WO2012057104A1 - Triazine ring-containing polymer and film forming composition containing same - Google Patents

Triazine ring-containing polymer and film forming composition containing same Download PDF

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WO2012057104A1
WO2012057104A1 PCT/JP2011/074482 JP2011074482W WO2012057104A1 WO 2012057104 A1 WO2012057104 A1 WO 2012057104A1 JP 2011074482 W JP2011074482 W JP 2011074482W WO 2012057104 A1 WO2012057104 A1 WO 2012057104A1
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group
triazine ring
containing polymer
formula
carbon atoms
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PCT/JP2011/074482
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French (fr)
Japanese (ja)
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圭 安井
直也 西村
小澤　雅昭
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日産化学工業株式会社
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Priority to JP2012540858A priority Critical patent/JP5794235B2/en
Publication of WO2012057104A1 publication Critical patent/WO2012057104A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133345—Insulating layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8794—Arrangements for heating and cooling

Definitions

  • the present invention relates to a triazine ring-containing polymer and a film-forming composition containing the same.
  • Patent Document 1 a method for increasing the refractive index using a hybrid material obtained by mixing a siloxane polymer and a fine particle dispersion material in which zirconia or titania is dispersed has been reported.
  • Patent Document 2 a method of introducing a condensed cyclic skeleton having a high refractive index into a part of the siloxane polymer has been reported.
  • melamine resin is well known as a triazine resin, but its decomposition temperature is much lower than that of heat-resistant materials such as graphite.
  • aromatic polyimides and aromatic polyamides have been mainly used as heat-resistant organic materials composed of carbon and nitrogen. However, these materials have a linear structure, so that the heat-resistant temperature is not so high.
  • a triazine-based condensation material has also been reported as a nitrogen-containing polymer material having heat resistance (Patent Document 4).
  • hyperbranched polymers are roughly classified into hyperbranched polymers and dendrimers.
  • the hyperbranched polymer is, for example, an ABx type polyfunctional monomer (where A and B are functional groups that react with each other, and the number X of B is 2 or more) that has an irregular branched structure obtained by polymerizing. It is a branched polymer.
  • a dendrimer is a highly branched polymer having a regular branched structure. Hyperbranched polymers are characterized by being easier to synthesize than dendrimers and easier to synthesize high molecular weight polymers.
  • a hyperbranched polymer having a triazine ring has been reported as a flame retardant application (Non-patent Document 1).
  • the present invention has been made in view of the above circumstances, and a triazine that can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage by itself without adding a metal oxide.
  • An object of the present invention is to provide a ring-containing polymer and a film-forming composition containing the same.
  • a hyperbranched polymer including a repeating unit having a triazine ring and an aromatic ring has a high refractive index
  • the polymer alone has high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage.
  • PCT / JP2010 / 057771 has already been found to be suitable as a film-forming composition for producing an electronic device (PCT / JP2010 / 057771), but it is desired to further improve the solubility in a specific solvent. It was.
  • the present inventors can obtain a polymer having excellent solubility in various solvents by using a diamine compound having a fluorine atom, and also having this fluorine atom. It has been found that the refractive index can be adjusted while maintaining solubility by using a diamine compound and another aromatic diamine such as a phenylenediamine compound in combination and changing the ratio of use (copolymerization ratio). Was completed.
  • a triazine ring-containing polymer comprising a repeating unit structure represented by the following formula (1) or formula (2): ⁇ Wherein R, R ′, R ′′ and R ′ ′′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and Ar 1 represents a group represented by the formula (3) to Represents at least one selected from the group represented by (8), [Wherein, X 1 and X 2 each independently represent a fluoro group or a fluoroalkyl group having 1 to 10 carbon atoms, and R 1 to R 61 each independently represent a hydrogen atom, a halogen atom, W 1 and W 2 represent a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkoxy group which may have a branched structure having 1 to 10 carbon atoms.
  • Ar 2 represents at least one selected from the group represented by formulas (9) to (19).
  • R 62 to R 141 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group optionally having a branched structure of 1 to 10 carbon atoms, or 1 carbon atom.
  • R 145 to R 148 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom
  • Y 3 and Y 4 each independently represent an alkylene group that may have a single bond or a branched structure of 1 to 10 carbon atoms.
  • At least one terminal is an alkyl group, aralkyl group, aryl group, alkylamino group, alkoxysilyl group-containing alkylamino group, aralkylamino group, arylamino group, alkoxy group, aralkyloxy group, aryloxy group, or ester group. Any of the capped triazine ring-containing polymers of 1 to 9, 11.
  • triazine ring end Having at least one triazine ring end, and the triazine ring end is an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, an alkoxy group, an aralkyloxy group 10 triazine ring-containing polymers capped with groups, aryloxy groups, or ester groups, 12
  • a film-forming composition comprising any one of the triazine ring-containing polymers of 1 to 11, 13.
  • An electronic device comprising a substrate and 13 films formed on the substrate; 15.
  • An optical member comprising a substrate and 13 films formed on the substrate; 16.
  • a solid-state imaging device comprising a charge-coupled device or a complementary metal oxide semiconductor, comprising at least one layer of 13 films, 17.
  • a solid-state imaging device comprising 13 films as a planarizing layer on a color filter is provided.
  • the present invention it is possible to provide a triazine ring-containing polymer that can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage independently without using a metal oxide.
  • a polymer skeleton of the present invention high heat resistance and high transparency can be maintained even when 1) a secondary amine is used as a polymer spacer and 2) a primary amine is substituted at the terminal.
  • the hyperbranched polymer of the present invention exhibits a high refractive index because the tribranched structure and the aryl (Ar) portion are closely gathered to increase the electron density. It is done.
  • R and R ′ is a hydrogen atom (in the case of formula (1)), or when at least one of R, R ′, R ′′ and R ′ ′′ is a hydrogen atom (in formula (2))
  • the nitrogen atom on the triazine ring and the hydrogen atom of the amine site are hydrogen-bonded, and the triazine ring and the aryl (Ar) moiety are more closely gathered to increase the electron density. it is conceivable that.
  • a fluorine atom-containing diamine compound is used for at least a part of the diamine compound, various types including relatively low-polarity solvents that are widely used in the field of electronic devices despite being high molecular weight compounds.
  • it has excellent handling properties because it has a low viscosity when dissolved in a solvent.
  • it can express a high refractive index with a polymer alone without containing a metal oxide, even when a dry process such as etching or ashing is performed, the etch rate becomes constant, and a film with a uniform film thickness can be obtained. Increases process margin when manufacturing devices.
  • the triazine ring-containing polymer of the present invention can be used as a high heat resistant insulating material.
  • a film prepared using the triazine ring-containing polymer of the present invention having the above-described characteristics is a liquid crystal display, an organic electroluminescence (EL) display, an optical semiconductor (LED) element, a solid-state imaging element, an organic thin film solar cell, It can be suitably used as a member for producing electronic devices such as dye-sensitized solar cells and organic thin film transistors (TFTs).
  • a buried film and a planarizing film on a photodiode, a planarizing film before and after a color filter, a microlens, and a planarizing film and a conformal film on a microlens which are members of a solid-state imaging device that requires a high refractive index.
  • a buried film and a planarizing film on a photodiode, a planarizing film before and after a color filter, a microlens, and a planarizing film and a conformal film on a microlens which are members of a solid-state imaging device that requires a high refractive index.
  • FIG. 1 is a diagram showing a 1 H-NMR spectrum of a polymer compound [1] obtained in Example 1.
  • FIG. 3 is a diagram showing a 1 H-NMR spectrum of a polymer compound [2] obtained in Example 2.
  • FIG. 3 is a diagram showing a 1 H-NMR spectrum of a polymer compound [3] obtained in Example 3.
  • FIG. 4 is a diagram showing a 1 H-NMR spectrum of a polymer compound [4] obtained in Example 4.
  • FIG. 6 is a diagram showing a 1 H-NMR spectrum of a polymer compound [5] obtained in Example 5.
  • FIG. 2 is a diagram showing a 1 H-NMR spectrum of a polymer compound [6] obtained in Comparative Example 1.
  • FIG. 1 is a diagram showing a 1 H-NMR spectrum of a polymer compound [1] obtained in Example 1.
  • FIG. 3 is a diagram showing a 1 H-NMR spectrum of a polymer compound [2] obtained in Example 2.
  • FIG. 3 is
  • the triazine ring-containing polymer according to the present invention includes a repeating unit structure represented by the following formula (1) or (2).
  • R, R ′, R ′′, and R ′ ′′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms in view of further improving the heat resistance of the polymer. Is even more preferable.
  • the structure may be any of a chain, a branch, and a ring.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl group.
  • -Cyclopropyl group 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl -N-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl -Cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl Ru-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group,
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms in view of further improving the heat resistance of the polymer. preferable.
  • the structure of the alkyl moiety may be any of a chain, a branch, and a ring.
  • alkoxy group examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, 1-methyl- n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl -N-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-di- Til-n-butoxy group,
  • the number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 to 40. In view of further improving the heat resistance of the polymer, 6 to 16 carbon atoms are more preferable, and 6 to 13 are even more preferable. preferable.
  • Specific examples of the aryl group include phenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxy group.
  • the number of carbon atoms of the aralkyl group is not particularly limited, but preferably 7 to 20 carbon atoms, and the alkyl portion may be linear, branched or cyclic. Specific examples thereof include benzyl group, p-methylphenylmethyl group, m-methylphenylmethyl group, o-ethylphenylmethyl group, m-ethylphenylmethyl group, p-ethylphenylmethyl group, 2-propylphenylmethyl group. 4-isopropylphenylmethyl group, 4-isobutylphenylmethyl group, ⁇ -naphthylmethyl group and the like.
  • Ar 1 represents at least one selected from the group represented by formulas (3) to (8), and more preferably at least one selected from the group represented by formulas (3) and (4). At least one selected from the group represented by formulas (3 ′) and (4 ′) is even more preferable.
  • X 1 and X 2 each independently represent a fluoro group or a fluoroalkyl group having 1 to 10 carbon atoms
  • R 1 to R 61 each independently represent a hydrogen atom, a halogen atom, a carboxyl group, A sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkoxy group which may have a branched structure having 1 to 10 carbon atoms, wherein W 1 and W 2 are Independently represents O, S, CH 2 or SO 2 .
  • the fluoroalkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and examples thereof include trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, hepta.
  • a perfluoroalkyl group having 1 to 10 carbon atoms is preferable, a perfluoroalkyl group having 1 to 5 carbon atoms is particularly preferable, and a trifluoroalkyl group is more preferable.
  • a fluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group are preferred.
  • Examples of the alkyl group and alkoxy group are the same as those described above.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Ar 1 is preferably those represented by the following formula, but are not limited thereto.
  • the above formula (2) is a copolymer-type hyperbranched polymer obtained using two kinds of diamines, and Ar 2 is at least one selected from the group consisting of formulas (9) to (19). Among these, the group represented by the formula (9) is more preferable.
  • R 62 to R 141 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
  • W 3 and W 4 are each independently a single bond
  • CR 142 R 143 R 142 and R 143 are each independently a hydrogen atom or carbon
  • An alkyl group which may have a branched structure of 1 to 10 (note that these may be combined to form a ring)
  • C ⁇ O, O, S, SO, SO 2 or NR 144 R 144 represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms.
  • Examples of the halogen atom, alkyl group and alkoxy group are the same as those described above.
  • Y 1 and Y 2 each independently represent a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (20).
  • R 145 to R 148 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
  • An alkoxy group which may have a branched structure is represented, and Y 3 and Y 4 each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms. Examples of the halogen atom, alkyl group and alkoxy group are the same as those described above.
  • alkylene group that may have a branched structure having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.
  • aryl group represented by the above formulas (9) to (19) include those represented by the following formula, but are not limited thereto.
  • an aryl group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.
  • the weight average molecular weight of the triazine ring-containing hyperbranched polymer of the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000, and further improves heat resistance and shrinkage. 2,000 or more is preferable from the viewpoint of lowering the rate, 50,000 or less is preferable, and 30,000 or less is more preferable, from the viewpoint of further increasing the solubility and lowering the viscosity of the obtained solution. Is more preferable.
  • the weight average molecular weight in this invention is an average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (henceforth GPC) analysis.
  • the triazine ring-containing polymer represented by the formula (1) of the present invention can be obtained by reacting cyanuric halide with a fluorine atom-containing diamine compound.
  • the hyperbranched polymer having the structure (22 ′) can be obtained by reacting cyanuric halide (25) and a fluorine atom-containing diamine compound (26) in an appropriate organic solvent.
  • the fluorine atom-containing diamine that can be used in the present invention is not particularly limited, and examples thereof include 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane and 3,5-diaminobenzotrifluoride.
  • the hyperbranched polymer having a repeating structure (22 ′) is obtained by using an equivalent amount of cyanuric halide (25) and fluorine atom-containing diamine compound (26) in an appropriate organic solvent. It can also be synthesized from the compound (27) obtained by the reaction.
  • the copolymer type triazine ring-containing polymer represented by the formula (2) of the present invention can be obtained by reacting cyanuric halide with at least two kinds of diaminoaryl compounds.
  • the hyperbranched polymer having a repeating structure (24 ′) comprises cyanuric halide (25), fluorine atom-containing diamine compound (26) and m-phenylenediamine compound (31) in a suitable organic solvent. It can obtain by making it react.
  • the hyperbranched polymer having a repeating structure (24 ′) is obtained by using an equivalent amount of cyanuric halide (25) and a fluorine atom-containing diamine compound (26) in an appropriate organic solvent.
  • the hyperbranched polymer of the present invention can be produced inexpensively, easily and safely. Since this production method is significantly shorter than the reaction time for synthesizing a general polymer, it is a production method suitable for environmental considerations in recent years and can reduce CO 2 emissions. Moreover, stable production is possible even if the production scale is greatly increased, and the stable supply system at the industrialization level is not impaired.
  • the amount of each raw material charged is arbitrary as long as the desired hyperbranched polymer is obtained, but the diamino compound (26) 0.01 relative to 1 equivalent of the cyanuric halide (25). ⁇ 10 equivalents are preferred.
  • the diamino compound (26) in an amount of less than 3 equivalents relative to 2 equivalents of cyanuric halide (25).
  • cyanuric halide (25) in an amount of less than 2 equivalents relative to 3 equivalents of diamino compound (26).
  • the amount of each raw material charged is arbitrary as long as the desired hyperbranched polymer can be obtained, but the diamino compound (26) 0 with respect to 1 equivalent of the cyanuric halide (25). .01 to 10 equivalents are preferred.
  • the amount of each raw material charged is arbitrary as long as the target polymer is obtained, but the m-phenylenediamine compound (31) is used per 1 equivalent of cyanuric halide (25).
  • the total amount of the diamino compound (26) is preferably 0.01 to 10 equivalents, but the total amount of the m-phenylenediamine compound (31) and the diamino compound (26) is 3 equivalents with respect to 2 equivalents of the cyanuric halide (25). It is preferred to avoid using it. By shifting the equivalent of the functional group, formation of a gelled product can be prevented.
