carbon number of 1 or more and 4 or less.

[0060] The group Y may contain a polar group. As the polar group, at least one group selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH) and an amino group (-NH2) may be cited. However, as described above, a compound containing a polyalkylene glycol structure and having the first functional group and the second functional group belongs to compound (G-1). The polar group is preferably disposed at the end of the group Y.

[0061] Group Z C is a divalent or trivalent group. C There are no particular limitations, and examples include divalent or trivalent hydrocarbon groups which may contain heteroatoms (N, O, S, halogen atoms, etc.). The number of carbon atoms in the hydrocarbon group is, for example, 1 to 24. The hydrocarbon group may also have an unsaturated bond.

[0062] The group Z as a divalent group C , examples include: an alkylene group having a linear, branched or cyclic structure with a carbon number of 1 or more and 24 or less; an alkenylene group having a linear, branched or cyclic structure with a carbon number of 1 or more and 24 or less. The number of carbon atoms in the alkyl and alkenylene groups is preferably 1 or more and 12 or less, more preferably 1 or more and 8 or less, and further preferably 1 or more and 4 or less. The -CH2- contained in the alkyl and alkenylene groups can be replaced by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc. The group Z as a trivalent group C Examples of the group Z include the group Z which is the above-mentioned divalent group. C A group after removing one hydrogen atom.

[0063] Group Z C It may have a branched structure. Group Z having a branched structure C , a branch chain different from a branch chain containing a polyalkylene glycol structure represented by the above formula (G-2a) may have a polyalkylene glycol structure different from the polyalkylene glycol structure represented by the above formula (G-2a).

[0064] Among them, group Z C The linear or branched alkylene group having 1 to 6 carbon atoms is preferred, and the linear alkylene group having 1 to 4 carbon atoms is more preferred.

[0065] R C The alkylene group is preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 1 to 4 carbon atoms.

[0066] n in formula (G-2a) is an integer of 2 or more, preferably 2 or more and 540 or less, more preferably 2 or more and 120 or less, and further preferably 2 or more and 60 or less.

[0067] The molecular weight of compound (G-2) can be, for example, more than 150 and less than 10000. From the viewpoint of improving the stability and dispersibility of quantum dots (A) and the luminescent properties of the film, it is preferably more than 150 and less than 5000, more preferably more than 150 and less than 4000. The molecular weight can be a number average molecular weight or a weight average molecular weight. At this time, the number average molecular weight and the weight average molecular weight are respectively the number average molecular weight and the weight average molecular weight converted by standard polystyrene measured by GPC.

[0068] When the composition contains compound (G-2), the content ratio of compound (G-2) in the composition to quantum dots (A) is preferably 0.001 or more, more preferably 0.01 or more, further preferably 0.1 or more, preferably 2 or less, more preferably 1.5 or less, further preferably 1 or less. From the viewpoint of improving the stability and dispersibility of quantum dots (A) and the luminescent properties of the film, it is advantageous when the content ratio is within this range.

[0069] When the composition contains compound (G-2), from the viewpoint of improving the stability and dispersibility of quantum dots (A) and the luminescent properties of the film, the content of compound (G-2) in the composition relative to the total solid content of the composition is preferably 0.1 mass % or more, more preferably 1 mass % or more, further preferably 2 mass % or more, preferably 40 mass % or less, more preferably 20 mass % or less, further preferably 15 mass % or less, and further preferably 12 mass % or less.

[0070] When the composition contains an organic ligand (G), the content ratio of the organic ligand (G) to the quantum dots (A) in the composition is preferably 0.001 or more, more preferably 0.01 or more, and further preferably 0.02 or more, and preferably 1 or less, more preferably 0.8 or less, and further preferably 0.5 or less, in terms of mass ratio. From the perspective of improving the stability and dispersibility of the quantum dots (A) and the luminescent properties of the film, it is advantageous for the content ratio to be within this range. The content of the organic ligand (G) referred to herein is the total content of all organic ligands contained in the composition.

[0071] From the viewpoint of improving the stability and dispersibility of quantum dots (A) and the luminescent properties of the film, the total content of quantum dots (A) and organic ligands (G) in the composition is preferably 10% by mass or more, more preferably 12% by mass or more, further preferably 15% by mass or more, and also preferably 75% by mass or less, more preferably 70% by mass or less, and further preferably 65% ​​by mass or less, relative to the total amount of solid components in the composition.

[0072] [3] Vinyl copolymer (B) The vinyl copolymer (B) has a structural unit (B-1) derived from (meth)acrylic acid (hereinafter also referred to as "monomer (b-1)"), a structural unit (B-2) derived from a (meth)acrylate having a carboxyl group (hereinafter also referred to as "monomer (b-2)"), and a structural unit (B-3) derived from a (meth)acrylate not having a carboxyl group (hereinafter also referred to as "monomer (b-3)"). The composition may contain two or more vinyl copolymers (B).

[0073] Furthermore, the vinyl copolymer (B) satisfies the following conditions. -Contains tellurium compounds. - The molecular weight distribution is 2.0 or less. - Acid value is 100 mgKOH / g or more and 150 mgKOH / g or less.

[0074] According to the composition containing the above-mentioned vinyl copolymer (B), a film with good pattern formation and luminescent properties can be formed. As one reason for the good pattern formation, the molecular weight distribution of the vinyl copolymer (B) can be cited as narrow. It can be considered that due to the narrow molecular weight distribution, even if the pattern shape is fine, the boundary between the pattern area and the space area can be made clear during development. The narrow molecular weight distribution is advantageous in improving the solvent resistance and heat resistance of the film formed by the composition and the workability (stability over time) of the composition. In addition, another reason for being able to form a film with good luminescent properties is that the vinyl copolymer (B) contains a tellurium compound.

[0075] According to the composition containing the above-mentioned vinyl copolymer (B), the dispersibility of the quantum dots (A) in the composition and the film formed therefrom can be improved, thereby the luminescence characteristics of the film can be improved. In addition, since the dispersibility of the quantum dots (A) can be improved, the content of the quantum dots (A) in the composition and the film formed therefrom can also be improved (high concentration of the quantum dots (A)). This means that even if the thickness of the film is reduced, the luminescence characteristics of the same or higher level can be exerted. As reasons for improving the dispersibility of the quantum dots (A), it can be cited that the acid value of the vinyl copolymer (B) is within the above-mentioned range, the molecular weight distribution of the vinyl copolymer (B) is narrow, and the vinyl copolymer (B) has a specific structure including the type of monomers constituting it.

[0076] Furthermore, according to the composition containing the vinyl copolymer (B), since the dispersibility of the quantum dots (A) can be improved, a film having less or no aggregates and excellent appearance can be formed.

[0077] The monomer (b-1) which is one of the monomers forming the vinyl copolymer (B) is (meth)acrylic acid, as represented by the following formula (I): In the formula (I), X1 represents a hydrogen atom or a methyl group.

[0078] [Chemistry 8]

[0079] The monomer (b-2) which is another monomer forming the vinyl copolymer (B) is a (meth)acrylate having a carboxyl group, and examples thereof include monomers represented by the following formula (II).

[0080] [Chemistry 9]

[0081] In formula (II), X2 represents a hydrogen atom or a methyl group. Y1 represents a straight-chain, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms. Y2 represents a straight-chain, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms. At least one -CH2- in these hydrocarbon groups may be replaced by -C(=O)-, -O-, -S-, -NH-, etc.

[0082] The number of carbon atoms of the hydrocarbon group represented by Y1 is preferably 1 to 4, more preferably 1 to 3. Examples of the hydrocarbon group represented by Y1 and the hydrocarbon group represented by Y2 each independently include an alkylene group, a divalent aromatic group, and a divalent alicyclic group.

[0083] Specific examples of the monomer represented by formula (II) include 2-methacryloyloxyethyl succinate, 2-acryloyloxyethyl succinate, mono-2-(methacryloyloxy)ethyl phthalate, mono-2-(acryloyloxy)ethyl phthalate, 2-(methacryloyloxy)ethyl hexahydrophthalate, and 2-(acryloyloxy)ethyl hexahydrophthalate.

[0084] The monomer (b-3) which is another monomer forming the vinyl copolymer (B) is a (meth)acrylate having no carboxyl group, and examples thereof include monomers represented by the following formula (III).

[0085] [Chemistry 10]

[0086] In formula (III), X3 represents a hydrogen atom or a methyl group. R1 represents a straight-chain, branched or cyclic hydrocarbon group having a carbon number of 1 to 30. At least one -CH2- in the hydrocarbon group can be replaced by -C(=O)-, -O-, -S-, -NH-, etc. The number of carbon atoms in the hydrocarbon group represented by R1 is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. As the hydrocarbon group represented by R1, each independently includes, for example, an alkyl group, a monovalent aromatic group, and a monovalent alicyclic group.

[0087] Specific examples of the monomer (b-3) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate, 2,6 ] dec-8-yl ester (in the technical field, it is commonly known as "dicyclopentyl (meth)acrylate". In addition, it is sometimes referred to as "tricyclodecyl (meth)acrylate".), tricyclo[5.2.1.0 2,6 ] (Meth)acrylates such as decen-8-yl ester (in the technical field, it is commonly known as "dicyclopentenyl (meth)acrylate".), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propynyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate; (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, etc.

[0088] From the viewpoint of improving the pattern formability and light-emitting properties of the film, the vinyl copolymer (B) preferably has a structural unit derived from a monomer represented by formula (I), formula (II) or formula (III).

[0089] The content of the structural unit (B-1) derived from the monomer (b-1) in the vinyl copolymer (B) is preferably 2 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and is also preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less, in 100 mol% of the total structural units. The content of the structural unit (B-2) derived from the monomer (b-2) is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 5 mol% or more, and also preferably 50 mol% or less, more preferably 40 mol% or less, and further preferably 30 mol% or less in 100 mol% of the total structural units. The content of the structural unit (B-3) derived from the monomer (b-3) is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, and preferably 97 mol% or less, more preferably 90 mol% or less, and further preferably 85 mol% or less in 100 mol% of the total structural units.

[0090] Vinyl copolymer (B) can also further contain the structural unit (B-4) with ultraviolet curable functional group.By further containing structural unit (B-4), the solvent resistance and heat resistance etc. of film can be further improved.As ultraviolet curable functional group, ethylenic unsaturated bond can be enumerated, preferably ethylenic unsaturated double bond.As ultraviolet curable functional group, preferably ethylenic unsaturated bonds such as (meth) acryloyl, vinyl, allyl.Structural unit (B-4) preferably has ultraviolet curable functional group on side chain.