  • the total amount of m-phenylenediamine compound (31) and diamino compound (26) is less than 3 equivalents relative to 2 equivalents of cyanuric halide (25). It is preferable to use it in the quantity.
  • the total amount of m-phenylenediamine compound (31) and diamino compound (26) is less than 2 equivalents of cyanuric halide (25). It is preferable to use it in an amount.
  • the amount of each raw material charged is arbitrary as long as the desired hyperbranched polymer is obtained, but the diamino compound (31), (26) 0.01 to 10 equivalents are preferred respectively.
  • the molecular weight of the resulting hyperbranched polymer can be easily adjusted by appropriately adjusting the amounts of the diamino compound and the cyanuric halide.
  • a hyperbranched polymer having a large number of triazine ring ends is preferable in terms of having excellent transparency and light resistance.
  • organic solvent various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran, dioxane, dimethyl sulfoxide; N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea.
  • N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and mixed solvents thereof are preferable, and N, N-dimethylacetamide, N-methyl-2-pyrrolidone are particularly preferable. Is preferred.
  • the reaction temperature ranges from the melting point of the solvent used to the boiling point of the solvent. However, it is preferably about 0 to 150 ° C., more preferably 60 to 100 ° C. Particularly in the reactions of Schemes 1 and 3, the reaction temperature is preferably 60 to 150 ° C., preferably 80 to 150 ° C., and preferably 80 to 120 ° C. from the viewpoint of suppressing linearity and increasing the degree of branching.
  • the reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent. It is preferably about ⁇ 50 to 50 ° C., more preferably about ⁇ 20 to 50 ° C., still more preferably about ⁇ 10 to 50 ° C., and further preferably ⁇ 10 to 10 ° C.
  • the component previously dissolved in the solvent and the component added later may be either, but the diamino compounds (26) and (31) are added to the cooled solution of cyanuric halide (25).
  • the method of adding is preferable.
  • Components added later may be added neat or in a solution dissolved in an organic solvent as described above, but the latter method is preferred in view of ease of operation and ease of reaction control. It is.
  • the addition may be gradually added by dropping or the like, or may be added all at once.
  • the amount of base added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, per 1 equivalent of cyanuric halide (25). These bases may be used as an aqueous solution. In the polymer obtained, it is preferable that no raw material components remain, but some raw materials may remain as long as the effects of the present invention are not impaired. In any of the scheme methods, after completion of the reaction, the product can be easily purified by a reprecipitation method or the like.
  • At least one of the halogen atoms of the terminal triazine ring is substituted with an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, You may cap by an alkoxy group, an aralkyloxy group, an aryloxy group, an ester group, etc.
  • an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, and an arylamino group are preferable, an alkylamino group and an arylamino group are more preferable, and an arylamino group is further preferable.
  • ester group examples include a methoxycarbonyl group and an ethoxycarbonyl group.
  • alkylamino group include methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, s-butylamino group, t-butylamino group, n -Pentylamino group, 1-methyl-n-butylamino group, 2-methyl-n-butylamino group, 3-methyl-n-butylamino group, 1,1-dimethyl-n-propylamino group, 1,2 -Dimethyl-n-propylamino group, 2,2-dimethyl-n-propylamino group, 1-ethyl-n-propylamino group, n-hexylamino group, 1-methyl-n-pentylamino group, 2-methyl -N-p
  • aralkylamino group examples include benzylamino group, methoxycarbonylphenylmethylamino group, ethoxycarbonylphenylmethylamino group, p-methylphenylmethylamino group, m-methylphenylmethylamino group, and o-ethylphenylmethylamino group.
  • arylamino group examples include phenylamino group, methoxycarbonylphenylamino group, ethoxycarbonylphenylamino group, naphthylamino group, methoxycarbonylnaphthylamino group, ethoxycarbonylnaphthylamino group, anthranylamino group, pyrenylamino group, biphenylamino. Group, terphenylamino group, fluorenylamino group and the like.
  • the alkoxysilyl group-containing alkylamino group may be any of a monoalkoxysilyl group-containing alkylamino group, a dialkoxysilyl group-containing alkylamino group, or a trialkoxysilyl group-containing alkylamino group.
  • aryloxy group examples include a phenoxy group, a naphthoxy group, an anthranyloxy group, a pyrenyloxy group, a biphenyloxy group, a terphenyloxy group, and a fluorenyloxy group.
  • aralkyloxy group examples include benzyloxy group, p-methylphenylmethyloxy group, m-methylphenylmethyloxy group, o-ethylphenylmethyloxy group, m-ethylphenylmethyloxy group, p-ethylphenylmethyl group.
  • Examples include an oxy group, 2-propylphenylmethyloxy group, 4-isopropylphenylmethyloxy group, 4-isobutylphenylmethyloxy group, ⁇ -naphthylmethyloxy group, and the like.
  • examples of the alkyl group, the aralkyl group, and the aryl group include the same groups as those described above.
  • the organic monoamine is charged simultaneously, that is, by reacting the cyanuric halide compound with the diamino compound in the presence of the organic monoamine, the rigidity of the hyperbranched polymer is relaxed and the degree of branching is low.
  • a soft hyperbranched polymer can be obtained.
  • the hyperbranched polymer obtained by this method has excellent solubility in a solvent (inhibition of aggregation) and crosslinkability with a crosslinking agent, and is particularly used when used as a composition in combination with a crosslinking agent described later. It is advantageous.
  • the organic monoamine any of alkyl monoamine, aralkyl monoamine, and aryl monoamine can be used.
  • Alkyl monoamines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine, 1-methyl-n-butylamine, 2-methyl- n-butylamine, 3-methyl-n-butylamine, 1,1-dimethyl-n-propylamine, 1,2-dimethyl-n-propylamine, 2,2-dimethyl-n-propylamine, 1-ethyl-n -Propylamine, n-hexylamine, 1-methyl-n-pentylamine, 2-methyl-n-pentylamine, 3-methyl-n-pentylamine, 4-methyl-n-pentylamine, 1,1-dimethyl -N-butylamine, 1,2-dimethyl-n-butylamine, 1,3-dimethyl-n Butylamine, 2,
  • aralkyl monoamines include benzylamine, p-methoxycarbonylbenzylamine, p-ethoxycarbonylbenzylamine, p-methylbenzylamine, m-methylbenzylamine, o-methoxybenzylamine and the like.
  • aryl monoamine examples include aniline, p-methoxycarbonylaniline, p-ethoxycarbonylaniline, p-methoxyaniline, 1-naphthylamine, 2-naphthylamine, anthranylamine, 1-aminopyrene, 4-biphenylylamine, o- And phenylaniline, 4-amino-p-terphenyl, 2-aminofluorene, and the like.
  • the amount of the organic monoamine used is preferably 0.05 to 500 equivalents, more preferably 0.05 to 120 equivalents, and even more preferably 0.05 to 50 equivalents per equivalent of the cyanuric halide compound.
  • the reaction temperature is preferably 60 to 150 ° C., preferably 80 to 150 ° C., and preferably 80 to 120 ° C. from the viewpoint of suppressing linearity and increasing the degree of branching.
  • the mixing of the three components of the organic monoamine, the halogenated cyanuric compound, and the diamine compound may be performed at a low temperature.
  • the temperature is preferably about ⁇ 50 to 50 ° C., and about ⁇ 20 to 50 ° C. More preferred is ⁇ 20 to 10 ° C. After the low temperature charging, it is preferable to carry out the reaction by raising the temperature to the polymerization temperature at once (in one step).
  • the two components of the cyanuric halide compound and the diamine compound may be mixed at a low temperature.
  • the temperature is preferably about ⁇ 50 to 50 ° C., more preferably about ⁇ 20 to 50 ° C., 20 to 10 ° C. is more preferable. It is preferable to carry out the reaction by adding an organic monoamine after the low-temperature charging and raising the temperature to a temperature for polymerization (in one step). Moreover, you may perform reaction which makes a halogenated cyanuric compound and a diamine compound react in presence of such an organic monoamine using the organic solvent similar to the above-mentioned.
  • the polymer of the present invention described above can be used as a composition mixed with other compounds, and examples thereof include a composition with a leveling agent, a surfactant, a crosslinking agent, a resin and the like. These compositions can be used as a film-forming composition, and can be suitably used as a film-forming composition (also referred to as a polymer varnish) dissolved in various solvents.
  • the solvent used for dissolving the polymer may be the same as or different from the solvent used during the polymerization.
  • the solvent is not particularly limited as long as the compatibility with the polymer is not impaired, and one kind or a plurality of kinds can be arbitrarily selected and used.
  • solvents include toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether.
  • Ethylene glycol monoethyl ether ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dip Pyrene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1 -Methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfury
  • the solid content concentration in the film-forming composition is not particularly limited as long as it does not affect the storage stability, and may be appropriately set according to the target film thickness.
  • the solid content concentration is preferably 0.1 to 50% by mass, and more preferably 0.1 to 20% by mass.
  • the film-forming composition of the present invention contains other components other than the triazine ring-containing polymer and the solvent, for example, a leveling agent, a surfactant, a crosslinking agent, and the like. Also good.
  • surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol Polyoxyethylene alkyl allyl ethers such as ethers; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethyleneso Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, trade name
  • Fluorosurfactant such as FLORARD FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) Agent Ganosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 ( Big Chemie Japan Co., Ltd.).
  • surfactants may be used alone or in combination of two or more.
  • the amount of the surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. Even more preferred.
  • the crosslinking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with the triazine ring-containing polymer of the present invention.
  • examples of such compounds include melamine compounds having a crosslinkable substituent such as a methylol group and methoxymethyl group, substituted urea compounds, compounds containing a crosslinkable substituent such as an epoxy group or an oxetane group, and blocked isocyanates.
  • the blocked isocyanate group is also preferable from the viewpoint that the refractive index does not decrease because it is crosslinked by a urea bond and has a carbonyl group.
  • an epoxy compound it has two or more epoxy groups in one molecule, and when exposed to a high temperature during thermosetting, the epoxy is ring-opened and crosslinked with the triazine ring-containing polymer of the present invention by an addition reaction. The reaction proceeds.
  • crosslinking agent examples include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol Diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4 '-Methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentae Examples include lithi
  • epoxy resins having at least two epoxy groups YH-434, YH434L (manufactured by Tohto Kasei Co., Ltd.), epoxy resins having a cyclohexene oxide structure, Epolide GT-401 and GT -403, GT-301, GT-302, Celoxide 2021, 3000 (manufactured by Daicel Chemical Industries, Ltd.), bisphenol A type epoxy resin, Epicoat (currently jER) 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (Japan Epoxy Resin Co., Ltd.), Bisphenol F type epoxy resin, Epicoat (currently jER) 807 (Japan Epoxy Resin Co., Ltd.) , Epicoat (a phenol novolac type epoxy resin) , JER) 152, 154 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPPN 201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.
  • EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-522, EX-421, EX-313, EX-314, EX-321 can also be used.
  • the acid anhydride compound is a carboxylic acid anhydride obtained by dehydrating and condensing two molecules of carboxylic acid. When exposed to a high temperature during thermosetting, the anhydride ring is opened and the triazine ring of the present invention is contained. A crosslinking reaction proceeds with the polymer by an addition reaction.
  • Specific examples of the acid anhydride compound include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, maleic anhydride.
  • (meth) acrylic compound As a (meth) acrylic compound, it has two or more (meth) acrylic groups in one molecule, and when exposed to a high temperature during thermosetting, it undergoes an addition reaction with the triazine ring-containing polymer of the present invention. The crosslinking reaction proceeds.
  • Examples of the compound having a (meth) acryl group include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, and ethoxylated tri Methylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerol mono Ethylene oxide polyacrylate Polyglycerin polyethylene glycol polyacrylate, dipentaerythrito
  • the compound having the (meth) acryl group is available as a commercial product. Specific examples thereof include NK ester A-200, same A-400, same A-600, same A-1000, same A- TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A- BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE-100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A -GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO, ATM-4E, ATM-35E KAYAR) D (registered trademark) DPEA-12, PEG400DA, THE-330, RP-1040 (above, Nippon Kayaku Co., Ltd.), M-210, M-350 (above, Toagosei Co
  • the isocyanate group (—NCO) has two or more blocked isocyanate groups blocked by an appropriate protective group in one molecule and is exposed to a high temperature during thermal curing
  • the protecting group (block portion) is dissociated by thermal dissociation, and the resulting isocyanate group causes a crosslinking reaction with the resin.
  • two or more groups represented by the following formula in one molecule (note these The groups may be the same or different from each other).
  • R b represents an organic group in the block part.
  • Such a compound can be obtained, for example, by reacting an appropriate blocking agent with a compound having two or more isocyanate groups in one molecule.
  • the compound having two or more isocyanate groups in one molecule include, for example, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), polyisocyanate of trimethylhexamethylene diisocyanate, and dimers thereof. , Trimers, and reaction products of these with diols, triols, diamines, or triamines.
  • the blocking agent examples include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol; phenol, o-nitrophenol , P-chlorophenol, phenols such as o-, m- or p-cresol; lactams such as ⁇ -caprolactam, oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime
  • pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole
  • thiols such as dodecanethiol and benzenethiol.
  • a compound containing a blocked isocyanate is also available as a commercial product.
  • Specific examples thereof include B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B -7005, B-7030, B-7075, B-5010 (Mitsui Chemicals Polyurethane Co., Ltd.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (above, manufactured by Asahi Kasei Chemicals Corporation), Karenz MOI-BM (registered trademark) (above, manufactured by Showa Denko Co., Ltd.), and the like.
  • an aminoplast compound As an aminoplast compound, it has two or more methoxymethylene groups in one molecule, and when exposed to a high temperature during thermosetting, it undergoes a crosslinking reaction by a demethanol condensation reaction with the triazine ring-containing polymer of the present invention. Is something that progresses.
  • Examples of the melamine-based compound include Cymel series such as hexamethoxymethylmelamine CYMEL (registered trademark) 303, tetrabutoxymethylglycoluril 1170, tetramethoxymethylbenzoguanamine 1123 (above, manufactured by Nihon Cytec Industries, Ltd.), Nicalac (registered trademark) MW-30HM, MW-390, MW-100LM, MX-750LM, which are methylated melamine resins, MX-270, MX-280, MX-290, which are methylated urea resins. (Nicarak series, etc., manufactured by Sanwa Chemical Co., Ltd.).
  • Cymel series such as hexamethoxymethylmelamine CYMEL (registered trademark) 303, tetrabutoxymethylglycoluril 1170, tetramethoxymethylbenzoguanamine 1123 (above, manufactured by Nihon Cytec Industries, Ltd.), Nicalac (register
  • the oxetane compound has two or more oxetanyl groups in one molecule and undergoes a crosslinking reaction by an addition reaction with the triazine ring-containing polymer of the present invention when exposed to a high temperature during thermosetting. It is.
  • the compound having an oxetane group include OX-221-containing oxetane group, OX-SQ-H, and OX-SC (manufactured by Toagosei Co., Ltd.).
  • the phenoplast compound has two or more hydroxymethylene groups in one molecule and undergoes a crosslinking reaction by dehydration condensation reaction with the triazine ring-containing polymer of the present invention when exposed to a high temperature during thermosetting. It is a progression.
  • phenoplast compound examples include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, Bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane, bis (3-formyl-4-hydroxyphenyl) methane Bis (4-hydroxy-2,5-dimethylphenyl) formylmethane, ⁇ , ⁇ -bis (4-hydroxy-2,5-dimethylphenyl) -4-formyltoluene and the like.
  • the phenoplast compound is also available as a commercial product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF. BI25X-TPA (above, manufactured by Asahi Organic Materials Co., Ltd.).
  • crosslinking agents may be used alone or in combination of two or more.
  • the amount of the crosslinking agent used is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer, but considering the solvent resistance, the lower limit is preferably 10 parts by mass, more preferably 20 parts by mass. Furthermore, in consideration of controlling the refractive index, the upper limit is preferably 50 parts by mass, more preferably 30 parts by mass.
  • the crosslinking agent and the reactive terminal substituent of the triazine ring-containing polymer react with each other, and effects such as improved film density, improved heat resistance, and improved thermal relaxation ability can be achieved There is.
  • the said other component can be added at the arbitrary processes at the time of preparing the composition of this invention.
  • the film-forming composition of the present invention can be applied to a substrate and then heated as necessary to form a desired film.
  • the coating method of the composition is arbitrary, for example, spin coating method, dip method, flow coating method, ink jet method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer printing method, brush Methods such as coating, blade coating, and air knife coating can be employed.
  • the firing temperature is not particularly limited for the purpose of evaporating the solvent, and can be performed at 40 to 400 ° C., for example. In these cases, the temperature may be changed in two or more steps for the purpose of expressing a higher uniform film forming property or allowing the reaction to proceed on the substrate.
  • the baking method is not particularly limited, and for example, it may be evaporated using a hot plate or an oven in an appropriate atmosphere such as air, an inert gas such as nitrogen, or in a vacuum.
  • the firing temperature and firing time may be selected in accordance with the process steps of the target electronic device, and the firing conditions may be selected so that the physical properties of the obtained film meet the required characteristics of the electronic device.
  • the film made of the composition of the present invention thus obtained can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage, so that it can be used for liquid crystal displays, organic electroluminescence (EL ) It can be suitably used as a member for producing electronic devices such as displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin film solar cells, dye-sensitized solar cells, and organic thin film transistors (TFTs).
  • LED optical semiconductor
  • TFTs organic thin film transistors
  • thermoplastic resin examples include polyolefin resins such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer); PS (polystyrene) Polystyrene resins such as HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer); polycarbonate resin; Polyvinyl resin; Polyamide resin; (Meth) acrylic resin such as PMMA (polymethyl methacrylate); PET (polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate
  • thermosetting resins examples include phenol resin, urea resin, melamine resin, unsaturated polyester resin. , Polyurethane resin, epoxy resin and the like. These resins may be used alone or in combination of two or more, and the amount used is preferably 1 to 10,000 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. The amount is preferably 1 to 1,000 parts by mass.
  • a composition with a (meth) acrylic resin can be obtained by blending a (meth) acrylate compound into the composition and polymerizing the (meth) acrylate compound.
  • (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri Oxyethyl (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, tricyclodecany
  • Polymerization of these (meth) acrylate compounds can be carried out by light irradiation or heating in the presence of a photo radical initiator or a heat radical initiator.
  • a photo radical initiator or a heat radical initiator examples include acetophenones, benzophenones, Michler's benzoylbenzoate, amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.
  • photocleavable photoradical polymerization initiators are preferred.
  • the photocleavable photoradical polymerization initiator is described in the latest UV curing technology (p. 159, publisher: Kazuhiro Takahisa, publisher: Technical Information Association, Inc., published in 1991).
  • radical photopolymerization initiators are, for example, trade names: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG24-61, Darocur, manufactured by Ciba Japan 1116, 1173, manufactured by BASF, Inc.
  • Product name Lucillin TPO, manufactured by UCB, Inc.
  • Product name Ubekrill P36, manufactured by Fratteri Lamberti, Inc.
  • the photopolymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylate compound.
  • the solvent used for the polymerization include the same solvents as those exemplified above for the film-forming composition.
  • the obtained polymer compound [1] is a compound having a structural unit represented by the formula (1).
  • the weight average molecular weight Mw measured by polystyrene conversion by GPC of the high molecular compound [1] was 8,900, and the polydispersity Mw / Mn was 4.92.
  • the 5% weight reduction temperature by TG-DTA was 339 ° C.
  • the measurement result of 1 H-NMR spectrum is shown in FIG.
  • the obtained polymer compound [1] is a compound having a structural unit represented by the formula (2).
  • the weight average molecular weight Mw measured by polystyrene conversion by GPC of the high molecular compound [2] was 4,600, and the polydispersity Mw / Mn was 2.27.
  • the 5% weight reduction temperature by TG-DTA was 405 ° C.
  • aniline (7.58 g, 81.3 mmol, manufactured by Junsei Chemical Co., Ltd.) was added and the mixture was stirred for 30 minutes to stop the polymerization.
  • a 28% aqueous ammonia solution (4.94 g) was reprecipitated in a mixed solution dissolved in 490 mL of water and 165 mL of methanol.
  • the precipitate was filtered, redissolved in 78 mL of THF, and reprecipitated in 560 mL of ion exchange water.
  • the resulting precipitate was filtered and dried in a vacuum dryer at 120 ° C. for 6 hours to obtain 8.1 g of the intended polymer compound [3].
  • the measurement result of 1 H-NMR spectrum is shown in FIG.
  • the obtained polymer compound [3] is a compound having a structural unit represented by the formula (2).
  • the weight average molecular weight Mw measured in terms of polystyrene by GPC of the polymer compound [3] was 6,200, and the polydispersity Mw / Mn was 3.60.
  • the 5% weight loss temperature by TG-DTA was 417 ° C.
  • the obtained polymer compound [4] is a compound having a structural unit represented by the formula (1).
  • the weight average molecular weight Mw measured by polystyrene conversion by GPC of the high molecular compound [4] was 1,100, and the polydispersity Mw / Mn was 1.43.
  • the 5% weight loss temperature by TG-DTA was 358 ° C.
  • the obtained polymer compound [5] is a compound having a structural unit represented by the formula (5).
  • the weight average molecular weight Mw measured by polystyrene conversion by GPC of the high molecular compound [5] was 1,500, and the polydispersity Mw / Mn was 1.40.
  • the 5% weight reduction temperature by TG-DTA was 352 ° C.
  • each of the polymer compounds obtained in Examples 1 to 5 has a high refractive index exceeding 1.6. Further, from the results of Examples 2 and 3, the refractive index increases when the use ratio of p-phenylenediamine is increased, and the refractive index of the obtained hyperbranched polymer can be adjusted by changing the copolymerization ratio. I know that there is. As will be described later, the solubility in various organic solvents does not decrease even if the content ratio of the phenylenediamine structure increases.
  • the weight average molecular weight Mw measured by polystyrene conversion by GPC of the high molecular compound [6] was 2,300, and the polydispersity Mw / Mn was 1.75.
  • the GPC measurement was performed under the following conditions. [GPC] Equipment: HLC-8200 GPC manufactured by Tosoh Corporation Column: Shodex OHpak SB-803HQ + SB-804HQ Column temperature: 40 ° C Solvent: Dimethylformamide Detector: UV (254 nm) Calibration curve: Standard polystyrene
  • the polymer compound of the present invention using a diamine compound containing a fluorine atom has better solubility in an organic solvent than the polymer compound of a comparative example using p-phenylenediamine.

Abstract

A polymer which contains a repeating unit structure having a triazine ring such as a repeating unit structure represented by formula (21) is capable of exhibiting high heat resistance, high transparency, high refractive index, high solubility and low volumetric shrinkage by itself, and is suitable for use as one component of a film forming composition.

Description

トリアジン環含有重合体およびそれを含む膜形成用組成物Triazine ring-containing polymer and film-forming composition containing the same
　本発明は、トリアジン環含有重合体およびそれを含む膜形成用組成物に関する。 The present invention relates to a triazine ring-containing polymer and a film-forming composition containing the same.
　これまで高分子化合物を高機能化する試みが種々行われてきている。例えば、高分子化合物を高屈折率化する方法として、芳香族環、ハロゲン原子、硫黄原子を導入する試みがなされている。中でも、硫黄原子を導入したエピスルフィド高分子化合物およびチオウレタン高分子化合物は、眼鏡用高屈折率レンズとして実用化されている。 Until now, various attempts have been made to improve the functionality of polymer compounds. For example, an attempt to introduce an aromatic ring, a halogen atom, or a sulfur atom has been made as a method for increasing the refractive index of a polymer compound. Among these, episulfide polymer compounds and thiourethane polymer compounds into which sulfur atoms are introduced have been put to practical use as high-refractive-index lenses for spectacles.
　また、高分子化合物のさらなる高屈折率化を達成し得る最も有力な方法として、無機の金属酸化物を用いる方法が知られている。
　例えば、シロキサンポリマーと、ジルコニアまたはチタニアなどを分散させた微粒子分散材料とを混合してなるハイブリッド材料を用いて屈折率を高める手法が報告されている（特許文献１）。
　さらに、シロキサンポリマーの一部に高屈折率な縮合環状骨格を導入する手法も報告されている（特許文献２）。 In addition, a method using an inorganic metal oxide is known as the most effective method capable of achieving a higher refractive index of a polymer compound.
For example, a technique for increasing the refractive index using a hybrid material obtained by mixing a siloxane polymer and a fine particle dispersion material in which zirconia or titania is dispersed has been reported (Patent Document 1).
Furthermore, a method of introducing a condensed cyclic skeleton having a high refractive index into a part of the siloxane polymer has been reported (Patent Document 2).
　また、高分子化合物に耐熱性を付与するための試みも数多くなされており、具体的には、芳香族環を導入することで、高分子化合物の耐熱性を向上し得ることがよく知られている。例えば、置換アリーレン繰り返し単位を主鎖に有するポリアリーレンコポリマーが報告され（特許文献３）、この高分子化合物は主として耐熱性プラスチックへの応用が期待されている。 There have also been many attempts to impart heat resistance to polymer compounds. Specifically, it is well known that the heat resistance of polymer compounds can be improved by introducing an aromatic ring. Yes. For example, a polyarylene copolymer having a substituted arylene repeating unit in the main chain has been reported (Patent Document 3), and this polymer compound is expected to be applied mainly to heat-resistant plastics.
　一方、メラミン樹脂は、トリアジン系の樹脂としてよく知られているが、黒鉛などの耐熱性材料に比べて遥かに分解温度が低い。
　これまで炭素および窒素からなる耐熱性有機材料としては、芳香族ポリイミドや芳香族ポリアミドが主として用いられているが、これらの材料は直鎖構造を有しているため耐熱温度はそれほど高くない。
　また、耐熱性を有する含窒素高分子材料としてトリアジン系縮合材料も報告されている（特許文献４）。 On the other hand, melamine resin is well known as a triazine resin, but its decomposition temperature is much lower than that of heat-resistant materials such as graphite.
Up to now, aromatic polyimides and aromatic polyamides have been mainly used as heat-resistant organic materials composed of carbon and nitrogen. However, these materials have a linear structure, so that the heat-resistant temperature is not so high.
A triazine-based condensation material has also been reported as a nitrogen-containing polymer material having heat resistance (Patent Document 4).
　ところで、近年、液晶ディスプレイ、有機エレクトロルミネッセンス（ＥＬ）ディスプレイ、光半導体（ＬＥＤ）素子、固体撮像素子、有機薄膜太陽電池、色素増感太陽電池、および有機薄膜トランジスタ（ＴＦＴ）等の電子デバイスを開発する際に、高機能な高分子材料が要求されるようになってきた。
　求められる具体的な特性としては、１）耐熱性、２）透明性、３）高屈折率、４）高溶解性、５）低体積収縮率などが挙げられる。 Recently, electronic devices such as liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin film solar cells, dye-sensitized solar cells, and organic thin film transistors (TFTs) have been developed. At the same time, high-performance polymer materials have been required.
Specific characteristics required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, and 5) low volume shrinkage.
　ところで、高分岐ポリマーは、ハイパーブランチポリマーとデンドリマーとに大別される。
　ハイパーブランチポリマーとは、例えば、ＡＢｘ型の多官能性モノマー（ここでＡとＢは互いに反応する官能基、Ｂの数Ｘは２以上）を重合させて得られる不規則な分岐構造を有する高分岐ポリマーである。
　一方、デンドリマーとは、規則的な分岐構造を有する高分岐ポリマーである。ハイパーブランチポリマーは、デンドリマーより合成が容易であり、高分子量体も合成しやすいという特徴がある。
　トリアジン環を有するハイパーブランチポリマーは難燃剤用途として合成された報告例がある（非特許文献１）。 By the way, hyperbranched polymers are roughly classified into hyperbranched polymers and dendrimers.
The hyperbranched polymer is, for example, an ABx type polyfunctional monomer (where A and B are functional groups that react with each other, and the number X of B is 2 or more) that has an irregular branched structure obtained by polymerizing. It is a branched polymer.
On the other hand, a dendrimer is a highly branched polymer having a regular branched structure. Hyperbranched polymers are characterized by being easier to synthesize than dendrimers and easier to synthesize high molecular weight polymers.
A hyperbranched polymer having a triazine ring has been reported as a flame retardant application (Non-patent Document 1).
特開２００７－２４６８７７号公報JP 2007-246877 A 特開２００８－２４８３２号公報JP 2008-24832 A 米国特許第５８８６１３０号明細書US Pat. No. 5,886,130 特開２０００－５３６５９号公報JP 2000-53659 A
　本発明は、上記事情に鑑みてなされたものであり、金属酸化物を添加しなくとも、ポリマー単独で高耐熱性、高透明性、高屈折率、高溶解性、低体積収縮を達成できるトリアジン環含有重合体、およびこれを含む膜形成用組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and a triazine that can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage by itself without adding a metal oxide. An object of the present invention is to provide a ring-containing polymer and a film-forming composition containing the same.
　本発明者らは、トリアジン環および芳香環を有する繰り返し単位を含むハイパーブランチポリマーが高屈折率を有し、ポリマー単独で高耐熱性、高透明性、高屈折率、高溶解性、低体積収縮を達成でき、電子デバイスを作製する際の膜形成用組成物として好適であることを既に見出している（ＰＣＴ／ＪＰ２０１０／０５７７６１）が、特定の溶媒への溶解性をさらに向上させることが望まれていた。 The present inventors have found that a hyperbranched polymer including a repeating unit having a triazine ring and an aromatic ring has a high refractive index, and the polymer alone has high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage. Has already been found to be suitable as a film-forming composition for producing an electronic device (PCT / JP2010 / 057771), but it is desired to further improve the solubility in a specific solvent. It was.