[0091] For the vinyl copolymer (B) containing the structural unit (B-4), the carboxyl group of the structural unit (B-1) and / or (B-2) of the vinyl polymer containing the structural unit (B-1) to (B-3) can be reacted with a compound (b-4) having both an epoxy group and an ultraviolet curable functional group in the molecule, usually at about 80°C or more and 130°C or less, and at least a part of the structural unit (B-1) and / or (B-2) can be converted into a structural unit (B-4) and manufactured. According to this method, a structural unit (B-4) having an ultraviolet curable functional group introduced into the side chain can be formed by the reaction of the carboxyl group and the epoxy group.

[0092] Examples of the compound (b-4) having both an epoxy group and an ultraviolet curable functional group in the molecule include glycidyl (meth)acrylate, 4-glycidyloxybutyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. Examples of the reaction catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as benzyltriethylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine. Examples of the polymerization inhibitor include oxygen, p-hydroxyanisole, hydroquinone, trimethylhydroquinone, N-nitrosophenylhydroxylamine, 2,2,6,6-tetramethylpiperidin-1-oxyl radical, and derivatives of 2,2,6,6-tetramethylpiperidin-1-oxyl radical.

[0093] The weight average molecular weight per 1 mol of ethylenically unsaturated bonds of the vinyl copolymer (B), i.e., the ethylenically unsaturated bond equivalent, is preferably more than 1000, more preferably 2000 or more, further preferably 3000 or more, further preferably 8000 or less, more preferably 6000 or less, further preferably 4000 or less. When the ethylenically unsaturated bond equivalent is within the above range, it is advantageous in further improving the solvent resistance and heat resistance of the film. The ethylenically unsaturated bond equivalent of the vinyl copolymer (B) can be measured by the method described in the column of Examples described later.

[0094] The vinyl copolymer (B) may contain structural units other than structural units (B-1) to (B-4). In particular, from the viewpoint of improving the pattern forming properties and light-emitting properties of the film, the total content of structural units (B-1) to (B-4) in 100 mol% of the total structural units is preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and particularly preferably 100 mol%.

[0095] The vinyl copolymer (B) contains a tellurium compound. The tellurium compound is usually a compound derived from a chain transfer agent described later used in the manufacture of the vinyl copolymer (B). Converted to metal tellurium, the content of the tellurium compound in the vinyl copolymer (B) is usually more than 0 ppm, preferably more than 10 ppm, more preferably more than 20 ppm, usually less than 350 ppm, preferably less than 200 ppm, more preferably less than 100 ppm. The ppm described here is a mass reference. When the content of the tellurium compound is within the above range, it is advantageous in terms of obtaining a film with good pattern formation and luminescent properties, and is particularly advantageous in terms of obtaining a film with good luminescent properties. The content of the tellurium compound in the vinyl copolymer (B) can be measured according to the method described in the column of the examples described later.

[0096] The molecular weight distribution of vinyl copolymer (B) is less than 2.0, preferably less than 1.9, more preferably less than 1.8, further preferably less than 1.7, further preferably less than 1.6, particularly preferably less than 1.55. For the molecular weight distribution, the smaller the value, the narrower the molecular weight distribution, and the copolymer with the same molecular weight is formed, and the width of the molecular weight distribution is the narrowest when the value is 1.0. That is, the lower limit of the molecular weight distribution is 1.0. When the molecular weight distribution is within the above range, it is advantageous in terms of obtaining a film with good pattern formation and luminescent properties, and further in terms of promoting the dispersibility of quantum dots (A), the solvent resistance and heat resistance of the film, and the shelf life (stability over time) of the composition. The vinyl copolymer (B) with a molecular weight distribution within the above range can be appropriately manufactured, for example, according to the method described later.

[0097] When the weight average molecular weight of the vinyl copolymer (B) is Mw and the number average molecular weight is Mn, the molecular weight distribution is expressed as Mw / Mn. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the vinyl copolymer (B) can be measured by the method described in the Examples section below.

[0098] The weight average molecular weight (Mw) of the vinyl copolymer (B) is, for example, 3000 or more and 20000 or less, and is preferably 4500 or more, more preferably 6000 or more, and is further preferably 14000 or less, and more preferably 9500 or less, from the viewpoint of improving the pattern forming property and light emitting property of the film. The Mw of the vinyl copolymer (B) can be adjusted by appropriately combining reaction conditions such as the selection of the raw materials used, the charging method, and the reaction temperature and time.

[0099] The acid value of the vinyl copolymer (B) may be 100 mgKOH / g or more and 150 mgKOH / g or less, preferably 105 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 130 mgKOH / g or more, further preferably 145 mgKOH / g or less, more preferably 140 mgKOH / g or less. When the acid value is within the above range, it is advantageous in obtaining a film having good pattern forming properties and light emitting properties, and is particularly advantageous in obtaining a film having good pattern forming properties.

[0100] The acid value of the vinyl copolymer (B) is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the vinyl copolymer (B), and can be measured by the method described in the column of Examples described later. The acid value of the vinyl copolymer (B) can be controlled, for example, by adjusting the content of the structural unit (B-1) and / or the structural unit (B-2) in the vinyl copolymer (B).

[0101] The vinyl copolymer (B) may be a random copolymer or a block copolymer. From the viewpoint of obtaining a film having good pattern formation and luminescent properties, and further from the viewpoint of improving the dispersibility of the quantum dots (A), the solvent resistance and heat resistance of the film, and the shelf life (stability over time) of the composition, the vinyl copolymer (B) is preferably a block copolymer.

[0102] As block copolymer, block copolymer with A block and B block etc. can be enumerated.When containing two or more structural units in block, it can be contained in the block in any state of random copolymerization and block copolymerization.In one embodiment, vinyl copolymer (B) is preferably a block copolymer not containing other blocks except A block and B block.By configuring structural unit (B-1) and structural unit (B-2) in different blocks, it is inclined to be able to further enhance the pattern formation and luminescent properties of film, further can further enhance the dispersibility of quantum dot (A), the solvent resistance and heat resistance of film and the shelf life (stability over time) of composition.

[0103] As a block copolymer preferred from the above viewpoint, there can be mentioned: a block copolymer in which the A block has the structural unit (B-1) but does not have the structural unit (B-2), and the B block has the structural unit (B-2) but does not have the structural unit (B-1). The structural unit (B-3) is preferably contained in both the A block and the B block. In addition, the A block and / or the B block may contain the structural unit (B-4).

[0104] In the vinyl copolymer (B) having an A block containing structural units (B-1) and (B-3) and a B block containing structural units (B-2) and (B-3), the content of the structural unit (B-1) in the A block (when the A block further contains the structural unit (B-4), it is the total content with the content of the structural unit) is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, further preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less in 100 mol% of the total structural units in the A block. The content of the structural unit (B-2) in the B block (when the B block further contains the structural unit (B-4), it is the total content with the content of the structural unit) is preferably 10 mol% or more, more preferably 15 mol% or more, further preferably 80 mol% or less, more preferably 75 mol% or less, and even more preferably 70 mol% or less in 100 mol% of the total structural units in the B block.

[0105] The proportion of the total structural units of the A block in the total structural units of the vinyl copolymer (B) is, for example, 30 mol% or more, preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 60 mol% or more, and for example, 90 mol% or less, preferably 85 mol% or less, more preferably 80 mol% or less.

[0106] The vinyl copolymer (B) can be produced, for example, by free radical polymerization. Among them, from the perspective of better precise control of molecular weight distribution and easy production of polymers with uniform composition, living radical polymerization is preferred, and living radical polymerization using an organic tellurium compound as a chain transfer agent is more preferred. The living radical polymerization method is, for example, the method described in International Publication No. 2004 / 14848, International Publication No. 2004 / 14962, International Publication No. 2004 / 072126, and International Publication No. 2004 / 096870.

[0107] Examples of the living radical polymerization method using an organic tellurium compound include the following methods (a) to (d). (a) A monomer is polymerized using an organic tellurium compound represented by the formula (T1). (b) The monomers are polymerized using a mixture of the organic tellurium compound represented by the formula (T1) and an azo polymerization initiator. (c) A monomer is polymerized using a mixture of an organic tellurium compound represented by the formula (T1) and an organic ditellurium compound represented by the formula (T2). (d) The monomer is polymerized using a mixture of an organic tellurium compound represented by the formula (T1), an azo polymerization initiator, and an organic ditellurium compound represented by the formula (T2). Z A -Te-CZ B Z C Z D (T1) Z A -Te-Te-Z A (T2)

[0108] In formula (T1) and formula (T2), Z A represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms. B and Z C Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. D It represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propynyl group.

[0109] Examples of the organic tellurium compound represented by formula (T1) include ethyl 2-methyl-2-n-butyltelluryl propionate, ethyl 2-n-butyltelluryl propionate, (2-hydroxyethyl)-2-methyl-methyltelluryl propionate, and the like, which are described in International Publication No. 2004 / 14848, International Publication No. 2004 / 14962, International Publication No. 2004 / 072126, and International Publication No. 2004 / 096870.

[0110] Examples of the organic ditellurium compound represented by the formula (T2) include dimethyl ditellurium and dibutyl ditellurium. The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator generally used in free radical polymerization, and examples thereof include 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis(1-cyclohexanecarbonitrile) (ACHN), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70).

[0111] The polymerization reaction of living radical polymerization can be carried out by mixing the monomer with the organic tellurium compound of formula (T1) and the azo polymerization initiator and / or the organic ditellurium compound of formula (T2) which are further added for the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution, etc. according to the type of monomer in a container replaced with an inert gas, and heating as needed. Examples of the inert gas include nitrogen, argon, helium, etc., preferably argon and nitrogen. The amount of the monomer used in the above methods (a), (b), (c) and (d) can be appropriately adjusted according to the physical properties of the target vinyl copolymer (B).

[0112] The polymerization reaction of living free radical polymerization can be carried out even without a solvent, but a non-protic solvent or a protic solvent commonly used in free radical polymerization can also be used, and the above mixture is stirred and carried out. As a non-protic solvent, for example: anisole, benzene, toluene, propylene glycol monomethyl ether acetate, ethyl acetate, tetrahydrofuran (THF), etc. can be mentioned. In addition, as a protic solvent, for example: water, methanol, 1-methoxy-2-propanol, etc. can be mentioned. The solvent can be used alone or in combination of two or more. The amount of solvent used can be appropriately adjusted, for example, preferably the solvent is 0.01 mL or more and 50 mL or less relative to 1g of monomer. The reaction temperature and reaction time can be appropriately adjusted according to the molecular weight or molecular weight distribution of the obtained vinyl copolymer (B), usually stirring at above 0°C and below 150°C for more than 1 minute and less than 100 hours.

[0113] After completion of the polymerization reaction, the used solvent, residual monomers and the like can be removed by conventional separation and purification means to isolate the target vinyl copolymer (B) from the obtained reaction mixture. The growing end of the vinyl copolymer (B) obtained by the polymerization reaction is -TeZ A (Where Z A The tellurium atom can be removed from the growth end by separation and purification means after the polymerization reaction is completed. Even after the tellurium atom is removed, tellurium compounds derived from the chain transfer agent usually remain in the vinyl copolymer (B).