　そこで、本発明者らは、さらなる検討を重ねた結果、フッ素原子を有するジアミン化合物を用いることによって、各種溶媒に対する溶解性の非常に優れたポリマーを得ることができ、また、このフッ素原子を有するジアミン化合物とフェニレンジアミン化合物等のその他の芳香族ジアミンとを併用し、その使用比率（共重合比率）を変えることによって、溶解性を保持しつつ屈折率を調整することができることを見出し、本発明を完成した。 Therefore, as a result of further studies, the present inventors can obtain a polymer having excellent solubility in various solvents by using a diamine compound having a fluorine atom, and also having this fluorine atom. It has been found that the refractive index can be adjusted while maintaining solubility by using a diamine compound and another aromatic diamine such as a phenylenediamine compound in combination and changing the ratio of use (copolymerization ratio). Was completed.
　すなわち、本発明は、
１．　下記式（１）または式（２）で表される繰り返し単位構造を含むことを特徴とするトリアジン環含有重合体、
Figure JPOXMLDOC01-appb-C000010
 ｛式中、Ｒ、Ｒ’、Ｒ”およびＲ'''は、互いに独立して、水素原子、アルキル基、アルコキシ基、アリール基、またはアラルキル基を表し、Ａｒ1は、式（３）～（８）で示される群から選ばれる少なくとも１種を表し、
Figure JPOXMLDOC01-appb-C000011
 〔式中、Ｘ1およびＸ2は、互いに独立して、フルオロ基、または炭素数１～１０のフルオロアルキル基を表し、Ｒ1～Ｒ61は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホン基、炭素数１～１０の分岐構造を有していてもよいアルキル基、または炭素数１～１０の分岐構造を有していてもよいアルコキシ基を表し、Ｗ1およびＷ2は、互いに独立して、Ｏ、Ｓ、ＣＨ2、またはＳＯ2を表す。〕
　Ａｒ2は、式（９）～（１９）で示される群から選ばれる少なくとも１種を表す。
Figure JPOXMLDOC01-appb-C000012
 〔式中、Ｒ62～Ｒ141は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホン基、炭素数１～１０の分岐構造を有していてもよいアルキル基、または炭素数１～１０の分岐構造を有していてもよいアルコキシ基を表し、Ｗ3およびＷ4は、互いに独立して、単結合、ＣＲ142Ｒ143（Ｒ142およびＲ143は、互いに独立して、水素原子または炭素数１～１０の分岐構造を有していてもよいアルキル基（ただし、これらは一緒になって環を形成していてもよい。）を表す。）、Ｃ＝Ｏ、Ｏ、Ｓ、ＳＯ、ＳＯ2、またはＮＲ144（Ｒ144は、水素原子または炭素数１～１０の分岐構造を有していてもよいアルキル基を表す。）を表し、Ｙ1およびＹ2は、互いに独立して、単結合、炭素数１～１０の分岐構造を有していてもよいアルキレン基、または式（２０）
Figure JPOXMLDOC01-appb-C000013
 （式中、Ｒ145～Ｒ148は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホン基、炭素数１～１０の分岐構造を有していてもよいアルキル基、または炭素数１～１０の分岐構造を有していてもよいアルコキシ基を表し、Ｙ3およびＹ4は、互いに独立して、単結合または炭素数１～１０の分岐構造を有していてもよいアルキレン基を表す。）で示される基を表す。〕｝
２．　前記Ａｒ1が、式（３）および式（４）から選ばれる少なくとも１種である１のトリアジン環含有重合体、
３．　前記Ａｒ1が、式（３′）および式（４′）から選ばれる少なくとも１種である１のトリアジン環含有重合体、
Figure JPOXMLDOC01-appb-C000014
 （式中、Ｒ1～Ｒ11は前記と同じ。）
４．　前記Ａｒ2が、式（９）で示される基である１～３のいずれかのトリアジン環含有重合体、
５．　前記Ｘ1およびＸ2が、炭素数１～１０のパーフルオロアルキル基である１または２のトリアジン環含有重合体、
６．　前記繰り返し単位構造が、式（２１）で示される１のトリアジン環含有重合体、
Figure JPOXMLDOC01-appb-C000015
 ７．　前記繰り返し単位構造が、式（２２）で示される１のトリアジン環含有重合体、
Figure JPOXMLDOC01-appb-C000016
 ８．　前記繰り返し単位構造が、式（２３）で示される１のトリアジン環含有重合体、
Figure JPOXMLDOC01-appb-C000017
 ９．　前記繰り返し単位構造が、式（２４）で示される１のトリアジン環含有重合体、
Figure JPOXMLDOC01-appb-C000018
 １０．　少なくとも１つの末端が、アルキル基、アラルキル基、アリール基、アルキルアミノ基、アルコキシシリル基含有アルキルアミノ基、アラルキルアミノ基、アリールアミノ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、またはエステル基でキャップされている１～９のいずれかのトリアジン環含有重合体、
１１．　少なくとも１つのトリアジン環末端を有し、このトリアジン環末端が、アルキル基、アラルキル基、アリール基、アルキルアミノ基、アルコキシシリル基含有アルキルアミノ基、アラルキルアミノ基、アリールアミノ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、またはエステル基でキャップされている１０のトリアジン環含有重合体、
１２．　１～１１のいずれかのトリアジン環含有重合体を含む膜形成用組成物、
１３．　１～１１のいずれかのトリアジン環含有重合体を含む膜、
１４．　基材と、この基材上に形成された１３の膜とを備える電子デバイス、
１５．　基材と、この基材上に形成された１３の膜とを備える光学部材、
１６．　１３の膜を少なくとも１層備える、電荷結合素子または相補性金属酸化膜半導体からなる固体撮像素子、
１７．　１３の膜をカラーフィルター上の平坦化層として備える固体撮像素子
を提供する。 That is, the present invention
1. A triazine ring-containing polymer comprising a repeating unit structure represented by the following formula (1) or formula (2):
Figure JPOXMLDOC01-appb-C000010
 {Wherein R, R ′, R ″ and R ′ ″ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and Ar 1 represents a group represented by the formula (3) to Represents at least one selected from the group represented by (8),
Figure JPOXMLDOC01-appb-C000011
 [Wherein, X 1 and X 2 each independently represent a fluoro group or a fluoroalkyl group having 1 to 10 carbon atoms, and R 1 to R 61 each independently represent a hydrogen atom, a halogen atom, W 1 and W 2 represent a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkoxy group which may have a branched structure having 1 to 10 carbon atoms. Independently represent O, S, CH 2 , or SO 2 . ]
Ar 2 represents at least one selected from the group represented by formulas (9) to (19).
Figure JPOXMLDOC01-appb-C000012
 [Wherein R 62 to R 141 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group optionally having a branched structure of 1 to 10 carbon atoms, or 1 carbon atom. Represents an alkoxy group which may have a branched structure of ˜10, W 3 and W 4 are each independently a single bond, CR 142 R 143 (R 142 and R 143 are each independently hydrogen, An atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms (however, they may be combined to form a ring), C═O, O, S , SO, SO 2 , or NR 144 (R 144 represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms), and Y 1 and Y 2 are independent of each other. And an alkyle which may have a single bond and a branched structure having 1 to 10 carbon atoms. Group or formula (20)
Figure JPOXMLDOC01-appb-C000013
 (Wherein R 145 to R 148 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom) Represents an alkoxy group that may have a branched structure of ˜10, and Y 3 and Y 4 each independently represent an alkylene group that may have a single bond or a branched structure of 1 to 10 carbon atoms. Represents a group represented by: ]}
2. 1 triazine ring-containing polymer, wherein Ar 1 is at least one selected from Formula (3) and Formula (4);
3. 1 triazine ring-containing polymer, wherein Ar 1 is at least one selected from formula (3 ′) and formula (4 ′);
Figure JPOXMLDOC01-appb-C000014
 (Wherein R 1 to R 11 are the same as described above.)
4). The triazine ring-containing polymer of any one of 1 to 3, wherein Ar 2 is a group represented by the formula (9):
5. 1 or 2 triazine ring-containing polymer, wherein X 1 and X 2 are perfluoroalkyl groups having 1 to 10 carbon atoms,
6). The triazine ring-containing polymer having one repeating unit structure represented by formula (21):
Figure JPOXMLDOC01-appb-C000015
 7. Wherein the repeating unit structure is a triazine ring-containing polymer represented by formula (22):
Figure JPOXMLDOC01-appb-C000016
 8). The triazine ring-containing polymer having one repeating unit structure represented by formula (23):
Figure JPOXMLDOC01-appb-C000017
 9. The triazine ring-containing polymer having one repeating unit structure represented by formula (24):
Figure JPOXMLDOC01-appb-C000018
 10. At least one terminal is an alkyl group, aralkyl group, aryl group, alkylamino group, alkoxysilyl group-containing alkylamino group, aralkylamino group, arylamino group, alkoxy group, aralkyloxy group, aryloxy group, or ester group. Any of the capped triazine ring-containing polymers of 1 to 9,
11. Having at least one triazine ring end, and the triazine ring end is an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, an alkoxy group, an aralkyloxy group 10 triazine ring-containing polymers capped with groups, aryloxy groups, or ester groups,
12 A film-forming composition comprising any one of the triazine ring-containing polymers of 1 to 11,
13. A film comprising the triazine ring-containing polymer of any one of 1 to 11,
14 An electronic device comprising a substrate and 13 films formed on the substrate;
15. An optical member comprising a substrate and 13 films formed on the substrate;
16. A solid-state imaging device comprising a charge-coupled device or a complementary metal oxide semiconductor, comprising at least one layer of 13 films,
17. A solid-state imaging device comprising 13 films as a planarizing layer on a color filter is provided.
　本発明によれば、金属酸化物を用いることなく、単独で高耐熱性、高透明性、高屈折率、高溶解性、低体積収縮を達成し得るトリアジン環含有重合体を提供できる。
　本発明の重合体骨格とすることで、１）２級アミンをポリマーのスペーサーとして用いる、２）末端に１級アミンが置換している、場合においても高耐熱性、高透明性を維持できる。
　本発明のハイパーブランチポリマーが高屈折率を発現するのは、ハイパーブランチ型の構造にすることで、トリアジン環とアリール（Ａｒ）部分が密に集まり、電子密度が上がっているためであると考えられる。
　特に、上記ＲおよびＲ’の少なくとも１つが水素原子の場合（式（１）の場合）や、Ｒ、Ｒ’、Ｒ”およびＲ'''の少なくとも１つが水素原子の場合（式（２）の場合）、ハイパーブランチ型の構造にすることで、トリアジン環上の窒素原子とアミン部位の水素原子が水素結合し、よりトリアジン環とアリール（Ａｒ）部分が密に集まり、電子密度が上がるものと考えられる。
　また、少なくとも一部のジアミン化合物にフッ素原子含有ジアミン化合物を用いているから、高分子量の化合物であるにもかかわらず、電子デバイス分野で汎用されている比較的低極性の溶媒をはじめとした各種有機溶媒に対する溶解性に優れるとともに、溶剤に溶解したときに低粘度であるため、ハンドリング性に優れる。
　そして、金属酸化物を含まず、ポリマー単独で高屈折率を発現できることから、エッチングやアッシングなどのドライプロセスを経る場合でも、エッチレートが一定となり、均一な膜厚の被膜を得ることができ、デバイスを作製する際のプロセスマージンが拡大する。
　また、本発明のトリアジン環含有重合体は、高耐熱性絶縁材料として使用できる。
　以上のような特性を有する本発明のトリアジン環含有重合体を用いて作製した膜は、液晶ディスプレイ、有機エレクトロルミネッセンス（ＥＬ）ディスプレイ、光半導体（ＬＥＤ）素子、固体撮像素子、有機薄膜太陽電池、色素増感太陽電池、有機薄膜トランジスタ（ＴＦＴ）などの電子デバイスを作製する際の一部材として好適に利用できる。
　特に高屈折率が求められている固体撮像素子の部材である、フォトダイオード上の埋め込み膜および平坦化膜、カラーフィルター前後の平坦化膜、マイクロレンズ、マイクロレンズ上の平坦化膜およびコンフォーマル膜として好適に利用できる。 According to the present invention, it is possible to provide a triazine ring-containing polymer that can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage independently without using a metal oxide.
By using the polymer skeleton of the present invention, high heat resistance and high transparency can be maintained even when 1) a secondary amine is used as a polymer spacer and 2) a primary amine is substituted at the terminal.
It is considered that the hyperbranched polymer of the present invention exhibits a high refractive index because the tribranched structure and the aryl (Ar) portion are closely gathered to increase the electron density. It is done.
In particular, when at least one of R and R ′ is a hydrogen atom (in the case of formula (1)), or when at least one of R, R ′, R ″ and R ′ ″ is a hydrogen atom (in formula (2)) In the case of a hyperbranched structure, the nitrogen atom on the triazine ring and the hydrogen atom of the amine site are hydrogen-bonded, and the triazine ring and the aryl (Ar) moiety are more closely gathered to increase the electron density. it is conceivable that.
In addition, since a fluorine atom-containing diamine compound is used for at least a part of the diamine compound, various types including relatively low-polarity solvents that are widely used in the field of electronic devices despite being high molecular weight compounds. In addition to excellent solubility in organic solvents, it has excellent handling properties because it has a low viscosity when dissolved in a solvent.
And, since it can express a high refractive index with a polymer alone without containing a metal oxide, even when a dry process such as etching or ashing is performed, the etch rate becomes constant, and a film with a uniform film thickness can be obtained. Increases process margin when manufacturing devices.
The triazine ring-containing polymer of the present invention can be used as a high heat resistant insulating material.
A film prepared using the triazine ring-containing polymer of the present invention having the above-described characteristics is a liquid crystal display, an organic electroluminescence (EL) display, an optical semiconductor (LED) element, a solid-state imaging element, an organic thin film solar cell, It can be suitably used as a member for producing electronic devices such as dye-sensitized solar cells and organic thin film transistors (TFTs).
In particular, a buried film and a planarizing film on a photodiode, a planarizing film before and after a color filter, a microlens, and a planarizing film and a conformal film on a microlens, which are members of a solid-state imaging device that requires a high refractive index. Can be suitably used.
実施例１で得られた高分子化合物［１］の1Ｈ－ＮＭＲスペクトルを示す図である。1 is a diagram showing a 1 H-NMR spectrum of a polymer compound [1] obtained in Example 1. FIG. 実施例２で得られた高分子化合物［２］の1Ｈ－ＮＭＲスペクトルを示す図である。3 is a diagram showing a 1 H-NMR spectrum of a polymer compound [2] obtained in Example 2. FIG. 実施例３で得られた高分子化合物［３］の1Ｈ－ＮＭＲスペクトルを示す図である。3 is a diagram showing a 1 H-NMR spectrum of a polymer compound [3] obtained in Example 3. FIG. 実施例４で得られた高分子化合物［４］の1Ｈ－ＮＭＲスペクトルを示す図である。4 is a diagram showing a 1 H-NMR spectrum of a polymer compound [4] obtained in Example 4. FIG. 実施例５で得られた高分子化合物［５］の1Ｈ－ＮＭＲスペクトルを示す図である。6 is a diagram showing a 1 H-NMR spectrum of a polymer compound [5] obtained in Example 5. FIG. 比較例１で得られた高分子化合物［６］の1Ｈ－ＮＭＲスペクトルを示す図である。2 is a diagram showing a 1 H-NMR spectrum of a polymer compound [6] obtained in Comparative Example 1. FIG.
　以下、本発明についてさらに詳しく説明する。
　本発明に係るトリアジン環含有重合体は下記式（１）または（２）で表される繰り返し単位構造を含むものである。 Hereinafter, the present invention will be described in more detail.
The triazine ring-containing polymer according to the present invention includes a repeating unit structure represented by the following formula (1) or (2).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　上記式中、Ｒ、Ｒ’、Ｒ”およびＲ'''は、互いに独立して、水素原子、アルキル基、アルコキシ基、アリール基、またはアラルキル基を表す。
　本発明において、アルキル基の炭素数としては特に限定されるものではないが、１～２０が好ましく、ポリマーの耐熱性をより高めることを考慮すると、炭素数１～１０がより好ましく、１～３がより一層好ましい。また、その構造は、鎖状、分岐状、環状のいずれでもよい。 In the above formula, R, R ′, R ″, and R ′ ″ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
In the present invention, the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms in view of further improving the heat resistance of the polymer. Is even more preferable. Further, the structure may be any of a chain, a branch, and a ring.
　アルキル基の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、シクロプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、シクロブチル基、１－メチル－シクロプロピル基、２－メチル－シクロプロピル基、ｎ－ペンチル基、１－メチル－ｎ－ブチル基、２－メチル－ｎ－ブチル基、３－メチル－ｎ－ブチル基、１，１－ジメチル－ｎ－プロピル基、１，２－ジメチル－ｎ－プロピル基、２，２－ジメチル－ｎ－プロピル基、１－エチル－ｎ－プロピル基、シクロペンチル基、１－メチル－シクロブチル基、２－メチル－シクロブチル基、３－メチル－シクロブチル基、１，２－ジメチル－シクロプロピル基、２，３－ジメチル－シクロプロピル基、１－エチル－シクロプロピル基、２－エチル－シクロプロピル基、ｎ－ヘキシル基、１－メチル－ｎ－ペンチル基、２－メチル－ｎ－ペンチル基、３－メチル－ｎ－ペンチル基、４－メチル－ｎ－ペンチル基、１，１－ジメチル－ｎ－ブチル基、１，２－ジメチル－ｎ－ブチル基、１，３－ジメチル－ｎ－ブチル基、２，２－ジメチル－ｎ－ブチル基、２，３－ジメチル－ｎ－ブチル基、３，３－ジメチル－ｎ－ブチル基、１－エチル－ｎ－ブチル基、２－エチル－ｎ－ブチル基、１，１，２－トリメチル－ｎ－プロピル基、１，２，２－トリメチル－ｎ－プロピル基、１－エチル－１－メチル－ｎ－プロピル基、１－エチル－２－メチル－ｎ－プロピル基、シクロヘキシル基、１－メチル－シクロペンチル基、２－メチル－シクロペンチル基、３－メチル－シクロペンチル基、１－エチル－シクロブチル基、２－エチル－シクロブチル基、３－エチル－シクロブチル基、１，２－ジメチル－シクロブチル基、１，３－ジメチル－シクロブチル基、２，２－ジメチル－シクロブチル基、２，３－ジメチル－シクロブチル基、２，４－ジメチル－シクロブチル基、３，３－ジメチル－シクロブチル基、１－ｎ－プロピル－シクロプロピル基、２－ｎ－プロピル－シクロプロピル基、１－イソプロピル－シクロプロピル基、２－イソプロピル－シクロプロピル基、１，２，２－トリメチル－シクロプロピル基、１，２，３－トリメチル－シクロプロピル基、２，２，３－トリメチル－シクロプロピル基、１－エチル－２－メチル－シクロプロピル基、２－エチル－１－メチル－シクロプロピル基、２－エチル－２－メチル－シクロプロピル基、２－エチル－３－メチル－シクロプロピル基等が挙げられる。 Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl group. -Cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl -N-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl -Cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl Ru-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1 -Dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl Group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2- Trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1 Ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3- Dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-isopropyl-cyclopropyl group 2-isopropyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2 -Methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cycl And a ropropyl group and a 2-ethyl-3-methyl-cyclopropyl group.
　上記アルコキシ基の炭素数としては特に限定されるものではないが、１～２０が好ましく、ポリマーの耐熱性をより高めることを考慮すると、炭素数１～１０がより好ましく、１～３がより一層好ましい。また、そのアルキル部分の構造は、鎖状、分岐状、環状のいずれでもよい。 The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms in view of further improving the heat resistance of the polymer. preferable. Further, the structure of the alkyl moiety may be any of a chain, a branch, and a ring.
　アルコキシ基の具体例としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基、ｎ－ペントキシ基、１－メチル－ｎ－ブトキシ基、２－メチル－ｎ－ブトキシ基、３－メチル－ｎ－ブトキシ基、１，１－ジメチル－ｎ－プロポキシ基、１，２－ジメチル－ｎ－プロポキシ基、２，２－ジメチル－ｎ－プロポキシ基、１－エチル－ｎ－プロポキシ基、ｎ－ヘキシルオキシ基、１－メチル－ｎ－ペンチルオキシ基、２－メチル－ｎ－ペンチルオキシ基、３－メチル－ｎ－ペンチルオキシ基、４－メチル－ｎ－ペンチルオキシ基、１，１－ジメチル－ｎ－ブトキシ基、１，２－ジメチル－ｎ－ブトキシ基、１，３－ジメチル－ｎ－ブトキシ基、２，２－ジメチル－ｎ－ブトキシ基、２，３－ジメチル－ｎ－ブトキシ基、３，３－ジメチル－ｎ－ブトキシ基、１－エチル－ｎ－ブトキシ基、２－エチル－ｎ－ブトキシ基、１，１，２－トリメチル－ｎ－プロポキシ基、１，２，２－トリメチル－ｎ－プロポキシ基、１－エチル－１－メチル－ｎ－プロポキシ基、１－エチル－２－メチル－ｎ－プロポキシ基等が挙げられる。 Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, 1-methyl- n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl -N-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-di- Til-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1 , 2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, etc. Can be mentioned.
　上記アリール基の炭素数としては特に限定されるものではないが、６～４０が好ましく、ポリマーの耐熱性をより高めることを考慮すると、炭素数６～１６がより好ましく、６～１３がより一層好ましい。
　アリール基の具体例としては、フェニル基、ｏ－クロルフェニル基、ｍ－クロルフェニル基、ｐ－クロルフェニル基、ｏ－フルオロフェニル基、ｐ－フルオロフェニル基、ｏ－メトキシフェニル基、ｐ－メトキシフェニル基、ｐ－ニトロフェニル基、ｐ－シアノフェニル基、α－ナフチル基、β－ナフチル基、ｏ－ビフェニリル基、ｍ－ビフェニリル基、ｐ－ビフェニリル基、１－アントリル基、２－アントリル基、９－アントリル基、１－フェナントリル基、２－フェナントリル基、３－フェナントリル基、４－フェナントリル基、９－フェナントリル基等が挙げられる。 The number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 to 40. In view of further improving the heat resistance of the polymer, 6 to 16 carbon atoms are more preferable, and 6 to 13 are even more preferable. preferable.
Specific examples of the aryl group include phenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxy group. Phenyl group, p-nitrophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, Examples include 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.
　アラルキル基の炭素数としては特に限定されるものではないが、炭素数７～２０が好ましく、そのアルキル部分は、直鎖、分岐、環状のいずれでもよい。
　その具体例としては、ベンジル基、ｐ－メチルフェニルメチル基、ｍ－メチルフェニルメチル基、ｏ－エチルフェニルメチル基、ｍ－エチルフェニルメチル基、ｐ－エチルフェニルメチル基、２－プロピルフェニルメチル基、４－イソプロピルフェニルメチル基、４－イソブチルフェニルメチル基、α－ナフチルメチル基等が挙げられる。 The number of carbon atoms of the aralkyl group is not particularly limited, but preferably 7 to 20 carbon atoms, and the alkyl portion may be linear, branched or cyclic.
Specific examples thereof include benzyl group, p-methylphenylmethyl group, m-methylphenylmethyl group, o-ethylphenylmethyl group, m-ethylphenylmethyl group, p-ethylphenylmethyl group, 2-propylphenylmethyl group. 4-isopropylphenylmethyl group, 4-isobutylphenylmethyl group, α-naphthylmethyl group and the like.
　上記Ａｒ1は、式（３）～（８）で示される群から選ばれる少なくとも１種を表すが、特に、式（３）および（４）で示される群から選ばれる少なくとも１種がより好ましく、式（３′）および（４′）で示される群から選ばれる少なくとも１種がより一層好ましい。 Ar 1 represents at least one selected from the group represented by formulas (3) to (8), and more preferably at least one selected from the group represented by formulas (3) and (4). At least one selected from the group represented by formulas (3 ′) and (4 ′) is even more preferable.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　上記Ｘ1およびＸ2は、互いに独立して、フルオロ基、または炭素数１～１０のフルオロアルキル基を表し、Ｒ1～Ｒ61は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホン基、炭素数１～１０の分岐構造を有していてもよいアルキル基、または炭素数１～１０の分岐構造を有していてもよいアルコキシ基を表し、Ｗ1およびＷ2は、互いに独立して、Ｏ、Ｓ、ＣＨ2、またはＳＯ2を表す。 X 1 and X 2 each independently represent a fluoro group or a fluoroalkyl group having 1 to 10 carbon atoms, and R 1 to R 61 each independently represent a hydrogen atom, a halogen atom, a carboxyl group, A sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkoxy group which may have a branched structure having 1 to 10 carbon atoms, wherein W 1 and W 2 are Independently represents O, S, CH 2 or SO 2 .
　ここで、炭素数１～１０のフルオロアルキル基としては、直鎖、分岐、環状のいずれでもよく、例えば、トリフルオロメチル基、ペンタフルオロエチル基、２，２，２－トリフルオロエチル基、ヘプタフルオロプロピル基、２，２，３，３，３－ペンタフルオロプロピル基、２，２，３，３－テトラフルオロプロピル基、２，２，２－トリフルオロ－１－（トリフルオロメチル）エチル基、ノナフルオロブチル基、４，４，４－トリフルオロブチル基、ウンデカフルオロペンチル基、２，２，３，３，４，４，５，５，５－ノナフルオロペンチル基、２，２，３，３，４，４，５，５－オクタフルオロペンチル基、トリデカフルオロヘキシル基、２，２，３，３，４，４，５，５，６，６，６－ウンデカフルオロヘキシル基、２，２，３，３，４，４，５，５，６，６－デカフルオロヘキシル基、３，３，４，４，５，５，６，６，６－ノナフルオロヘキシル基等が挙げられる。 Here, the fluoroalkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and examples thereof include trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, hepta. Fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group , Nonafluorobutyl group, 4,4,4-trifluorobutyl group, undecafluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2, 3,3,4,4,5,5-octafluoropentyl group, tridecafluorohexyl group, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group , 2, 2, 3, , 4,4,5,5,6,6- decafluoro hexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, and the like.
　特に、得られるハイパーブランチポリマーの有機溶媒に対する溶解性を高めることを考慮すると、炭素数１～１０のパーフルオロアルキル基が好ましく、特に、炭素数１～５のパーフルオロアルキル基がより好ましく、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基が好適である。
　また、上記アルキル基、アルコキシ基としては上記と同様のものが挙げられる。
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 In particular, in view of increasing the solubility of the obtained hyperbranched polymer in an organic solvent, a perfluoroalkyl group having 1 to 10 carbon atoms is preferable, a perfluoroalkyl group having 1 to 5 carbon atoms is particularly preferable, and a trifluoroalkyl group is more preferable. A fluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group are preferred.
Examples of the alkyl group and alkoxy group are the same as those described above.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
　Ａｒ1の具体例としては、下記式で示されるものが好適であるが、これらに限定されるものではない。 Specific examples of Ar 1 are preferably those represented by the following formula, but are not limited thereto.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　上記式（２）は、２種類のジアミンを用いて得られる共重合型のハイパーブランチポリマーであり、そのＡｒ2としては、式（９）～（１９）からなる群から選ばれる少なくとも１種であるが、これらの中でも、式（９）で示される基がより好ましい。 The above formula (2) is a copolymer-type hyperbranched polymer obtained using two kinds of diamines, and Ar 2 is at least one selected from the group consisting of formulas (9) to (19). Among these, the group represented by the formula (9) is more preferable.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　上記Ｒ62～Ｒ141は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホン基、炭素数１～１０の分岐構造を有していてもよいアルキル基、または炭素数１～１０の分岐構造を有していてもよいアルコキシ基を表し、Ｗ3およびＷ4は、互いに独立して、単結合、ＣＲ142Ｒ143（Ｒ142およびＲ143は、互いに独立して、水素原子または炭素数１～１０の分岐構造を有していてもよいアルキル基（ただし、これらは一緒になって環を形成していてもよい。）を表す。）、Ｃ＝Ｏ、Ｏ、Ｓ、ＳＯ、ＳＯ2、またはＮＲ144（Ｒ144は、水素原子または炭素数１～１０の分岐構造を有していてもよいアルキル基を表す。）を表す。
　これらハロゲン原子、アルキル基、アルコキシ基としては上記と同様のものが挙げられる。
　また、Ｙ1およびＹ2は、互いに独立して、単結合、炭素数１～１０の分岐構造を有していてもよいアルキレン基、または式（２０）で示される基を表す。 R 62 to R 141 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Represents an alkoxy group which may have a branched structure, W 3 and W 4 are each independently a single bond, CR 142 R 143 (R 142 and R 143 are each independently a hydrogen atom or carbon An alkyl group which may have a branched structure of 1 to 10 (note that these may be combined to form a ring), C═O, O, S, SO, SO 2 or NR 144 (R 144 represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms).
Examples of the halogen atom, alkyl group and alkoxy group are the same as those described above.
Y 1 and Y 2 each independently represent a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (20).
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　上記Ｒ145～Ｒ148は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホン基、炭素数１～１０の分岐構造を有していてもよいアルキル基、または炭素数１～１０の分岐構造を有していてもよいアルコキシ基を表し、Ｙ3およびＹ4は、互いに独立して、単結合または炭素数１～１０の分岐構造を有していてもよいアルキレン基を表す。
　これらハロゲン原子、アルキル基、アルコキシ基としては上記と同様のものが挙げられる。
　炭素数１～１０の分岐構造を有していてもよいアルキレン基としては、メチレン基、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基等が挙げられる。 R 145 to R 148 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. An alkoxy group which may have a branched structure is represented, and Y 3 and Y 4 each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms.
Examples of the halogen atom, alkyl group and alkoxy group are the same as those described above.
Examples of the alkylene group that may have a branched structure having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.