[0114] The vinyl copolymer (B) having the above-mentioned structural unit (B-4) can be obtained by manufacturing a vinyl polymer containing structural units (B-1) to (B-3), and then carrying out a reaction using a compound (b-4) having both an epoxy group and an ultraviolet curable functional group in the above-mentioned molecule.

[0115] Relative to the total amount of the solid content of the composition, the content of the vinyl copolymer (B) in the composition is, for example, more than 5% by mass, preferably more than 10% by mass, more preferably more than 15% by mass, more preferably more than 20% by mass, and also for example, less than 80% by mass, preferably less than 70% by mass, more preferably less than 60% by mass, more preferably less than 55% by mass. When the content of vinyl copolymer (B) is in the above range, it tends to be easy to promote the dispersibility of quantum dots (A), the solvent resistance and heat resistance of film, and the applicable period (stability over time) of the composition. In addition, it tends to be easy to promote the pattern formation and luminescent characteristics of film, further, it tends to be easy to promote the dispersibility of quantum dots (A), the solvent resistance and heat resistance of film, and the applicable period (stability over time) of the composition.

[0116] In the composition, the mass ratio (solid content ratio) of the vinyl copolymer (B) to the polymerizable compound (C) described below is, for example, 1 or more, preferably 1.5 or more, and more preferably 2 or more from the viewpoint of film pattern forming properties and light emitting properties.

[0117] [4] Polymerizable compound (C) The composition may further contain a polymerizable compound (C). The polymerizable compound (C) is a compound that can be polymerized by active free radicals, acids, etc. generated from a polymerization initiator (D) described later. Examples of the polymerizable compound (C) include photopolymerizable compounds such as compounds having ethylenically unsaturated bonds, such as (meth)acrylate compounds. Another example of a polymerizable compound (C) is a thermally polymerizable compound. The composition may also contain two or more polymerizable compounds (C).

[0118] The polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds in the molecule. The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more, more preferably 250 or more, and is preferably 2900 or less, more preferably 1500 or less.

[0119] Examples of the photopolymerizable compound having three or more ethylenically unsaturated bonds in the molecule include a compound (Ca) having three or more ethylenically unsaturated bonds in the molecule and having an acidic functional group, and a compound (Cb) having three or more ethylenically unsaturated bonds in the molecule and having no acidic functional group. The polymerizable compound (C) preferably contains at least one compound (Ca) and a compound (Cb), and may contain two or more compounds (Ca), two or more compounds (Cb), or at least one compound (Ca) and at least one compound (Cb). Examples of the acidic functional group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. Among them, the acidic functional group is preferably a carboxyl group.

[0120] By making the polymerizable compound (C) contain the compound (Ca), the dispersibility of the quantum dots (A) in the composition can be improved, and the light emitting properties of the film can be improved. In addition, by making the polymerizable compound (C) contain the compound (Ca), the curing property and heat resistance of the composition can be improved.

[0121] The ethylenically unsaturated bond possessed by the compound (Ca) is preferably a (meth)acryloyloxy group. The number of ethylenically unsaturated bonds possessed by one molecule of the compound (Ca) is preferably 3 or more and 5 or less, and more preferably 3. The number of acidic functional groups possessed by one molecule of the compound (Ca) is 1 or more. When there are two or more acidic functional groups, the acidic functional groups may be different or the same, and preferably have at least one carboxyl group.

[0122] Examples of the compound (Ca) include compounds obtained by subjecting a compound having three or more (meth)acryloyloxy groups and hydroxyl groups, such as pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate, to polybasic acid modification. Examples of the compound include compounds obtained by monoesterifying pentaerythritol tri(meth)acrylate with a dibasic acid (e.g., succinic acid, maleic acid) or an anhydride thereof, and compounds obtained by monoesterifying dipentaerythritol penta(meth)acrylate with a dibasic acid (e.g., succinic acid, maleic acid) or an anhydride thereof.

[0123] The ethylenically unsaturated bond contained in the compound (Cb) is preferably a (meth)acryloyloxy group. The number of ethylenically unsaturated bonds contained in one molecule of the compound (Cb) is preferably 3 or more and 6 or less.

[0124] Examples of the compound (Cb) include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like are preferred.

[0125] When the composition contains a polymerizable compound (C), the content of the polymerizable compound (C) in the composition relative to the total solid content of the composition is preferably 5% by mass or more, more preferably 7% by mass or more, further preferably 10% by mass or more, and further preferably 60% by mass or less, more preferably 45% by mass or less, further preferably 30% by mass or less. When the content of the polymerizable compound (C) is within the above range, the developability of the composition and the solvent resistance of the film tend to be improved.

[0126] [5]Polymerization initiator (D) The composition may further contain a polymerization initiator (D). The polymerization initiator (D) is a compound that can generate active radicals, acids, etc. by the action of light or heat to start polymerization of the polymerizable compound (C). The composition may contain one or more polymerization initiators (D). Examples of the polymerization initiator (D) include photopolymerization initiators such as oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds; and thermal polymerization initiators such as azo compounds and organic peroxides.

[0127] One example of the oxime compound is an oxime compound having a first molecular structure represented by the following formula (1). Hereinafter, this oxime compound is also referred to as "oxime compound (1)".

[0128] [Chemistry 11]

[0129] From the viewpoint of improving the light-emitting properties of the film, it is advantageous to contain an oxime compound (1) as a polymerization initiator (D). One reason for such an effect is presumably that, due to the unique molecular structure of the oxime compound (1), the absorption wavelength of the oxime compound (1) before and after the cleavage (decomposition) of the oxime compound (1) required for initiating photopolymerization by the oxime compound (1) changes significantly, and thus the photo-radical polymerization initiation ability of the oxime compound (1) is high.

[0130] In formula (1), R 1 Represents R 11 , OR 11 , COR 11 , SR 11 ,CONR 12 R 13 or CN. R 11 , R 12 and R 13 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 11 , R 12 or R 13 The hydrogen atoms of the groups represented by OR can also be 21 , COR 21 , SR 21 NR 22 Ra 23 ,CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 , CN, halogen atom or COOR 21 replace. R 21 , R 22 and R 23 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 21 , R 22 or R 23 The hydrogen atoms of the represented groups may also be substituted by CN, halogen atoms, hydroxyl groups or carboxyl groups. R 11 , R 12 , R 13 , R 21 , R 22 or R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be replaced by -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO interruptions are more than 1 time and less than 5 times. R 24 It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 11 , R 12 , R 13 , R 21 , R22 or R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 12 With R 13 and R 22 With R 23 They may form a ring together. * represents an atomic bond with a second molecular structure other than the first molecular structure of the oxime compound (1).

[0131] As R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The alkyl group having 1 to 20 carbon atoms may be exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a tert-octyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylethyl group, and the like.

[0132] As R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Examples of the aryl group having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, phenanthryl, and phenyl, biphenyl, naphthyl, anthracenyl, and the like substituted with one or more of the above alkyl groups.

[0133] As R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Examples of the aralkyl group having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenethyl.

[0134] As R in formula (1) 11 , R 12 , R 13 , R 21 , R22 , R 23 and R 24 The heterocyclic group having 2 or more and 20 or less carbon atoms represented by can be exemplified by pyridyl, pyrimidinyl, furanyl, thienyl, tetrahydrofuranyl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolyl, pyrazolidinyl, thiazolyl, isothiazolyl, oxazolidinyl, isoxazolidinyl, piperidinyl, piperazinyl, morpholinyl, and the like, preferably a 5- to 7-membered heterocyclic ring.

[0135] R in formula (1) 12 With R 13 and R 22 With R 23 They can also form a ring together to refer to R 12 With R 13 and R 22 With R 23 They may also form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected. As Ra in formula (1) 12 With Ra 13 and Ra 22 With Ra 23 They may form a ring together, and examples thereof include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, a lactam ring, and the like, and are preferably a 5- to 7-membered ring.

[0136] R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 and R 23 In the example of the halogen atom which may be a substituent, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0137] R in formula (1) 1 Preferably R 11 , an alkyl group having 1 to 20 carbon atoms is more preferred, an alkyl group having 1 to 10 carbon atoms is further preferred, and an alkyl group having 1 to 6 carbon atoms is further preferred.

[0138] An example of the second molecular structure connected to the first molecular structure represented by formula (1) is a structure represented by the following formula (2): The second molecular structure refers to another molecular structure portion of the oxime compound (1) other than the first molecular structure. The bond represented by "*" in formula (2) is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (2), the benzene ring having "-*" in formula (2) is directly bonded to the carbonyl group having "-*" in formula (1).

[0139] [Chemistry 12]

[0140] In formula (2), R 2 and R 3 Each independently represents R 11 , OR 11 , SR 11 , COR 11 ,CONR 12 R 13 NR 12 COR 11 ,OCOR 11 、COOR 11 SCOR 11 , OCSR 11 、COSR 11 ,CSOR 11 , CN or halogen atom. R 2 When there are multiple ones, these may be the same or different. R 3 When there are multiple ones, these may be the same or different. R 11 , R 12 and R 13 Means the same as above. s and t each independently represent an integer of 0 or more and 4 or less. L represents a sulfur atom, CR 31 R 32 , CO or NR 33 . R 31 , R 32 and R 33 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. R 31 , R 32 or R 33 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 31 , R 32 and R 33 Each of them may independently form a ring together with any adjacent benzene ring. R 4 It represents a hydroxyl group, a carboxyl group or a group represented by the following formula (2-1).

[0141] [Chemistry 13] (R4a ) v —L 2 —L 1 — (2-1) (In formula (2-1), L 1 Indicates -O-, -S-, -NR 22 -、-NR 22 CO-, -SO2-, -CS-, -OCO- or -COO-. R 22 Means the same as above. L 2 It represents a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, a group obtained by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms, or a group obtained by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms. L 2 When the group represented by has an alkylene moiety, the alkylene moiety may be replaced by -O-, -S-, -COO-, -OCO-, -NR 22 -、-NR 22 COO-、-OCONR 22 -, -SCO-, -COS-, -OCS- or -CSO- is interrupted once or more and 5 or less times, and the alkylene portion may be branched or cyclic. R 4 a means OR 41 , SR 41 ,CONR 42 R 43 NR 42 COR 43 ,OCOR 41 、COOR 41 SCOR 41 , OCSR 41 、COSR 41 ,CSOR 41 , CN or halogen atom. R 4 When there are multiple a's, they may be the same or different. R 41 , R 42 and R 43 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, and R 41 , R 42 and R 43When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 42 and R 43 They can also form a ring together. v represents an integer greater than or equal to 1 and less than or equal to 3. ) * represents a bond with the first molecular structure of the oxime compound (1).