　上記式（９）～（１９）で表されるアリール基の具体例としては、下記式で示されるものが挙げられるが、これらに限定されるものではない。 Specific examples of the aryl group represented by the above formulas (9) to (19) include those represented by the following formula, but are not limited thereto.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　これらの中でも、より高い屈折率のポリマーが得られることから、下記式で示されるアリール基がより好ましい。 Among these, an aryl group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　本発明における、好適な繰り返し単位構造としては、以下の式（２１）～（２４）で示されるものが挙げられるが、これらに限定されるものではない。 Favorable repeating unit structures in the present invention include those represented by the following formulas (21) to (24), but are not limited thereto.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　本発明のトリアジン環含有ハイパーブランチポリマーの重量平均分子量は、特に限定されるものではないが、５００～５００，０００が好ましく、５００～１００，０００がより好ましく、より耐熱性を向上させるとともに、収縮率を低くするという点から、２，０００以上が好ましく、より溶解性を高め、得られた溶液の粘度を低下させるという点から、５０，０００以下が好ましく、３０，０００以下がより好ましく、１０，０００以下がさらに好ましい。
　なお、本発明における重量平均分子量は、ゲルパーミエーションクロマトグラフィー（以下、ＧＰＣという）分析による標準ポリスチレン換算で得られる平均分子量である。 The weight average molecular weight of the triazine ring-containing hyperbranched polymer of the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000, and further improves heat resistance and shrinkage. 2,000 or more is preferable from the viewpoint of lowering the rate, 50,000 or less is preferable, and 30,000 or less is more preferable, from the viewpoint of further increasing the solubility and lowering the viscosity of the obtained solution. Is more preferable.
In addition, the weight average molecular weight in this invention is an average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (henceforth GPC) analysis.
　本発明のトリアジン環含有重合体（ハイパーブランチポリマー）の製造法について一例を挙げて説明する。
　本発明の式（１）で表されるトリアジン環含有重合体は、ハロゲン化シアヌルと、フッ素原子含有ジアミン化合物とを反応させて得ることができ、例えば、下記スキーム１に示されるように、繰り返し構造（２２’）を有するハイパーブランチポリマーは、ハロゲン化シアヌル（２５）およびフッ素原子含有ジアミン化合物（２６）を適当な有機溶媒中で反応させて得ることができる。 An example is given and demonstrated about the manufacturing method of the triazine ring containing polymer (hyperbranched polymer) of this invention.
The triazine ring-containing polymer represented by the formula (1) of the present invention can be obtained by reacting cyanuric halide with a fluorine atom-containing diamine compound. For example, as shown in Scheme 1 below, The hyperbranched polymer having the structure (22 ′) can be obtained by reacting cyanuric halide (25) and a fluorine atom-containing diamine compound (26) in an appropriate organic solvent.
　なお、本発明で用い得るフッ素原子含有ジアミンとしては、特に限定されるものではく、例えば、２，２－ビス（３－アミノ－４－メチルフェニル）ヘキサフルオロプロパン、３，５－ジアミノベンゾトリフルオリド、４，４’－ビス（４－アミノフェノキシ）オクタフルオロビフェニル、２，２－ビス（４－ヒドロキシ－３－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（３－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（３－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（２－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（２－アミノフェノキシ）３，５－ジメチルフェニル］ヘキサフルオロプロパン、ｐ－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ベンゼン、４，４’－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ビフェニル、４，４’－ビス（４－アミノ－３－トリフルオロメチルフェノキシ）ビフェニル、４，４’－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ジフェニルスルホン、４，４’－ビス（３－アミノ－５－トリフルオロメチルフェノキシ）ジフェニルスルホン、２，２－ビス［４－（４－アミノ－２－トリフルオロメチルフェノキシ）フェニル］ヘキサフルオロプロパン、４，４’－ビス［（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン等のフッ素原子含有ジアミノアリール化合物などが挙げられる。 The fluorine atom-containing diamine that can be used in the present invention is not particularly limited, and examples thereof include 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane and 3,5-diaminobenzotrifluoride. Lido, 4,4′-bis (4-aminophenoxy) octafluorobiphenyl, 2,2-bis (4-hydroxy-3-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoro Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) 3 5-dimethylphenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4 ′ -Bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5- Trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-bis [(4-aminophenoxy) phenyl] hexa And fluorine atom-containing diaminoaryl compounds such as fluoropropane.
Figure JPOXMLDOC01-appb-C000028
 （式中、Ｘは、互いに独立してハロゲン原子を表す。Ｒは上記と同じ意味を表す。）
Figure JPOXMLDOC01-appb-C000028
 (In the formula, X represents a halogen atom independently of each other. R represents the same meaning as described above.)
　また、下記スキーム２に示されるように、繰り返し構造（２２’）を有するハイパーブランチポリマーは、ハロゲン化シアヌル（２５）およびフッ素原子含有ジアミン化合物（２６）を適当な有機溶媒中で等量用いて反応させて得られる化合物（２７）から合成することもできる。 Moreover, as shown in the following scheme 2, the hyperbranched polymer having a repeating structure (22 ′) is obtained by using an equivalent amount of cyanuric halide (25) and fluorine atom-containing diamine compound (26) in an appropriate organic solvent. It can also be synthesized from the compound (27) obtained by the reaction.
Figure JPOXMLDOC01-appb-C000029
 （式中、Ｘは、互いに独立してハロゲン原子を表す。Ｒは上記と同じ意味を表す。）
Figure JPOXMLDOC01-appb-C000029
 (In the formula, X represents a halogen atom independently of each other. R represents the same meaning as described above.)
　一方、本発明の式（２）で表される共重合型のトリアジン環含有重合体は、ハロゲン化シアヌルと、少なくとも２種類のジアミノアリール化合物とを反応させて得ることができ、例えば、下記スキーム３に示されるように、繰り返し構造（２４’）を有するハイパーブランチポリマーは、ハロゲン化シアヌル（２５）、フッ素原子含有ジアミン化合物（２６）およびｍ－フェニレンジアミン化合物（３１）を適当な有機溶媒中で反応させて得ることができる。 On the other hand, the copolymer type triazine ring-containing polymer represented by the formula (2) of the present invention can be obtained by reacting cyanuric halide with at least two kinds of diaminoaryl compounds. As shown in FIG. 3, the hyperbranched polymer having a repeating structure (24 ′) comprises cyanuric halide (25), fluorine atom-containing diamine compound (26) and m-phenylenediamine compound (31) in a suitable organic solvent. It can obtain by making it react.
Figure JPOXMLDOC01-appb-C000030
 （式中、Ｘは、互いに独立してハロゲン原子を表す。Ｒは上記と同じ意味を表す。）
Figure JPOXMLDOC01-appb-C000030
 (In the formula, X represents a halogen atom independently of each other. R represents the same meaning as described above.)
　また、下記スキーム４に示されるように、繰り返し構造（２４’）を有するハイパーブランチポリマーは、ハロゲン化シアヌル（２５）およびフッ素原子含有ジアミン化合物（２６）を適当な有機溶媒中で等量用いて反応させて得られる化合物（２７）、並びにハロゲン化シアヌル（２５）およびｍ－フェニレンジアミン化合物（３１）を適当な有機溶媒中で等量用いて反応させて得られる化合物（３２）から合成することもできる。 Moreover, as shown in the following scheme 4, the hyperbranched polymer having a repeating structure (24 ′) is obtained by using an equivalent amount of cyanuric halide (25) and a fluorine atom-containing diamine compound (26) in an appropriate organic solvent. Synthesis from compound (27) obtained by reaction, and compound (32) obtained by reacting cyanuric halide (25) and m-phenylenediamine compound (31) in equal amounts in an appropriate organic solvent. You can also.
Figure JPOXMLDOC01-appb-C000031
 （式中、Ｘは、互いに独立してハロゲン原子を表す。Ｒは上記と同じ意味を表す。）
Figure JPOXMLDOC01-appb-C000031
 (In the formula, X represents a halogen atom independently of each other. R represents the same meaning as described above.)
　以上の方法を用いることで、本発明のハイパーブランチポリマーを、安価に、しかも簡便かつ安全に製造することができる。この製造方法は、一般的なポリマーを合成する際の反応時間よりも著しく短いことから、近年の環境への配慮に適合した製造方法であり、ＣＯ2排出量を低減できる。また、製造スケールを大幅に増加させても安定製造することが可能であり、工業化レベルでの安定供給体制を損なわない。 By using the above method, the hyperbranched polymer of the present invention can be produced inexpensively, easily and safely. Since this production method is significantly shorter than the reaction time for synthesizing a general polymer, it is a production method suitable for environmental considerations in recent years and can reduce CO 2 emissions. Moreover, stable production is possible even if the production scale is greatly increased, and the stable supply system at the industrialization level is not impaired.
　スキーム１の方法の場合、各原料の仕込み量としては、目的とするハイパーブランチポリマーが得られる限りにおいて任意であるが、ハロゲン化シアヌル（２５）１当量に対し、ジアミノ化合物（２６）０．０１～１０当量が好ましい。
　特に、スキーム１の方法の場合、ハロゲン化シアヌル（２５）２当量に対して、ジアミノ化合物（２６）を３当量用いることを避けることが好ましい。官能基の当量をずらすことで、ゲル化物の生成を防ぐことができる。
　種々の分子量のトリアジン環末端を多く有するハイパーブランチポリマーを得るために、ハロゲン化シアヌル（２５）２当量に対して、ジアミノ化合物（２６）を３当量未満の量で用いることが好ましい。
　一方、種々の分子量のアミン末端を多く有するハイパーブランチポリマーを得るために、ジアミノ化合物（２６）３当量に対して、ハロゲン化シアヌル（２５）を２当量未満の量で用いることが好ましい。
　また、スキーム２の方法の場合、各原料の仕込み量としては、目的とするハイパーブランチポリマーが得られる限りにおいて任意であるが、ハロゲン化シアヌル（２５）１当量に対し、ジアミノ化合物（２６）０．０１～１０当量が好ましい。 In the case of the method of Scheme 1, the amount of each raw material charged is arbitrary as long as the desired hyperbranched polymer is obtained, but the diamino compound (26) 0.01 relative to 1 equivalent of the cyanuric halide (25). ~ 10 equivalents are preferred.
In particular, in the case of the method of Scheme 1, it is preferable to avoid using 3 equivalents of diamino compound (26) per 2 equivalents of cyanuric halide (25). By shifting the equivalent of the functional group, formation of a gelled product can be prevented.
In order to obtain a hyperbranched polymer having many triazine ring terminals with various molecular weights, it is preferable to use the diamino compound (26) in an amount of less than 3 equivalents relative to 2 equivalents of cyanuric halide (25).
On the other hand, in order to obtain a hyperbranched polymer having many amine ends with various molecular weights, it is preferable to use cyanuric halide (25) in an amount of less than 2 equivalents relative to 3 equivalents of diamino compound (26).
In the case of the method of Scheme 2, the amount of each raw material charged is arbitrary as long as the desired hyperbranched polymer can be obtained, but the diamino compound (26) 0 with respect to 1 equivalent of the cyanuric halide (25). .01 to 10 equivalents are preferred.
　上記スキーム３の方法の場合、各原料の仕込み量としては、目的とする重合体が得られる限りにおいて任意であるが、ハロゲン化シアヌル（２５）１当量に対し、ｍ－フェニレンジアミン化合物（３１）およびジアミノ化合物（２６）の総量として０．０１～１０当量が好ましいが、ハロゲン化シアヌル（２５）２当量に対して、ｍ－フェニレンジアミン化合物（３１）およびジアミノ化合物（２６）の総量として３当量用いることを避けることが好ましい。官能基の当量をずらすことで、ゲル化物の生成を防ぐことができる。
　種々の分子量のトリアジン環末端を有するハイパーブランチポリマーを得るために、ハロゲン化シアヌル（２５）２当量に対して、ｍ－フェニレンジアミン化合物（３１）およびジアミノ化合物（２６）の総量として、３当量未満の量で用いることが好ましい。
　一方、種々の分子量のアミン末端を有するハイパーブランチポリマーを得るために、ｍ－フェニレンジアミン化合物（３１）およびジアミノ化合物（２６）の総量３当量に対して、ハロゲン化シアヌル（２５）２当量未満の量で用いることが好ましい。
　また、スキーム４の方法の場合、各原料の仕込み量としては、目的とするハイパーブランチポリマーが得られる限りにおいて任意であるが、ハロゲン化シアヌル（２５）１当量に対し、ジアミノ化合物（３１），（２６）それぞれ０．０１～１０当量が好ましい。 In the case of the method of Scheme 3, the amount of each raw material charged is arbitrary as long as the target polymer is obtained, but the m-phenylenediamine compound (31) is used per 1 equivalent of cyanuric halide (25). And the total amount of the diamino compound (26) is preferably 0.01 to 10 equivalents, but the total amount of the m-phenylenediamine compound (31) and the diamino compound (26) is 3 equivalents with respect to 2 equivalents of the cyanuric halide (25). It is preferred to avoid using it. By shifting the equivalent of the functional group, formation of a gelled product can be prevented.
In order to obtain a hyperbranched polymer having triazine ring ends of various molecular weights, the total amount of m-phenylenediamine compound (31) and diamino compound (26) is less than 3 equivalents relative to 2 equivalents of cyanuric halide (25). It is preferable to use it in the quantity.
On the other hand, in order to obtain hyperbranched polymers having amine ends with various molecular weights, the total amount of m-phenylenediamine compound (31) and diamino compound (26) is less than 2 equivalents of cyanuric halide (25). It is preferable to use it in an amount.
Further, in the case of the method of Scheme 4, the amount of each raw material charged is arbitrary as long as the desired hyperbranched polymer is obtained, but the diamino compound (31), (26) 0.01 to 10 equivalents are preferred respectively.
　以上のように、ジアミノ化合物やハロゲン化シアヌルの量を適宜調節することで、得られるハイパーブランチポリマーの分子量を容易に調節することができる。
　例えば、薄膜を作製した場合に、優れた透明性や耐光性を有するという点では、トリアジン環末端を多く有するハイパーブランチポリマーが好ましい。 As described above, the molecular weight of the resulting hyperbranched polymer can be easily adjusted by appropriately adjusting the amounts of the diamino compound and the cyanuric halide.
For example, when a thin film is produced, a hyperbranched polymer having a large number of triazine ring ends is preferable in terms of having excellent transparency and light resistance.
　上記有機溶媒としては、この種の反応において通常用いられる種々の溶媒を用いることができ、例えば、テトラヒドロフラン、ジオキサン、ジメチルスルホキシド；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン、テトラメチル尿素、ヘキサメチルホスホルアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピペリドン、Ｎ，Ｎ－ジメチルエチレン尿素、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルマロン酸アミド、Ｎ－メチルカプロラクタム、Ｎ－アセチルピロリジン、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ－エチル－２－ピロリドン、Ｎ，Ｎ－ジメチルプロピオン酸アミド、Ｎ，Ｎ－ジメチルイソブチルアミド、Ｎ－メチルホルムアミド、Ｎ，Ｎ’－ジメチルプロピレン尿素等のアミド系溶媒、およびそれらの混合溶媒が挙げられる。
　中でもＮ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、およびそれらの混合溶媒が好ましく、特に、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドンが好適である。 As the organic solvent, various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran, dioxane, dimethyl sulfoxide; N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea. , Hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N ′, N′-tetramethylmalonic acid amide, N-methylcaprolactam N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutyramide, N-methylformamide, N, N′-dimethylpropylene Amide solvents such as urea, and mixed solvents thereof That.
Among these, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and mixed solvents thereof are preferable, and N, N-dimethylacetamide, N-methyl-2-pyrrolidone are particularly preferable. Is preferred.
　スキーム１，３の反応およびスキーム２，４の第２段階の反応（繰り返し構造（２４’）を有するハイパーブランチポリマーの合成段階）において、反応温度は、用いる溶媒の融点から溶媒の沸点までの範囲で適宜設定すればよいが、特に、０～１５０℃程度が好ましく、６０～１００℃がより好ましい。
　特にスキーム１，３の反応では、リニア性を抑え、分岐度を高めるという点から、反応温度は６０～１５０℃が好ましく、８０～１５０℃が好ましく、８０～１２０℃が好ましい。 In the reactions of Schemes 1 and 3 and the second stage reaction of Schemes 2 and 4 (the synthesis stage of the hyperbranched polymer having the repeating structure (24 ′)), the reaction temperature ranges from the melting point of the solvent used to the boiling point of the solvent. However, it is preferably about 0 to 150 ° C., more preferably 60 to 100 ° C.
Particularly in the reactions of Schemes 1 and 3, the reaction temperature is preferably 60 to 150 ° C., preferably 80 to 150 ° C., and preferably 80 to 120 ° C. from the viewpoint of suppressing linearity and increasing the degree of branching.
　スキーム２，４の第１段階の方法（化合物（２７）および（３２）の合成段階）において、反応温度は、用いる溶媒の融点から溶媒の沸点までの範囲で適宜設定すればよいが、特に、－５０～５０℃程度が好ましく、－２０～５０℃程度がより好ましく、－１０～５０℃程度がより一層好ましく、－１０～１０℃がさらに好ましい。
　特にスキーム２，４の方法では、－５０～５０℃で反応させる第１工程と、この工程に続いて６０～１５０℃で反応させる第２工程とからなる２段階工程を採用することが好ましい。 In the first stage method of Schemes 2 and 4 (the synthesis stage of compounds (27) and (32)), the reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent. It is preferably about −50 to 50 ° C., more preferably about −20 to 50 ° C., still more preferably about −10 to 50 ° C., and further preferably −10 to 10 ° C.
In particular, in the methods of Schemes 2 and 4, it is preferable to employ a two-step process including a first process for reaction at −50 to 50 ° C. and a second process for reaction at 60 to 150 ° C. following this process.
　上記各反応において、各成分の配合順序は任意であるが、スキーム１，３の反応においては、ハロゲン化シアヌル（２５）またはジアミノ化合物（２６），（３１）および有機溶媒を含む溶液を６０～１５０℃、好ましくは８０～１５０℃に加熱し、この温度で、当該溶液中に、ジアミノ化合物（２６），（３１）またはハロゲン化シアヌル（２５）を加える方法が最適である。
　この場合、予め溶媒に溶かしておく成分および後から加える成分はどちらでもよいが、ジアミノ化合物（２６），（３１）の加熱溶液中に、ハロゲン化シアヌル（２５）を添加する手法が好ましい。 In each of the above reactions, the order of blending the components is arbitrary, but in the reactions of Schemes 1 and 3, a solution containing cyanuric halide (25) or diamino compounds (26) and (31) and an organic solvent is added to 60 to A method of heating to 150 ° C., preferably 80 to 150 ° C., and adding the diamino compound (26), (31) or cyanuric halide (25) to the solution at this temperature is optimal.
In this case, either a component previously dissolved in a solvent or a component added later may be used, but a method of adding cyanuric halide (25) to a heated solution of diamino compounds (26) and (31) is preferable.
　また、スキーム２，４の反応において、予め溶媒に溶かしておく成分および後から加える成分はどちらでもよいが、ハロゲン化シアヌル（２５）の冷却溶液中に、ジアミノ化合物（２６），（３１）を添加する手法が好ましい。
　後から加える成分は、ニートで加えても、上述したような有機溶媒に溶かした溶液で加えてもよいが、操作の容易さや反応のコントロールのし易さなどを考慮すると、後者の手法が好適である。
　また、添加は、滴下等によって徐々に加えても、全量一括して加えてもよい。 In the reactions of Schemes 2 and 4, the component previously dissolved in the solvent and the component added later may be either, but the diamino compounds (26) and (31) are added to the cooled solution of cyanuric halide (25). The method of adding is preferable.
Components added later may be added neat or in a solution dissolved in an organic solvent as described above, but the latter method is preferred in view of ease of operation and ease of reaction control. It is.
The addition may be gradually added by dropping or the like, or may be added all at once.
　スキーム１，３において、加熱した状態で、両化合物を混合した後は、（段階的に温度を上げることなく）一段階で反応させた場合でも、ゲル化することなく、目的とするトリアジン環含有ハイパーブランチポリマーを得ることができる。 In Schemes 1 and 3, after mixing both compounds in the heated state, even if they are reacted in one step (without increasing the temperature stepwise), the desired triazine ring is contained without gelation. A hyperbranched polymer can be obtained.
　また、上記スキーム１，３の反応およびスキーム２，４の第２段階の反応では、重合時または重合後に通常用いられる種々の塩基を添加してもよい。
　この塩基の具体例としては、炭酸カリウム、水酸化カリウム、炭酸ナトリウム、水酸化ナトリウム、炭酸水素ナトリウム、ナトリウムエトキシド、酢酸ナトリウム、炭酸リチウム、水酸化リチウム、酸化リチウム、酢酸カリウム、酸化マグネシウム、酸化カルシウム、水酸化バリウム、リン酸三リチウム、リン酸三ナトリウム、リン酸三カリウム、フッ化セシウム、酸化アルミニウム、アンモニア、トリメチルアミン、トリエチルアミン、ジイソプロピルメチルアミン、ジイソプロピルエチルアミン、Ｎ－メチルピペリジン、２，２，６，６－テトラメチル－Ｎ－メチルピペリジン、ピリジン、４－ジメチルアミノピリジン、Ｎ－メチルモルホリン等が挙げられる。 In the reactions of Schemes 1 and 3 and the second stage reactions of Schemes 2 and 4, various bases usually used during polymerization or after polymerization may be added.
Specific examples of this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, oxidized Calcium, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, trimethylamine, triethylamine, diisopropylmethylamine, diisopropylethylamine, N-methylpiperidine, 2,2, Examples include 6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.
　塩基の添加量は、ハロゲン化シアヌル（２５）１当量に対して１～１００当量が好ましく、１～１０当量がより好ましい。なお、これらの塩基は水溶液にして用いてもよい。
　得られるポリマーには、原料成分が残存していないことが好ましいが、本発明の効果を損なわなければ一部の原料が残存していてもよい。
　いずれのスキームの方法においても、反応終了後、生成物は再沈法等によって容易に精製できる。 The amount of base added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, per 1 equivalent of cyanuric halide (25). These bases may be used as an aqueous solution.
In the polymer obtained, it is preferable that no raw material components remain, but some raw materials may remain as long as the effects of the present invention are not impaired.
In any of the scheme methods, after completion of the reaction, the product can be easily purified by a reprecipitation method or the like.
　なお、本発明においては、少なくとも１つの末端トリアジン環のハロゲン原子の一部を、アルキル基、アラルキル基、アリール基、アルキルアミノ基、アルコキシシリル基含有アルキルアミノ基、アラルキルアミノ基、アリールアミノ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、エステル基等でキャップしてもよい。
　これらの中でも、アルキルアミノ基、アルコキシシリル基含有アルキルアミノ基、アラルキルアミノ基、アリールアミノ基が好ましく、アルキルアミノ基、アリールアミノ基がより好ましく、アリールアミノ基がさらに好ましい。 In the present invention, at least one of the halogen atoms of the terminal triazine ring is substituted with an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, You may cap by an alkoxy group, an aralkyloxy group, an aryloxy group, an ester group, etc.
Among these, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, and an arylamino group are preferable, an alkylamino group and an arylamino group are more preferable, and an arylamino group is further preferable.
　エステル基の具体例としては、メトキシカルボニル基、エトキシカルボニル基等が挙げられる。
　アルキルアミノ基の具体例としては、メチルアミノ基、エチルアミノ基、ｎ－プロピルアミノ基、イソプロピルアミノ基、ｎ－ブチルアミノ基、イソブチルアミノ基、ｓ－ブチルアミノ基、ｔ－ブチルアミノ基、ｎ－ペンチルアミノ基、１－メチル－ｎ－ブチルアミノ基、２－メチル－ｎ－ブチルアミノ基、３－メチル－ｎ－ブチルアミノ基、１，１－ジメチル－ｎ－プロピルアミノ基、１，２－ジメチル－ｎ－プロピルアミノ基、２，２－ジメチル－ｎ－プロピルアミノ基、１－エチル－ｎ－プロピルアミノ基、ｎ－ヘキシルアミノ基、１－メチル－ｎ－ペンチルアミノ基、２－メチル－ｎ－ペンチルアミノ基、３－メチル－ｎ－ペンチルアミノ基、４－メチル－ｎ－ペンチルアミノ基、１，１－ジメチル－ｎ－ブチルアミノ基、１，２－ジメチル－ｎ－ブチルアミノ基、１，３－ジメチル－ｎ－ブチルアミノ基、２，２－ジメチル－ｎ－ブチルアミノ基、２，３－ジメチル－ｎ－ブチルアミノ基、３，３－ジメチル－ｎ－ブチルアミノ基、１－エチル－ｎ－ブチルアミノ基、２－エチル－ｎ－ブチルアミノ基、１，１，２－トリメチル－ｎ－プロピルアミノ基、１，２，２－トリメチル－ｎ－プロピルアミノ基、１－エチル－１－メチル－ｎ－プロピルアミノ基、１－エチル－２－メチル－ｎ－プロピルアミノ基等が挙げられる。 Specific examples of the ester group include a methoxycarbonyl group and an ethoxycarbonyl group.
Specific examples of the alkylamino group include methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, s-butylamino group, t-butylamino group, n -Pentylamino group, 1-methyl-n-butylamino group, 2-methyl-n-butylamino group, 3-methyl-n-butylamino group, 1,1-dimethyl-n-propylamino group, 1,2 -Dimethyl-n-propylamino group, 2,2-dimethyl-n-propylamino group, 1-ethyl-n-propylamino group, n-hexylamino group, 1-methyl-n-pentylamino group, 2-methyl -N-pentylamino group, 3-methyl-n-pentylamino group, 4-methyl-n-pentylamino group, 1,1-dimethyl-n-butylamino group, 1,2- Methyl-n-butylamino group, 1,3-dimethyl-n-butylamino group, 2,2-dimethyl-n-butylamino group, 2,3-dimethyl-n-butylamino group, 3,3-dimethyl- n-butylamino group, 1-ethyl-n-butylamino group, 2-ethyl-n-butylamino group, 1,1,2-trimethyl-n-propylamino group, 1,2,2-trimethyl-n- Examples thereof include a propylamino group, a 1-ethyl-1-methyl-n-propylamino group, and a 1-ethyl-2-methyl-n-propylamino group.
　アラルキルアミノ基の具体例としては、ベンジルアミノ基、メトキシカルボニルフェニルメチルアミノ基、エトキシカルボニルフェニルメチルアミノ基、ｐ－メチルフェニルメチルアミノ基、ｍ－メチルフェニルメチルアミノ基、ｏ－エチルフェニルメチルアミノ基、ｍ－エチルフェニルメチルアミノ基、ｐ－エチルフェニルメチルアミノ基、２－プロピルフェニルメチルアミノ基、４－イソプロピルフェニルメチルアミノ基、４－イソブチルフェニルメチルアミノ基、ナフチルメチルアミノ基、メトキシカルボニルナフチルメチルアミノ基、エトキシカルボニルナフチルメチルアミノ基等が挙げられる。
　アリールアミノ基の具体例としては、フェニルアミノ基、メトキシカルボニルフェニルアミノ基、エトキシカルボニルフェニルアミノ基、ナフチルアミノ基、メトキシカルボニルナフチルアミノ基、エトキシカルボニルナフチルアミノ基、アントラニルアミノ基、ピレニルアミノ基、ビフェニルアミノ基、ターフェニルアミノ基、フルオレニルアミノ基等が挙げられる。 Specific examples of the aralkylamino group include benzylamino group, methoxycarbonylphenylmethylamino group, ethoxycarbonylphenylmethylamino group, p-methylphenylmethylamino group, m-methylphenylmethylamino group, and o-ethylphenylmethylamino group. M-ethylphenylmethylamino group, p-ethylphenylmethylamino group, 2-propylphenylmethylamino group, 4-isopropylphenylmethylamino group, 4-isobutylphenylmethylamino group, naphthylmethylamino group, methoxycarbonylnaphthylmethyl An amino group, an ethoxycarbonyl naphthylmethylamino group, etc. are mentioned.
Specific examples of the arylamino group include phenylamino group, methoxycarbonylphenylamino group, ethoxycarbonylphenylamino group, naphthylamino group, methoxycarbonylnaphthylamino group, ethoxycarbonylnaphthylamino group, anthranylamino group, pyrenylamino group, biphenylamino. Group, terphenylamino group, fluorenylamino group and the like.
　アルコキシシリル基含有アルキルアミノ基としては、モノアルコキシシリル基含有アルキルアミノ基、ジアルコキシシリル基含有アルキルアミノ基、トリアルコキシシリル基含有アルキルアミノ基のいずれでもよく、その具体例としては、３－トリメトキシシリルプロピルアミノ基、３－トリエトキシシリルプロピルアミノ基、３－ジメチルエトキシシリルプロピルアミノ基、３－メチルジエトキシシリルプロピルアミノ基、Ｎ－（２－アミノエチル）－３－ジメチルメトキシシリルプロピルアミノ基、Ｎ－（２－アミノエチル）－３－メチルジメトキシシリルプロピルアミノ基、Ｎ－（２－アミノエチル）－３－トリメトキシシリルプロピルアミノ基等が挙げられる。 The alkoxysilyl group-containing alkylamino group may be any of a monoalkoxysilyl group-containing alkylamino group, a dialkoxysilyl group-containing alkylamino group, or a trialkoxysilyl group-containing alkylamino group. Methoxysilylpropylamino group, 3-triethoxysilylpropylamino group, 3-dimethylethoxysilylpropylamino group, 3-methyldiethoxysilylpropylamino group, N- (2-aminoethyl) -3-dimethylmethoxysilylpropylamino group Group, N- (2-aminoethyl) -3-methyldimethoxysilylpropylamino group, N- (2-aminoethyl) -3-trimethoxysilylpropylamino group, and the like.
　アリールオキシ基の具体例としては、フェノキシ基、ナフトキシ基、アントラニルオキシ基、ピレニルオキシ基、ビフェニルオキシ基、ターフェニルオキシ基、フルオレニルオキシ基等が挙げられる。
　アラルキルオキシ基の具体例としては、ベンジルオキシ基、ｐ－メチルフェニルメチルオキシ基、ｍ－メチルフェニルメチルオキシ基、ｏ－エチルフェニルメチルオキシ基、ｍ－エチルフェニルメチルオキシ基、ｐ－エチルフェニルメチルオキシ基、２－プロピルフェニルメチルオキシ基、４－イソプロピルフェニルメチルオキシ基、４－イソブチルフェニルメチルオキシ基、α－ナフチルメチルオキシ基等が挙げられる。
　その他、アルキル基、アラルキル基、アリール基としては上述した基と同様のものが挙げられる。 Specific examples of the aryloxy group include a phenoxy group, a naphthoxy group, an anthranyloxy group, a pyrenyloxy group, a biphenyloxy group, a terphenyloxy group, and a fluorenyloxy group.