[0142] R in formula (2) 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , R 31 , R 32 and R 33 And R in the above formula (2-1) 22 , R 41 , R 42 and R 43 Examples of alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, and aralkyl groups having 7 to 30 carbon atoms are the same as those for R in formula (1). 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The same example.

[0143] R in formula (2) 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 And R in the above formula (2-1) 22 Examples of heterocyclic groups having 2 to 20 carbon atoms are similar to those in formula (1) with respect to R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The same example.

[0144] R in formula (2) 31 , R 32 and R 33 Each of the two rings may independently form a ring with any adjacent benzene ring. 31 , R 32 and R33 Each of them may independently form a ring together with any adjacent benzene ring and the nitrogen atom to which it is connected. R in formula (2) 31 , R 32 and R 33 Examples of rings that can be formed together with any adjacent benzene ring are as follows: 12 With Ra 13 and Ra 22 With Ra 23 The examples of loops that can be formed together are the same.

[0145] In the above formula (2-1), L 2 It represents a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0146] Examples of the group formed by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms include, for example, when v is 1, methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, tridecylene, tetradecylene, pentadecylene, ethane-1,1-diyl, propane-2,2-diyl and the like.

[0147] As a group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, for example, when v is 1, arylene groups such as 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 1,4-naphthylene, 2,5-dimethyl-1,4-phenylene, diphenylmethane-4,4'-diyl, 2,2-diphenylpropane-4,4'-diyl, diphenylsulfide-4,4'-diyl and diphenylsulfone-4,4'-diyl can be mentioned.

[0148] Examples of the group obtained by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms include, for example, a group represented by the following formula (a) and a group represented by the following formula (b) when v is 1.

[0149] [Chemistry 14] [In formulas (a) and (b), L 3 and L 5 represents an alkylene group having 1 to 10 carbon atoms, L4 and L 6 represents a single bond or an alkylene group having 1 to 10 carbon atoms.]

[0150] Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene.

[0151] As a group obtained by removing v hydrogen atoms from a heterocyclic group having 2 or more and 20 carbon atoms, for example, when v is 1, examples include divalent heterocyclic groups such as 2,5-pyridinediyl, 2,6-pyridinediyl, 2,5-pyrimidinediyl, 2,5-thiophenediyl, 3,4-tetrahydrofurandiyl, 2,5-tetrahydrofurandiyl, 2,5-furandiyl, 3,4-thiazolediyl, 2,5-benzofurandiyl, 2,5-benzothiophenediyl, N-methylindole-2,5-diyl, 2,5-benzothiazolediyl and 2,5-benzoxazolediyl.

[0152] As R in formula (2) 2 and R 3 And R in the above formula (2-1) 4a Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0153] From the viewpoint of solubility in the solvent (E) and / or developability of the composition, a preferred example of the structure represented by formula (2) is a structure represented by the following formula (2a).

[0154] [Chemistry 15] [In formula (2a), L' represents a sulfur atom or NR 50 , R 50 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, R 2 , R 3 , R 4 , s and t have the same meanings as above.]

[0155] From the same viewpoint as above, another preferred example of the structure represented by formula (2) is a structure represented by the following formula (2b).

[0156] [Chemistry 16] [In formula (2b), R 44 It represents a hydroxyl group, a carboxyl group or a group represented by the following formula (2-2).

[0157] [Chemistry 17] R 44a -L 12 —L 11 — (2-2) (In formula (2-2), L 11 Indicates -O- or *-OCO-, * indicates the same as L 12 The bond, L 12 represents an alkylene group having 1 to 20 carbon atoms, which may be interrupted by 1 to 3 -O- groups, and R 44a Represents OR 55 or COOR 55 , R 55 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )]

[0158] R 44 The group represented by the formula (2-2) is preferred. In this case, it is advantageous in terms of the solubility of the oxime compound (1) in the solvent (E) and the developability of the composition.

[0159] L 12 The number of carbon atoms of the alkylene group represented is preferably 1 or more and 10 or less, more preferably 1 or more and 4 or less. R 44 a is preferably a hydroxyl group or a carboxyl group, more preferably a hydroxyl group.

[0160] The method for producing the oxime compound (1) having the second molecular structure represented by formula (2) is not particularly limited, and it can be produced, for example, according to the method described in JP-A-2011-132215.

[0161] Another example of the second molecular structure connected to the first molecular structure represented by formula (1) is a structure represented by the following formula (3). In formula (3), the bond represented by "*" is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (3), the benzene ring having "-*" in formula (3) is directly bonded to the carbonyl group having "-*" in formula (1).

[0162] [Chemistry 18]

[0163] In formula (3), R 5It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 5 When the group represented has an alkyl portion, the alkyl portion may be branched or cyclic. R 5 The hydrogen atoms of the groups represented by R 21 , OR 21 , COR 21 , SR 21 NR 22 R 23 ,CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 NR 22 COR 21 ,OCOR 21 、COOR 21 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 SCOR 21 , OCSR 21 、COSR 21 ,CSOR 21 , hydroxyl, nitro, CN, halogen atom or COOR 21 replace. R 21 , R 22 and R 23 Means the same as above. R 21 , R 22 or R 23 The hydrogen atoms of the represented groups may also be substituted by CN, halogen atoms, hydroxyl groups or carboxyl groups. R 21 , R 22 and R 23 When the group represented by has an alkylene portion, the alkylene portion may be replaced by -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- are interrupted more than 1 time and less than 5 times. R 24 Means the same as above. R 21 , R 22 and R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 22 With R 23 They can also form a ring together. R 6 , R 7 , R 8 and R 9 Each independently represents R 61 , OR 61 , SR 61 , COR 62 ,CONR 63 R 64 NR 65 COR 61 ,OCOR 61 、COOR 62 SCOR 61 , OCSR 61 、COSR 62 ,CSOR 61 , hydroxyl, nitro, CN or halogen atom. R 61 , R 62 , R 63 , R 64 and R 65 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atoms of the groups represented by OR can also be 21 , COR 21 , SR 21 NR 22 Ra 23 ,CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR21 )-R 22 , CN, halogen atom or COOR 21 replace. R 6 With R 7 , R 7 With R 8 and R 8 With R 9 They may also form a ring together. * represents a bond with the first molecular structure of the oxime compound (1).

[0164] R in formula (3) 5 , R 21 , R 22 , R 23 , R 24 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aralkyl groups having 7 to 30 carbon atoms, and heterocyclic groups having 2 to 20 carbon atoms are the same as those for R in formula (1). 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The same example.

[0165] R in formula (3) 22 With R 23 They can also form a ring together, which means R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected. R in formula (3) 22 With R 23 Examples of the rings that can be formed together are similar to those in formula (1) regarding Ra 12 With Ra 13 and Ra 22 With Ra 23 The examples of loops that can be formed together are the same.

[0166] As R in formula (3) 6 , R 7 , R 8 and R 9 The halogen atom represented by R 5 , R 21 , R 22 , R23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom that replaces the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0167] From the viewpoint of solubility in the solvent (E) and / or developability of the composition, in a preferred embodiment, R 5 It is a group represented by the following formula (3-1).

[0168] [Chemistry 19] [In the formula (3-1), Z represents a group obtained by removing one hydrogen atom from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing one hydrogen atom from an aryl group having 6 to 30 carbon atoms, a group obtained by removing one hydrogen atom from an aralkyl group having 7 to 30 carbon atoms, or a group obtained by removing one hydrogen atom from a heterocyclic group having 2 to 20 carbon atoms, When the group represented by Z has an alkylene moiety, the alkylene moiety may be replaced by -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- is interrupted 1 or more times but less than 5 times, and the alkylene portion may be branched or cyclic, R 21 , R 22 and R 24 Means the same as above.]

[0169] From the same viewpoint as described above, Z in formula (3-1) is preferably a methylene group, an ethylene group or a phenylene group. From the same point of view as above, R in formula (3-1) 21 and R 22 It is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and more preferably a methyl group, an ethyl group or a phenyl group. From the same viewpoint as above, in another preferred embodiment, R 7 For nitro.

[0170] The method for producing the oxime compound (1) having the second molecular structure represented by formula (3) is not particularly limited, and it can be produced, for example, according to the methods described in JP-A-2000-80068 and JP-A-2011-178776.

[0171] Another example of the second molecular structure connected to the first molecular structure represented by formula (1) is a structure represented by the following formula (4). The bond represented by "*" in formula (4) is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (4), the benzene ring having "-*" in formula (4) is directly bonded to the carbonyl group having "-*" in formula (1).

[0172] [Chemistry 20]

[0173] In formula (4), R 71 It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 71 When the group represented has an alkyl portion, the alkyl portion may be branched or cyclic. R 71 The hydrogen atoms of the groups represented by R 21 , OR 21 , COR 21 , SR 21 NR 22 R 23 ,CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 NR 22 COR 21 ,OCOR 21 、COOR 21 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 SCOR 21 , OCSR 21 、COSR 21 ,CSOR 21 , hydroxyl, nitro, CN, halogen atom or COOR 21 replace. R 21 , R 22 and R 23 Means the same as above. R 21 , R 22or R 23 The hydrogen atoms of the represented groups may also be substituted by CN, halogen atoms, hydroxyl groups or carboxyl groups. R 21 , R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be replaced by -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- are interrupted more than 1 time and less than 5 times. R 24 Means the same as above. R 21 , R 22 and R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 22 With R 23 They can also form a ring together. R 72 , R 73 and 3 Rs 74 Each independently represents R 61 , OR 61 , SR 61 , COR 62 ,CONR 63 R 64 NR 65 COR 61 ,OCOR 61 、COOR 62 SCOR 61 , OCSR 61 、COSR 62 ,CSOR 61 , hydroxyl, nitro, CN or halogen atom. R 61 , R 62 , R 63 , R 64 and R 65 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 61 , R 62 , R 63 , R 64 or R 65The hydrogen atoms of the groups represented by OR can also be 21 , COR 21 , SR 21 NR 22 Ra 23 ,CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 , CN, halogen atom or COOR 21 replace. R 72 With R 73 and 2 R 74 They may form a ring together. * represents a bond with the first molecular structure of the oxime compound (1).

[0174] R in formula (4) 71 , R 21 , R 22 , R 23 , R 24 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aralkyl groups having 7 to 30 carbon atoms, and heterocyclic groups having 2 to 20 carbon atoms are the same as those for R in formula (1). 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The same example.

[0175] R in formula (4) 22 With R 23 They can also form a ring together, which means R 22 With R 23 They may also form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected. R in formula (4) 22 With R 23 Examples of the rings that can be formed together are similar to those in formula (1) regarding Ra 12 With Ra13 and Ra 22 With Ra 23 The examples of loops that can be formed together are the same.

[0176] As R in formula (4) 72 , R 73 and R 74 The halogen atom represented by R 71 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom that replaces the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0177] The method for producing the oxime compound (1) having the second molecular structure represented by formula (4) is not particularly limited, and it can be produced, for example, according to the methods described in International Publication Nos. 2017 / 051680 and 2020 / 004601.

[0178] Another example of the second molecular structure connected to the first molecular structure represented by formula (1) is a structure represented by the following formula (5). The bond represented by "*" in formula (5) is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (5), the pyrrole ring having "-*" in formula (5) is directly bonded to the carbonyl group having "-*" in formula (1).

[0179] [Chemistry 21]

[0180] In formula (5), R 81 It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 81 When the group represented has an alkyl portion, the alkyl portion may be branched or cyclic. R 81 The hydrogen atoms of the groups represented by R 21 , OR 21 , COR 21 , SR 21 NR 22 R 23 ,CONR 22 R 23、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 NR 22 COR 21 ,OCOR 21 、COOR 21 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 SCOR 21 , OCSR 21 、COSR 21 ,CSOR 21 , hydroxyl, nitro, CN, halogen atom or COOR 21 replace. R 21 , R 22 and R 23 Means the same as above. R 21 , R 22 or R 23 The hydrogen atoms of the represented groups may also be substituted by CN, halogen atoms, hydroxyl groups or carboxyl groups. R 21 , R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be replaced by -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- are interrupted more than 1 time but less than 5 times. R 24 Means the same as above. R 21 , R 22 and R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 22 With R 23 They can also form a ring together. R 82 , R 83 , R 84 , R 85 and R 86 Each independently represents R 61 , OR 61 , SR 61, COR 62 ,CONR 63 R 64 NR 65 COR 61 ,OCOR 61 、COOR 62 SCOR 61 , OCSR 61 、COSR 62 ,CSOR 61 , hydroxyl, nitro, CN or halogen atom. R 61 , R 62 , R 63 , R 64 and R 65 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atoms of the groups represented by OR can also be 21 , COR 21 , SR 21 NR 22 Ra 23 ,CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 , CN, halogen atom or COOR 21 replace. R 83 With R 84 , R 84 With R 85 and R 85 With R 86 They may form a ring together. * represents a bond with the first molecular structure of the oxime compound (1).

[0181] R in formula (5) 81 , R 21 , R 22 , R 23 , R24 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aralkyl groups having 7 to 30 carbon atoms, and heterocyclic groups having 2 to 20 carbon atoms are the same as those for R in formula (1). 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The same example.

[0182] R in formula (5) 22 With R 23 They can also form a ring together, which means R 22 With R 23 They may also form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected. R in formula (5) 22 With R 23 Examples of the rings that can be formed together are similar to those in formula (1) regarding Ra 12 With Ra 13 and Ra 22 With Ra 23 The examples of loops that can be formed together are the same.

[0183] As R in formula (5) 82 , R 83 , R 84 , R 85 and R 86 The halogen atom represented by R 81 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom that replaces the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0184] The method for producing the oxime compound (1) having the second molecular structure represented by formula (5) is not particularly limited, and it can be produced, for example, according to the methods described in International Publication Nos. 2017 / 051680 and 2020 / 004601.

[0185] Another example of the second molecular structure connected to the first molecular structure represented by formula (1) is a structure represented by the following formula (6). The bond represented by "*" in formula (6) is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (6), the benzene ring having "-*" in formula (6) is directly bonded to the carbonyl group having "-*" in formula (1).

[0186] [Chemistry 22]

[0187] In formula (6), the four R 91 , R 92 , R 93 , R 94 , R 95 , R 96 and R 97 Each independently represents R 61 , OR 61 , SR 61 , COR 62 ,CONR 63 R 64 NR 65 COR 61 ,OCOR 61 、COOR 62 SCOR 61 , OCSR 61 、COSR 62 ,CSOR 61 , hydroxyl, nitro, CN or halogen atom. R 61 , R 62 , R 63 , R 64 and R 65 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atoms of the groups represented by OR can also be 21 , COR 21 , SR 21 NR 22 Ra 23 ,CONR 22 R 23 、-NR 22 -OR23 、-N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 , CN, halogen atom or COOR 21 replace. R 21 , R 22 and R 23 Means the same as above. R 92 With R 93 , R 94 With R 95 , R 95 With R 96 and R 96 With R 97 They may form a ring together. * represents a bond with the first molecular structure of the oxime compound (1).

[0188] R in formula (6) 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aralkyl groups having 7 to 30 carbon atoms, and heterocyclic groups having 2 to 20 carbon atoms are the same as those for R in formula (1). 11 , R 12 , R 13 , R 21 , R 22 and R 23 The same example.

[0189] R in formula (6) 22 With R 23 They can also form a ring together, which means R 22 With R 23 They may also form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected. R in formula (6) 22 With R 23 Examples of the rings that can be formed together are similar to those in formula (1) regarding Ra 12 With Ra 13 and Ra 22 With Ra 23 The examples of loops that can be formed together are the same.

[0190] As R in formula (6) 91 , R 92 , R 93 , R 94 , R 95 , R 96 and R 97 The halogen atom represented by R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom that replaces the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0191] The method for producing the oxime compound (1) having the second molecular structure represented by formula (6) is not particularly limited, and it can be produced, for example, according to the methods described in International Publication Nos. 2017 / 051680 and 2020 / 004601.

[0192] Another example of the photopolymerization initiator is a photopolymerization initiator other than the oxime compound (1). Examples of the photopolymerization initiator include oxime compounds other than the oxime compound (1), alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds.

[0193] Examples of oxime compounds other than the oxime compound (1) include oxime compounds having a structural portion represented by the following formula (d1): * represents a bond.

[0194] [Chemistry 23]

[0195] Examples of the oxime compound having a structural moiety represented by formula (d1) include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentyl]propane-1-imine]

[0063] N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-2-imine; compounds described in Japanese Patent Application Publication No. 2011-132215, International Publication No. 2008 / 78678, International Publication No. 2008 / 78686, and International Publication No. 2012 / 132558, etc. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02, OXE03 (all manufactured by BASF), N-1919, NCI-930, and NCI-831 (all manufactured by ADEKA) can also be used.

[0196] Among them, the oxime compound having a structural part represented by formula (d1) is preferably at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, and more preferably N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine.

[0197] The alkylphenone compound is a compound having a structural part represented by the following formula (d2) or a structural part represented by the following formula (d3). In these structural parts, the benzene ring may have a substituent.

[0198] [Chemistry 24]

[0199] Examples of the compound having a structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one, etc. Commercially available products such as OMNIRAD (registered trademark) 369, 907, and 379 (all manufactured by IGM Resins) can also be used.

[0200] Examples of the compound having a structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-〔4-(2-hydroxyethoxy)phenyl〕propane-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, benzil dimethyl ketal, and the like.

[0201] From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d2).

[0202] Examples of the biimidazole compound include compounds represented by formula (d5).

[0203] [Chemistry 25] [In formula (d5), R E ~R J represents an aryl group having 6 or more and 10 or less carbon atoms which may have a substituent.]

[0204] Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl and naphthyl, and preferably phenyl. Examples of the substituent include a halogen atom, an alkoxy group having 1 to 4 carbon atoms, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and preferably a methoxy group.

[0205] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open No. 06-75372 and Japanese Patent Application Laid-Open No. 06-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole. Tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, see Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), imidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups (for example, see Japanese Patent Application Laid-Open No. 7-10913, etc.). Among them, compounds represented by the following formula or mixtures thereof are preferred.

[0206] [Chemistry 26]

[0207] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc. Among them, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine is preferred.

[0208] Examples of the acylphosphine compound include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide. Commercially available products such as OMNIRAD (registered trademark) 819 (manufactured by IGM Resins) may also be used.

[0209] Other examples of photopolymerization initiators other than the oxime compound (1) include: benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(diethylamino)benzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, and titanocene compounds.

[0210] When the composition contains a polymerization initiator (D), the content of the polymerization initiator (D) in the composition is preferably 0.1 parts by mass or more, preferably 300 parts by mass or less, and more preferably 200 parts by mass or less relative to 100 parts by mass of the polymerizable compound (C). In addition, the content of the polymerization initiator (D) in the composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and more preferably 30 parts by mass or less, and more preferably 20 parts by mass or less relative to 100 parts by mass of the total amount of the vinyl copolymer (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the composition tends to be highly sensitive, shortening the exposure time, and therefore tends to improve the productivity of the film.

[0211] [6]Polymerization initiator (D1) The composition may further contain a polymerization initiator aid (D1) while containing a polymerization initiator (D). The polymerization initiator aid (D1) is a compound or sensitizer for promoting the polymerization of the polymerizable compound (C) initiated by the polymerization initiator (D). Examples of the polymerization initiator aid (D1) include photopolymerization initiators such as amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds, and thermal polymerization initiators. The composition may also contain two or more polymerization initiators (D1).

[0212] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone.

[0213] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0214] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0215] Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0216] When the composition contains a polymerization initiator aid (D1), the content of the polymerization initiator aid (D1) in the composition is preferably 0.1 parts by mass or more, more preferably 300 parts by mass or less, and more preferably 200 parts by mass or less, relative to 100 parts by mass of the polymerizable compound (C). In addition, the content of the polymerization initiator aid (D1) in the composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and more preferably 30 parts by mass or less, and more preferably 20 parts by mass or less, relative to 100 parts by mass of the total amount of the vinyl copolymer (B) and the polymerizable compound (C). When the content of the polymerization initiator aid (D1) is within the above range, further high sensitivity of the composition can be sought.

[0217] [7]Solvent (E) The composition may contain one or more solvents (E). The solvent (E) is preferably capable of dissolving the vinyl copolymer (B), the polymerizable compound (C) and the polymerization initiator (D). Examples of the solvent (E) include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0218] Examples of the ester solvent include methyl lactate, ethyl lactate, n-butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0219] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, and methyl anisole.

[0220] Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0221] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0222] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0223] The solvent (E) preferably contains one or more selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and aromatic hydrocarbon solvents.

[0224] The solvent (E) is a component other than the solid component, and for example, the solvent contained in the dispersion of the quantum dots (A) and the solution of the vinyl copolymer (B) is also included in the solvent (E). The content of the solvent (E) in the composition is the ratio of the total mass of the total solvent contained in the composition relative to the total amount of the composition, and relative to the total amount of the composition, for example, 40% by mass or more, preferably 55% by mass or more, and for example, 95% by mass or less, preferably 90% by mass or less. In other words, the solid content of the composition is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 60% by mass or less, preferably 45% by mass or less. When the content of the solvent (E) is within the above range, the flatness of the composition layer during coating is better, and it tends to be easy to form a film of appropriate thickness.

[0225] [8] Light scattering agent (F) The composition may further contain a light scattering agent (F). The film formed by the composition may exhibit light scattering properties. The composition may also contain two or more light scattering agents (F). From the viewpoint of improving the luminescent properties of the film, the composition preferably further contains a light scattering agent (F).

[0226] As the light scattering agent (F), inorganic particles such as metal or metal oxide particles and glass particles can be cited. As metal oxides, TiO2, SiO2, BaTiO3, ZnO, etc. can be cited. From the perspective of efficient light scattering, TiO2 particles are preferred. The particle size of the light scattering agent (F) is, for example, about 0.03 μm or more, preferably 0.05 μm or more, for example, about 20 μm or less, preferably 1 μm or less, and more preferably 0.5 μm or less.

[0227] As the light scattering agent (F), a solution prepared by dispersing the light scattering agent in part or all of the solvent (E) with a dispersant may be used. As the dispersant, a commercially available product may be used. Examples of commercially available products include DISPERBYK-101, 102, 103, 106, 107, 108, 109, 110, 111, 116, 118, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 192, 2000, 2001, 2020, 2025, 2050, 2070, 2080, 2090, 2100, 2111, 2120, 2130, 2140, 2151, 2162, 2173, 2184, 2190, 2203, 2219 095, 2150, 2155; ANTI-TERRA-U, U100, 203, 204, 250, BYK-P104, P104S, P105, 220S, 6919; BYK-LPN6919, 21116; LACTIMON, LACTIMON-WS; Bykumen, etc.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 1700 manufactured by Japan Lubrizol 0, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc.; EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, manufactured by BASF 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc.; Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno.

[0228] When the composition contains a light scattering agent (F), the content of the light scattering agent (F) in the composition relative to the total solid content of the composition is, for example, 0.001 mass % or more and 50 mass % or less. From the viewpoint of improving the light scattering ability and light emitting characteristics of the film, it is preferably 1 mass % or more, more preferably 2 mass % or more, further preferably 3 mass % or more, further preferably 30 mass % or less, more preferably 20 mass % or less, further preferably 15 mass % or less, and further preferably 10 mass % or less.

[0229] [9] Antioxidants (H) The composition may further contain an antioxidant (H). As the antioxidant (H), there is no particular limitation as long as it is an antioxidant commonly used in industry, and phenol-based antioxidants, phosphorus-based antioxidants, phosphorus / phenol composite antioxidants, sulfur-based antioxidants, etc. can be used. The composition may also contain two or more antioxidants (H).

[0230] The phosphorus / phenol complex antioxidant is, for example, a compound having one or more phosphorus atoms and a phenol structure in each molecule. Among them, the antioxidant (H) preferably contains a phosphorus / phenol complex antioxidant from the viewpoint of the developability of the composition and the luminescent properties of the film.

[0231] Examples of the phenolic antioxidant include Irganox (registered trademark) 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation), Irganox 1330 (Irganox 1330: 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF Corporation), Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), same as 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), same as 1035 (Irganox 1035: diethylene sulfide bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), same as 1135 (Irganox 1135: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester of phenylpropionic acid, manufactured by BASF Corporation), same as 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Corporation), same as 3125 (Irganox 3125, manufactured by BASF Corporation), same as 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, manufactured by BASF Corporation), ADEKASTAB (registered trademark) AO-80 (ADEKASTAB AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, manufactured by ADEKA Co., Ltd.), SUMILIZER (registered trademark) BHT, same as GA-80, same as GS (all manufactured by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (Cyanox 1790, manufactured by SAITECH Co., Ltd.), vitamin E (manufactured by Eisai Co., Ltd.), etc.

[0232] Examples of the phosphorus antioxidant include Irgafos (registered trademark) 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Corporation), Irgafos 12 (Irgafos 12: tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphaheptain-6-yl]oxy]ethyl]amine, manufactured by BASF Corporation), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite, manufactured by BASF Corporation), ADEKA STAB (registered trademark) 329K, same as PEP36, same as PEP-8 (all manufactured by ADEKA Corporation), Sandstab P-EPQ (manufactured by Clariant), Weston (registered trademark) 618, same as 619G (all manufactured by GE), Ultranox 626 (manufactured by GE), etc.

[0233] Examples of the phosphorus / phenol composite antioxidant include SUMILIZER (registered trademark) GP (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]-dioxaphosphine) (manufactured by Sumitomo Chemical Co., Ltd.).

[0234] Examples of the sulfur-based antioxidant include dilauryl thiodipropionate, dialkylthiodipropionate compounds such as dimyristyl or distearyl, and β-alkylmercaptopropionate compounds of polyhydric alcohols such as tetrakis[methylene(3-dodecylthio)propionate]methane.

[0235] When the composition contains an antioxidant (H), the content of the antioxidant (H) in the composition is, for example, more than 1 part by mass and less than 50 parts by mass relative to 100 parts by mass of the vinyl copolymer (B). From the viewpoint of the luminescent properties and heat resistance of the film, it is preferably more than 5 parts by mass, more preferably more than 7 parts by mass, further preferably less than 40 parts by mass, more preferably less than 30 parts by mass.

[0236]

[10] Leveling agent (I) The composition may further contain a leveling agent (I). Examples of the leveling agent (I) include silicone surfactants, fluorine-based surfactants, and silicone surfactants having fluorine atoms. These may also have polymerizable groups in the side chains. From the viewpoint of the developability of the composition and the luminescent properties of the film, the leveling agent (I) is preferably a fluorine-based surfactant. The composition may also contain two or more leveling agents (I).

[0237] Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule, and specifically include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

[0238] As the fluorine-based surfactant, there can be mentioned surfactants having a fluorine carbon chain in the molecule, etc. Specifically, there can be mentioned Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFACE (registered trademark) F142D, F171, F172, F173, F177, F183, F554, F575, R30, RS-718-K (manufactured by DIC Corporation), F TOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Material Electronics Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemicals Laboratories, Ltd.).

[0239] Examples of silicone surfactants having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and specifically, MEGAFACE (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0240] When the composition contains a leveling agent (I), the content of the leveling agent (I) in the composition relative to the total amount of the composition is, for example, 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, and for example, 1.0% by mass or less, preferably 0.75% by mass or less, more preferably 0.5% by mass or less. When the content of the leveling agent (I) is within the above range, the flatness of the film can be improved.

[0241]

[11] Other ingredients If necessary, the composition may further contain additives known in the art, such as a polymerization inhibitor, a filler, other polymer compounds, an adhesion promoter, a light stabilizer, and a chain transfer agent.

[0242] <Method for producing composition> The composition can be produced by a method including a step of mixing predetermined components and other components used as needed. The method for producing the composition may further include a step of preparing the vinyl copolymer (B).

[0243] <Film and method for producing the same> The film of the present invention is a film formed from the composition of the present invention. The film can be used as a wavelength conversion layer in a display device, etc. The film can be provided on a substrate, for example, by method a: comprising a step of applying the composition to a substrate and then drying it; or method b: after manufacturing the film by a method comprising a step of applying the composition to a support and then drying it, the film is peeled off from the support and attached to the substrate via an adhesive layer.

[0244] In one embodiment, the composition is a non-curable resin composition R1. A film formed from the resin composition R1 can be formed, for example, by applying the composition to a substrate or a support and then drying it.

[0245] In other embodiments, the composition is a curable resin composition R2 further containing a polymerizable compound (D) and a polymerization initiator (E). The vinyl copolymer (B) contained in the curable resin composition R2 can be curable or non-curable. The film formed by the curable resin composition R2 is a cured film. The cured film can be obtained by applying the curable resin composition R2 to a substrate or a support and drying it, and curing it by the action of light and / or heat. One embodiment of the curable resin composition R2 is a photocurable resin composition R3 containing a photopolymerizable compound and a photopolymerization initiator.

[0246] The film may be provided on the entire substrate or may be provided in a pattern on a portion of the substrate. Methods for forming the film in a pattern on the substrate include photolithography, inkjet, printing, etc. Printing methods include stencil printing, screen printing, and printing and coating using an applicator.

[0247] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda lime glass with a silica coating on the surface; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; substrates having aluminum, silver, and silver / copper / palladium alloy thin films formed on these base materials; and components that the display device contains or may contain. Examples of components that the display device contains or may contain include a primary light source (e.g., a blue light source), a light guide plate, a diffusion film (diffusion layer), a light reflecting component (reflection film, etc.), a brightness enhancing component, a prism sheet, a barrier layer, and a protective layer (over coat layer).

[0248] The patterned film formed from the resin composition R1 can be formed on the substrate as follows. First, the resin composition R1 is applied to the substrate via a mask to form a patterned composition layer. Examples of the coating method of the resin composition include spin coating, slit coating, slit & spin coating, and the like.

[0249] Next, the film is obtained by drying the composition layer (removing volatile components such as solvents). Examples of drying methods include: heating drying, reduced pressure drying, or a combination of these. The temperature for heating drying is preferably 30°C or more, more preferably 50°C or more, and also preferably 250°C or less, and more preferably 235°C or less. The heating time is preferably 10 seconds or more, more preferably 30 seconds or more, preferably 180 minutes or less, and more preferably 90 minutes or less. When reduced pressure drying is performed, it is preferably performed under a pressure of 50 Pa or more and 150 Pa or less. The drying of the composition layer can be performed in multiple stages, for example, by implementing multiple drying steps with different drying temperatures.

[0250] The patterned cured film formed by the photocurable resin composition R3 can be formed on a substrate, for example, by using a method using photolithography. First, the photocurable resin composition R3 is applied to the substrate, and volatile components such as the solvent are removed by heating and drying (pre-baking) and / or drying under reduced pressure to obtain a composition layer. As the coating method, the same method as described above can be cited.

[0251] The temperature for heat drying is preferably 30° C. or higher, more preferably 50° C. or higher, further preferably 120° C. or lower, and more preferably 110° C. or lower. The heating time is preferably 10 seconds or longer, more preferably 30 seconds or longer, further preferably 60 minutes or lower, and more preferably 30 minutes or lower. When the reduced pressure drying is performed, it is preferably performed at a pressure of 50 Pa or higher and 150 Pa or lower, and at a temperature range of 20° C. or higher and 25° C. or lower.

[0252] Next, the composition layer is exposed via a photomask for forming a target pattern shape. As a light source for exposure, a light source emitting a wavelength of light of 250 nm or more and 450 nm or less is preferred. For example, according to the absorption wavelength of the photopolymerization initiator, a bandpass filter can be used to selectively extract light near 436 nm, near 408 nm, or near 365 nm from the light of the wavelength. As a light source, specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. can be cited.

[0253] In order to evenly irradiate the entire exposure surface with parallel light or to accurately align the photomask and the substrate on which the composition layer is formed, it is preferred to use an exposure device such as a mask alignment exposure machine and a stepper. The exposed composition layer is cured by polymerizing the vinyl copolymer (B), the photopolymerizable compound, etc. contained in the composition layer.

[0254] By bringing the exposed composition layer into contact with a developer and then developing, the unexposed portion of the composition layer is dissolved in the developer and removed to obtain a patterned cured film. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide, and organic solvents can be cited. The concentration in the aqueous solution of the alkaline compound is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and also preferably 10% by mass or less, and more preferably 5% by mass or less. As the organic solvent, the same solvent as the above-mentioned solvent (E) can be cited. The developer may also contain a surfactant. The developing method may be any one of a paddle method, a dipping method, a spray method, etc. Furthermore, the substrate may be tilted at any angle during the development.

[0255] For the patterned film obtained by development, it is preferred to further heat (post-bake). The heating temperature is preferably above 150°C, more preferably above 160°C, further preferably below 250°C, and more preferably below 235°C. The heating time is preferably above 1 minute, more preferably above 10 minutes, further preferably below 120 minutes, and more preferably below 60 minutes. Since the polymerization of the unreacted vinyl copolymer (B), photopolymerizable compound, etc. contained in the film can be promoted by heating after development, a cured film with better chemical resistance can be obtained. Even when development is not performed, it is preferred to further heat (post-bake) the exposed composition layer.

[0256] On the other hand, as a method for forming a cured film on the entire surface of a substrate, there is a method of applying a curable resin composition to a substrate, drying it as necessary to form a composition layer, and heating and / or exposing the entire surface of the composition layer.

[0257] The thickness of the film is, for example, 1 μm or more, preferably 1.5 μm or more, more preferably 2 μm or more, and for example, 20 μm or less, preferably 18 μm or less, more preferably 14 μm or less, and further preferably 12 μm or less. When the thickness of the film is too small, when the film as a wavelength conversion layer is irradiated with primary light, there is a tendency for the proportion of primary light that is not fully absorbed by the film or not scattered to pass through the film to increase. The shape and size of the patterned film are not particularly limited. For the patterned film, for example, its plane viewing angle shape is a square shape.

[0258] The film involved in one embodiment is a wavelength conversion layer that absorbs primary light from a primary light source and emits green light, preferably a wavelength conversion layer that converts the wavelength of the blue light of the primary light into the wavelength of green light. The green light emitted by the wavelength conversion layer preferably contains a peak with a maximum value in the wavelength range of 500nm to 560nm in the luminescence spectrum, more preferably contains a peak with a maximum value in the wavelength range of 520nm to 545nm, and further preferably contains a peak with a maximum value in the wavelength range of 525nm to 535nm. The half width of the peak is preferably 15nm or more, and is also preferably 80nm or less, more preferably 60nm or less, more preferably 50nm or less, and particularly preferably 45nm or less.

[0259] The film involved in other embodiments is a wavelength conversion layer that absorbs primary light from a primary light source and emits red light, preferably a wavelength conversion layer that converts the wavelength of the blue light of the primary light into the wavelength of red light. The red light emitted by the wavelength conversion layer preferably contains a peak with a maximum value in the wavelength range of more than 610nm and less than 750nm in the luminescence spectrum, more preferably contains a peak with a maximum value in the wavelength range of more than 620nm and less than 650nm, and further preferably contains a peak with a maximum value in the wavelength range of more than 625nm and less than 645nm. The half width of the peak is preferably more than 15nm, and is also preferably less than 80nm, more preferably less than 60nm, more preferably less than 50nm, and particularly preferably less than 45nm.

[0260] <Display device> The display device of the present invention is equipped with at least a light source and the above-mentioned film. As the display device, for example, a liquid crystal display device, an organic EL display device or an inorganic EL display device can be cited, and specifically, the display devices described in Japanese Patent Publication No. 2006-309219, Japanese Patent Publication No. 2006-310303, Japanese Patent Publication No. 2013-15812, Japanese Patent Publication No. 2009-251129, Japanese Patent Publication No. 2014-2363, etc. can be cited.

[0261] In a display device according to one embodiment, a backlight as a blue light source and a plurality of patterns arranged on the visible side of the backlight are provided. The plurality of patterns may be a red pattern, a green pattern and a white (transparent, achromatic) pattern, and at least one of the red pattern and the green pattern may be the film according to the present invention. The color pattern containing the red pattern or the green pattern of quantum dots has the function of changing the wavelength of the incident light and then emitting it. Example

[0262] The present invention will be described in further detail below by way of examples. Unless otherwise specified, "%" and "parts" in the examples are % by mass and parts by mass.

[0263] <Measurement and Evaluation> (1) Film thickness measurement The film thickness was measured using a film thickness measuring device (DEKTAKXT; manufactured by Bruker Corporation).

[0264] (2) Measurement of the luminescence spectrum of quantum dots (A) The absolute PL quantum yield measurement device ("C9920-02" manufactured by Hamamatsu Photonics, excitation light 450 nm, room temperature, atmospheric air) was used to measure the quantum dot (A) dispersion diluted to an absorbance of 0.4 at a wavelength of 450 nm.

[0265] (3) Determination of Molecular Weight and Molecular Weight Distribution of Vinyl Copolymer (B) Gel permeation chromatography (GPC) was performed using a high performance liquid chromatograph (manufactured by Tosoh, model: HLC-8320) under the following conditions, and a calibration curve (calibration curve) was prepared using the following standard substances to measure the weight average molecular weight (Mw) and number average molecular weight (Mn). Molecular weight distribution (Mw / Mn) was calculated based on these measured values. Measurement sample: A sample obtained by methylating the carboxyl groups of the vinyl copolymer (B) using a trimethylsilyldiazomethane-hexane solution (concentration: 0.6 mol / L) Sample concentration: 10 mg / mL Sample injection volume: 10 μL Flow rate: 0.35mL / min Column: TSKgel SuperMultipore HZ-H (Made in Tosoh Corporation) 2 pieces Column temperature: 40°C Mobile phase: Tetrahydrofuran (THF) Detector: Differential refractive index detector Standard material: Polystyrene (manufactured by Tosoh Corporation, TSK Standard)

[0266] (4) Determination of Ethylene Unsaturated Bond Equivalent of Vinyl Copolymer (B) The weight average molecular weight per 1 mol of ethylenically unsaturated bonds, that is, the ethylenically unsaturated bond equivalent was determined based on the following formula. Ethylenically unsaturated bond equivalent 〔g / mol〕=W〔g〕 / M〔mol〕 In the formula, W represents the mass of the vinyl copolymer (B) [g], and M represents the molar number of ethylenic double bonds contained in the vinyl copolymer (B) W [g] [mol]. M is obtained by measuring the number of ethylenic double bonds contained per 1 g of the copolymer according to the test method for base value described in JIS 0070:1992.

[0267] (5) Measurement of acid value of vinyl copolymer (B) The sample to be measured (vinyl copolymer) was dissolved in THF, several drops of phenolphthalein ethanol solution were added as an indicator, and neutralization titration was performed using 0.1 mol / L potassium hydroxide / 2-propanol solution. The acid value (Av) was calculated according to the following formula. Av=56.11×Vs×0.1×f / w Av: Acid value [mgKOH / g] Vs: Amount of 0.1 mol / L potassium hydroxide / 2-propanol solution required for titration [mL] f: Titer of 0.1 mol / L potassium hydroxide / propanol solution w: mass of the sample to be measured (g) (converted to solid content)

[0268] (6) Content of tellurium compound in vinyl copolymer (B) The weighed sample (vinyl copolymer) was mixed with concentrated nitric acid and ultrapure water, and irradiated with microwaves for ashing (decomposition of the vinyl polymer). The tellurium content in the ashing solution was measured by inductively coupled plasma mass spectrometry (ICP / MS), and the amount of tellurium compound relative to the vinyl copolymer was calculated in terms of metal (mass ppm).

[0269] (7) Determination of solid content of vinyl copolymer (B) solution About 1 g of the vinyl copolymer (B) solution was weighed in an aluminum cup, dried at 180°C for 1 hour, and then the mass was measured. The solid content (mass %) of the vinyl copolymer (B) solution was calculated from the mass loss.

[0270] (8) Evaluation of film pattern forming properties The composition was applied to a 5 cm square glass substrate (EAGLE XG; manufactured by Corning) by spin coating to a thickness of 6.0 μm after post-baking, and then pre-baked at 100° C. for 3 minutes in a clean oven to obtain a composition layer. After cooling, the substrate on which the composition layer was formed and a quartz glass photomask were spaced 150 μm apart, and an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used in an atmospheric gas atmosphere at a temperature of 200 mJ / cm 2 The light was irradiated with an exposure amount (wavelength 365nm basis). As a photomask, a photomask for forming a 1:1 line and space pattern of 20μm was used. The composition layer after light irradiation was immersed in an aqueous solution containing 0.14% nonionic surfactant and 0.048% potassium hydroxide at 25°C for 20 seconds for development, and after washing with water, it was post-baked in an oven at 180°C for 30 minutes to obtain a pattern consisting of a cured film with a line and space pattern (10 lines and 10 spaces each) with a line width of 20μm.

[0271] The obtained pattern was observed using a microscope (magnification 1000 times; VHX-2000; manufactured by Keyence Corporation), and pattern formability was evaluated according to the following evaluation criteria. A: The pattern is formed into lines according to the mask B: Other than A (there are sites where spaces are not properly formed, there are sites where line patterns are not properly formed or where line patterns are collapsed, etc.)

[0272] (9) Evaluation of film luminescence properties (9-1) Quantum yield QY The composition was applied to a 5 cm square glass substrate (EAGLE XG; manufactured by Corning) by spin coating to a thickness of 6 μm after post-baking, and then pre-baked at 100° C. for 3 minutes in a clean oven to obtain a composition layer. An exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used in an atmospheric gas atmosphere at a rate of 200 mJ / cm 2 The substrate on which the composition layer was formed was irradiated with light at an exposure amount (based on a wavelength of 365 nm) of 1.5 %. After development, post-baking was performed at 180° C. for 30 minutes to obtain a substrate having a cured film. The quantum yield QY was measured using a PL quantum yield measuring device (automatic control electric monochromatic light source type, C9920-02G; manufactured by Hamamatsu Photonics Co., Ltd.). For the measuring part, an integrating sphere unit was used, and a substrate sample with a cured film cut into 1 cm square was set in the integrating sphere. The reflected light obtained by irradiating the excitation light from directly above the sample was measured to obtain the luminous efficiency. A xenon lamp was used as the light source, and light with a wavelength of 450 nm was used as the excitation light. The results are shown in Table 4. The QY obtained in Comparative Example 1 was used as a reference, and ΔQY was calculated as a relative value (%) when ΔQY in Comparative Example 1 was taken as 100% according to the following formula. ΔQY〔%〕=(QY of the target example or comparative example / QY of comparative example 1)×100

[0273] (9-2) External quantum efficiency EQE A substrate having a cured film was obtained in the same manner as in the above (9-1). A light diffuser was placed on a backlight having a blue LED light with a peak wavelength of 450 nm as a point light source as a backlight unit. The backlight unit was mounted with the light diffuser facing upward, and a spectroradiometer ("SR-UL1R" manufactured by TOPCON Co., Ltd.) was set at a height of 60 cm from the surface of the light diffuser. A substrate having a cured film made of the composition was placed on the diffuser. In this state, the backlight was turned on, and the luminous intensity L of the cured film was measured as the integrated radiant flux of the light emitted from the cured film in the range of wavelengths of 480 nm to 780 nm. g 〔W·sr -1 m -2 ·nm -1 Next, a 5 cm square glass substrate (EAGLEXG; manufactured by Corning) was placed on the diffuser, the backlight was turned on, and the luminous intensity L of the backlight was measured. f 〔W·sr -1 m -2 ·nm -1 〕As the integrated radiant flux in the wavelength range of 380 nm to 480 nm. The luminous intensity was measured using the above-mentioned spectroradiometer ("SR-UL1R" manufactured by TOPCON Corporation). The external quantum efficiency EQE was calculated according to the following formula. EQE〔%〕=luminous intensity of cured film / luminous intensity of backlight=L g / L f

[0274] The EQE obtained in Comparative Example 1 was used as a reference, and ΔEQE was calculated as a relative value (%) according to the following formula, with ΔEQE of Comparative Example 1 being 100%. ΔEQE〔%〕=(EQE of the subject example or comparative example / EQE of comparative example 1)×100

[0275] (10) Evaluation of film appearance A substrate having a cured film was obtained in the same manner as in the above (9-1). The obtained cured film was observed using a microscope (500 times magnification; VHX-2000; manufactured by Keyence Co., Ltd.), and the appearance was evaluated according to the following evaluation criteria. The results are shown in Table 4. A: No abnormality was confirmed B: Confirm the presence of aggregates

[0276] <Preparation Example 1: Preparation of Quantum Dot (A1) Dispersion Liquid> A toluene dispersion a of quantum dots (A1) containing oleic acid (green luminescent InP / ZnSeS quantum dots) was prepared as an organic ligand (G1). When the luminescence spectrum of the quantum dots was measured, the maximum peak wavelength of the green luminescence peak was 530 nm and the half width of the green luminescence peak was 42 nm.

[0277] After removing toluene from the above-mentioned toluene dispersion a by vacuum distillation, 70 parts of cyclohexyl acetate (E2) were added to 30 parts of the total amount of quantum dots (A1) and organic ligands (G1) to prepare quantum dot (A1) dispersion b. The composition of quantum dot (A1) dispersion b is shown in Table 1.

[0278] [Table 1]

[0279] The composition ratio of quantum dots (A1) to organic ligand (G1) was determined by TG-DTA. The remaining amount after heating the mixture to 550°C at a heating rate of 5°C / min after toluene was removed was measured and the remaining amount was calculated as the weight of the organic ligand (G1).

[0280] <Synthesis Examples 1 to 7: Synthesis of Vinyl Copolymers (B1) to (B7)> In a nitrogen-substituted glove box, monomers ((b-1) to (b-3)) previously substituted with nitrogen, 2-methyl-2-n-butyltelluryl-ethyl propionate (BTEE), dibutyl ditelluride (DBDT), 2,2'-azobis(isobutyronitrile) (AIBN) and propylene glycol monomethyl ether acetate (PGMEA) were reacted to obtain a copolymer having the composition described in Table 2. After the reaction, the reaction solution was diluted with THF and injected into heptane with stirring. The precipitated polymer was filtered and dissolved in PGMEA after drying to obtain vinyl copolymer (B1) to (B7) solutions. The solid content of the vinyl copolymer (B1) to (B7) solution was 40% by mass.

[0281] Table 2 shows the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), acid value and tellurium compound content of the obtained vinyl copolymers (B1) to (B7).

[0282] [Table 2]

[0283] <Synthesis Examples 8 to 12: Synthesis of Vinyl Copolymers (B8) to (B12)> In a nitrogen-substituted glove box, monomers ((b-1) to (b-3)) substituted with nitrogen in advance, BTEE, DBDT, AIBN and PGMEA were reacted to obtain a copolymer intermediate having the composition described in Table 3. After the reaction was completed, the reaction solution was diluted with THF and injected into heptane under stirring. The precipitated polymer was filtered and dried to obtain a copolymer intermediate.

[0284] Next, the copolymer intermediate obtained above, the monomer (b-4) of the type and molar ratio described in Table 3, triethylamine (molar ratio relative to 1 mole of monomer (b-4): 0.20) and PGMEA were mixed under an atmospheric gas atmosphere, and reacted by stirring at 120° C. for 7 hours to prepare vinyl copolymer (B8) to (B12) solutions. The solid content of the vinyl copolymer (B8) to (B12) solution was 40% by mass.

[0285] The weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), ethylenic unsaturated bond equivalent, acid value and tellurium compound content of the obtained vinyl copolymers (B8) to (B12) are shown in Table 3.

[0286] <Synthesis Example 13: Synthesis of Vinyl Copolymer (B13)> In a nitrogen-substituted glove box, monomers ((b-1) to (b-3)) substituted with nitrogen in advance, BTEE, DBDT, AIBN and PGMEA were reacted to obtain a copolymer intermediate having the composition described in Table 3. After the reaction, the reaction solution was diluted with THF and injected into heptane under stirring. The precipitated polymer was filtered and dried to obtain a copolymer intermediate.

[0287] Next, the copolymer intermediate obtained above, the monomer (b-4) of the type and molar ratio described in Table 3, triethylamine (molar ratio relative to 1 mole of monomer (b-4): 0.20), 2,2,6,6-tetramethylpiperidin-1-oxyl radical (0.1 mass part relative to 100 mass parts of the copolymer intermediate) and PGMEA were mixed under an atmospheric gas atmosphere, and reacted by stirring at 120° C. for 7 hours to obtain a vinyl copolymer (B13) solution. The solid content of the vinyl copolymer (B13) solution was 40 mass%.

[0288] [Table 3]

[0289] The meanings of the abbreviations in Tables 2 and 3 are as follows. MAA: Methacrylic acid MMA: Methyl Methacrylate BMA: Butyl Methacrylate MOESA: 2-Methacryloyloxyethyl succinate MOEBDA: mono-2-(methacryloyloxy)ethyl phthalate GMA: Glycidyl Methacrylate ECHMA: 3,4-Epoxycyclohexylmethyl methacrylate ECHAA: 3,4-Epoxycyclohexylmethyl acrylate 4HBAGE: 4-Hydroxybutyl acrylate glycidyl ether

[0290] <Examples 1 to 8, Comparative Examples 1 to 5> For the quantum dot (A1) dispersion b, the components in Table 4 were mixed in the amounts described in the same table to prepare a composition. In Table 4, the number of components other than the solvent (E) represents the solid content conversion value. The compositions of Examples 1 to 8 and Comparative Examples 1 to 5 were the same except that the copolymer described in Table 4 (one of the vinyl copolymers (B1) to (B10)) was used as the vinyl copolymer (B).

[0291] The evaluation results of the pattern forming properties, luminescent properties, and appearance of the films formed by the compositions of Examples 1 to 8 and Comparative Examples 1 to 5 are shown in Table 4. In addition, since the pattern forming properties of Comparative Examples 2 and 3 were poor, the evaluation of luminescent properties was not performed. Regarding the pattern forming properties, in Comparative Example 2, the cured film remained at the site where the space should be formed. In Comparative Example 3, the cured film at the site where the line should be formed partially disappeared due to development.

[0292] [Table 4]

[0293] The details of the abbreviations of the components shown in Table 4 are as follows. Organic ligand (G1): Oleic acid Polymerizable compound (C1): Carboxyl group-containing multifunctional (meth)acrylate (trade name "Aronix M-510" manufactured by Toagosei Co., Ltd.) Polymerization initiator (D1): "Irgacure (registered trademark) OXE-02" manufactured by BASF Light scattering agent (F1): 60 parts of titanium oxide particles, 10 parts (converted to solid content) of vinyl copolymer (B), and 30 parts of PGMEA in total were mixed, and the titanium oxide particles were fully dispersed using a ball mill and used to prepare the composition. The number of parts of the light scattering agent (F1) listed in Table 4 is the number of parts of the titanium oxide particles. Antioxidant (H1): "SUMILIZER-GP" manufactured by Sumitomo Chemical Co., Ltd. Leveling agent (I1): polyether-modified silicone oil (trade name "Toray Silicone SH8400" manufactured by Dow Corning Toray Co., Ltd.) Solvent (E1): Propylene glycol monomethyl ether acetate (PGMEA) Solvent (E2): Cyclohexyl acetate

Claims

1. A composition comprising quantum dots (A) and a vinyl copolymer (B); The vinyl copolymer (B) has a structural unit derived from (meth)acrylic acid, a structural unit derived from a (meth)acrylate having a carboxyl group, and a structural unit derived from a (meth)acrylate having no carboxyl group, contains a tellurium compound, has a molecular weight distribution of 2.0 or less, and has an acid value of 100 mgKOH / g to 150 mgKOH / g.

2. The composition according to claim 1, wherein the vinyl copolymer (B) has structural units derived from monomers represented by formula (I), formula (II) and formula (III); In formula (I), X1 represents a hydrogen atom or a methyl group; In formula (II), X2 represents a hydrogen atom or a methyl group, Y1 represents a linear, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms, and Y2 represents a linear, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms; In the formula (III), X3 represents a hydrogen atom or a methyl group, and R1 represents a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms. 3 . The composition according to claim 1 , wherein the vinyl copolymer (B) further comprises a structural unit having an ultraviolet curable functional group. 4 . The composition according to claim 1 , wherein the vinyl copolymer (B) has a weight average molecular weight per mol of ethylenically unsaturated bonds, that is, an ethylenically unsaturated bond equivalent of more than 1,000 and not more than 8,000. 5 . The composition according to claim 1 , wherein the content of the tellurium compound in the vinyl copolymer (B) is more than 0 ppm and is 350 ppm or less, calculated as metal tellurium. The composition according to claim 1 , further comprising a polymerizable compound (C) and a polymerization initiator (D). The composition according to claim 1 , further comprising a solvent (E).

8. The composition according to claim 1, wherein the quantum dot (A) is at least one selected from the group consisting of compounds of Group 12 elements and Group 16 elements, compounds of Group 13 elements and Group 15 elements, compounds of Group 13 elements and Group 16 elements, and compounds of Group 14 elements and Group 16 elements. 9 . The composition according to claim 1 , wherein the content of the quantum dots (A) is 50 to 350 parts by mass based on 100 parts by mass of the vinyl copolymer (B). 10 . A film formed from the composition according to claim 1 .

11. A display device comprising the film according to claim 10.

Images