Specific examples of the aralkyloxy group include benzyloxy group, p-methylphenylmethyloxy group, m-methylphenylmethyloxy group, o-ethylphenylmethyloxy group, m-ethylphenylmethyloxy group, p-ethylphenylmethyl group. Examples include an oxy group, 2-propylphenylmethyloxy group, 4-isopropylphenylmethyloxy group, 4-isobutylphenylmethyloxy group, α-naphthylmethyloxy group, and the like.
In addition, examples of the alkyl group, the aralkyl group, and the aryl group include the same groups as those described above.
　これらの基は、トリアジン環上のハロゲン原子を対応する置換基を与える化合物で置換することで容易に導入することができ、例えば、下記式スキーム５，６に示されるように、アニリン誘導体を加えて反応させることで、少なくとも１つの末端にフェニルアミノ基を有するハイパーブランチポリマー（３３），（３４）が得られる。 These groups can be easily introduced by substituting a halogen atom on the triazine ring with a compound that gives a corresponding substituent. For example, as shown in the following schemes 5 and 6, an aniline derivative is added. To obtain hyperbranched polymers (33) and (34) having a phenylamino group at at least one terminal.
Figure JPOXMLDOC01-appb-C000032
 （式中、ＸおよびＲは上記と同じ意味を表す。）
Figure JPOXMLDOC01-appb-C000032
 (Wherein X and R represent the same meaning as described above.)
Figure JPOXMLDOC01-appb-C000033
 （式中、ＸおよびＲは上記と同じ意味を表す。）
Figure JPOXMLDOC01-appb-C000033
 (Wherein X and R represent the same meaning as described above.)
　この際、有機モノアミンの同時仕込みを行う、すなわち、有機モノアミンの存在下で、ハロゲン化シアヌル化合物と、ジアミノ化合物とを反応させることで、ハイパーブランチポリマーの剛直性が緩和された、分岐度の低い柔らかいハイパーブランチポリマーを得ることができる。
　この手法によって得られたハイパーブランチポリマーは、溶剤への溶解性（凝集抑制）や、架橋剤との架橋性に優れたものとなるため、後述する架橋剤と組み合わせた組成物として用いる場合に特に有利である。
　ここで、有機モノアミンとしては、アルキルモノアミン、アラルキルモノアミン、アリールモノアミンのいずれを用いることもできる。 At this time, the organic monoamine is charged simultaneously, that is, by reacting the cyanuric halide compound with the diamino compound in the presence of the organic monoamine, the rigidity of the hyperbranched polymer is relaxed and the degree of branching is low. A soft hyperbranched polymer can be obtained.
The hyperbranched polymer obtained by this method has excellent solubility in a solvent (inhibition of aggregation) and crosslinkability with a crosslinking agent, and is particularly used when used as a composition in combination with a crosslinking agent described later. It is advantageous.
Here, as the organic monoamine, any of alkyl monoamine, aralkyl monoamine, and aryl monoamine can be used.
　アルキルモノアミンとしては、メチルアミン、エチルアミン、ｎ－プロピルアミン、イソプロピルアミン、ｎ－ブチルアミン、イソブチルアミン、ｓ－ブチルアミン、ｔ－ブチルアミン、ｎ－ペンチルアミン、１－メチル－ｎ－ブチルアミン、２－メチル－ｎ－ブチルアミン、３－メチル－ｎ－ブチルアミン、１，１－ジメチル－ｎ－プロピルアミン、１，２－ジメチル－ｎ－プロピルアミン、２，２－ジメチル－ｎ－プロピルアミン、１－エチル－ｎ－プロピルアミン、ｎ－ヘキシルアミン、１－メチル－ｎ－ペンチルアミン、２－メチル－ｎ－ペンチルアミン、３－メチル－ｎ－ペンチルアミン、４－メチル－ｎ－ペンチルアミン、１，１－ジメチル－ｎ－ブチルアミン、１，２－ジメチル－ｎ－ブチルアミン、１，３－ジメチル－ｎ－ブチルアミン、２，２－ジメチル－ｎ－ブチルアミン、２，３－ジメチル－ｎ－ブチルアミン、３，３－ジメチル－ｎ－ブチルアミン、１－エチル－ｎ－ブチルアミン、２－エチル－ｎ－ブチルアミン、１，１，２－トリメチル－ｎ－プロピルアミン、１，２，２－トリメチル－ｎ－プロピルアミン、１－エチル－１－メチル－ｎ－プロピルアミン、１－エチル－２－メチル－ｎ－プロピルアミン、２－エチルヘキシルアミン等が挙げられる。 Alkyl monoamines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine, 1-methyl-n-butylamine, 2-methyl- n-butylamine, 3-methyl-n-butylamine, 1,1-dimethyl-n-propylamine, 1,2-dimethyl-n-propylamine, 2,2-dimethyl-n-propylamine, 1-ethyl-n -Propylamine, n-hexylamine, 1-methyl-n-pentylamine, 2-methyl-n-pentylamine, 3-methyl-n-pentylamine, 4-methyl-n-pentylamine, 1,1-dimethyl -N-butylamine, 1,2-dimethyl-n-butylamine, 1,3-dimethyl-n Butylamine, 2,2-dimethyl-n-butylamine, 2,3-dimethyl-n-butylamine, 3,3-dimethyl-n-butylamine, 1-ethyl-n-butylamine, 2-ethyl-n-butylamine, 1, 1,2-trimethyl-n-propylamine, 1,2,2-trimethyl-n-propylamine, 1-ethyl-1-methyl-n-propylamine, 1-ethyl-2-methyl-n-propylamine, Examples include 2-ethylhexylamine.
　アラルキルモノアミンの具体例としては、ベンジルアミン、ｐ－メトキシカルボニルベンジルアミン、ｐ－エトキシカルボニルベンジルアミン、ｐ－メチルベンジルアミン、ｍ－メチルベンジルアミン、ｏ－メトキシベンジルアミン等が挙げられる。
　アリールモノアミンの具体例としては、アニリン、ｐ－メトキシカルボニルアニリン、ｐ－エトキシカルボニルアニリン、ｐ－メトキシアニリン、１－ナフチルアミン、２－ナフチルアミン、アントラニルアミン、１－アミノピレン、４－ビフェニリルアミン、ｏ－フェニルアニリン、４－アミノ－ｐ－ターフェニル、２－アミノフルオレン等が挙げられる。 Specific examples of aralkyl monoamines include benzylamine, p-methoxycarbonylbenzylamine, p-ethoxycarbonylbenzylamine, p-methylbenzylamine, m-methylbenzylamine, o-methoxybenzylamine and the like.
Specific examples of the aryl monoamine include aniline, p-methoxycarbonylaniline, p-ethoxycarbonylaniline, p-methoxyaniline, 1-naphthylamine, 2-naphthylamine, anthranylamine, 1-aminopyrene, 4-biphenylylamine, o- And phenylaniline, 4-amino-p-terphenyl, 2-aminofluorene, and the like.
　この場合、有機モノアミンの使用量は、ハロゲン化シアヌル化合物１当量に対して、０．０５～５００当量が好ましく、０．０５～１２０当量がより好ましく、０．０５～５０当量がより一層好ましい。
　この場合の反応温度も、リニア性を抑え、分岐度を高めるという点から、６０～１５０℃が好ましく、８０～１５０℃が好ましく、８０～１２０℃が好ましい。
　ただし、有機モノアミン、ハロゲン化シアヌル化合物、ジアミン化合物の３成分の混合は、低温下で行ってもよく、その場合の温度としては、－５０～５０℃程度が好ましく、－２０～５０℃程度がより好ましく、－２０～１０℃がさらに好ましい。低温仕込み後は、重合させる温度まで一気に（一段階で）昇温して反応を行うことが好ましい。 In this case, the amount of the organic monoamine used is preferably 0.05 to 500 equivalents, more preferably 0.05 to 120 equivalents, and even more preferably 0.05 to 50 equivalents per equivalent of the cyanuric halide compound.
In this case, the reaction temperature is preferably 60 to 150 ° C., preferably 80 to 150 ° C., and preferably 80 to 120 ° C. from the viewpoint of suppressing linearity and increasing the degree of branching.
However, the mixing of the three components of the organic monoamine, the halogenated cyanuric compound, and the diamine compound may be performed at a low temperature. In this case, the temperature is preferably about −50 to 50 ° C., and about −20 to 50 ° C. More preferred is −20 to 10 ° C. After the low temperature charging, it is preferable to carry out the reaction by raising the temperature to the polymerization temperature at once (in one step).
　また、ハロゲン化シアヌル化合物とジアミン化合物の２成分の混合を低温下で行ってもよく、その場合の温度としては、－５０～５０℃程度が好ましく、－２０～５０℃程度がより好ましく、－２０～１０℃がさらに好ましい。低温仕込み後、有機モノアミンを加え、重合させる温度まで一気に（一段階で）昇温して反応を行うことが好ましい。
　また、このような有機モノアミンの存在下で、ハロゲン化シアヌル化合物と、ジアミン化合物とを反応させる反応は、上述と同様の有機溶媒を用いて行ってもよい。 Further, the two components of the cyanuric halide compound and the diamine compound may be mixed at a low temperature. In this case, the temperature is preferably about −50 to 50 ° C., more preferably about −20 to 50 ° C., 20 to 10 ° C. is more preferable. It is preferable to carry out the reaction by adding an organic monoamine after the low-temperature charging and raising the temperature to a temperature for polymerization (in one step).
Moreover, you may perform reaction which makes a halogenated cyanuric compound and a diamine compound react in presence of such an organic monoamine using the organic solvent similar to the above-mentioned.
　上述した本発明の重合体は、他の化合物と混合した組成物として用いることができ、例えば、レベリング剤、界面活性剤、架橋剤、樹脂等との組成物が挙げられる。
　これらの組成物は、膜形成用組成物として用いることができ、各種の溶剤に溶かした膜形成用組成物（ポリマーワニスともいう）として好適に使用できる。
　重合体を溶解するのに用いる溶剤は、重合時に用いた溶媒と同じものでも別のものでもよい。この溶剤は、重合体との相溶性を損なわなければ特に限定されず、１種でも複数種でも任意に選択して用いることができる。 The polymer of the present invention described above can be used as a composition mixed with other compounds, and examples thereof include a composition with a leveling agent, a surfactant, a crosslinking agent, a resin and the like.
These compositions can be used as a film-forming composition, and can be suitably used as a film-forming composition (also referred to as a polymer varnish) dissolved in various solvents.
The solvent used for dissolving the polymer may be the same as or different from the solvent used during the polymerization. The solvent is not particularly limited as long as the compatibility with the polymer is not impaired, and one kind or a plurality of kinds can be arbitrarily selected and used.
　このような溶剤の具体例としては、トルエン、ｐ－キシレン、ｏ－キシレン、ｍ－キシレン、エチルベンゼン、スチレン、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、プロピレングリコール、プロピレングリコールモノエチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノイソプロピルエーテル、エチレングリコールメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、ジエチレングリコールジメチルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコ－ルモノブチルエーテル、ジエチレングリコールジエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル、トリエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコール、１－オクタノール、エチレングリコール、ヘキシレングリコール、トリメチレングリコール、１－メトキシ－２－ブタノール、シクロヘキサノール、ジアセトンアルコール、フルフリルアルコール、テトラヒドロフルフリルアルコール、プロピレングリコール、ベンジルアルコール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、γ－ブチロラクトン、アセトン、メチルエチルケトン、メチルイソプロピルケトン、ジエチルケトン、メチルイソブチルケトン、メチルノーマルブチルケトン、シクロヘキサノン、酢酸エチル、酢酸イソプロピル、酢酸ノーマルプロピル、酢酸イソブチル、酢酸ノーマルブチル、乳酸エチル、メタノール、エタノール、イソプロパノール、ｔｅｒｔ－ブタノール、アリルアルコール、ノーマルプロパノール、２－メチル－２－ブタノール、イソブタノール、ノーマルブタノール、２－メチル－１－ブタノール、１－ペンタノール、２－メチル－１－ペンタノール、２－エチルヘキサノール、１－メトキシ－２－プロパノール、テトラヒドロフラン、１，４－ジオキサン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、１，３－ジメチル－２－イミダゾリジノン、ジメチルスルホキシド、Ｎ－シクロヘキシル－２－ピロリジノン等が挙げられ、これらは単独で用いても、２種以上混合して用いてもよい。 Specific examples of such solvents include toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether. , Ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dip Pyrene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1 -Methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl ketone T, diethyl ketone, methyl isobutyl ketone, methyl normal butyl ketone, cyclohexanone, ethyl acetate, isopropyl acetate, normal propyl acetate, isobutyl acetate, normal butyl acetate, ethyl lactate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, normal Propanol, 2-methyl-2-butanol, isobutanol, normal butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-methoxy-2-propanol Tetrahydrofuran, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfone Kishido, N- cyclohexyl-2-pyrrolidinone and the like. These may be used singly or may be used in combination of two or more.
　この際、膜形成用組成物中の固形分濃度は、保存安定性に影響を与えない範囲であれば特に限定されず、目的とする膜の厚みに応じて適宜設定すればよい。具体的には、溶解性および保存安定性の観点から、固形分濃度０．１～５０質量％が好ましく、より好ましくは０．１～２０質量％である。 At this time, the solid content concentration in the film-forming composition is not particularly limited as long as it does not affect the storage stability, and may be appropriately set according to the target film thickness. Specifically, from the viewpoint of solubility and storage stability, the solid content concentration is preferably 0.1 to 50% by mass, and more preferably 0.1 to 20% by mass.
　本発明の膜形成用組成物では、本発明の効果を損なわない限りにおいて、トリアジン環含有重合体および溶剤以外のその他の成分、例えば、レベリング剤、界面活性剤、架橋剤等が含まれていてもよい。
　界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類；ポリオキシエチレンオクチルフェノールエーテル、ポリオキシエチレンノニルフェノールエーテル等のポリオキシエチレンアルキルアリルエーテル類；ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類；ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類；ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤、商品名エフトップＥＦ３０１、ＥＦ３０３、ＥＦ３５２（三菱マテリアル電子化成（株）製（旧（株）ジェムコ製）、商品名メガファックＦ１７１、Ｆ１７３、Ｒ－０８、Ｒ－３０、Ｆ－５５３、Ｆ－５５４（ＤＩＣ（株）製）、フロラードＦＣ４３０、ＦＣ４３１（住友スリーエム（株）製）、商品名アサヒガードＡＧ７１０，サーフロンＳ－３８２、ＳＣ１０１、ＳＣ１０２、ＳＣ１０３、ＳＣ１０４、ＳＣ１０５、ＳＣ１０６（旭硝子（株）製）等のフッ素系界面活性剤、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、ＢＹＫ－３０２、ＢＹＫ－３０７、ＢＹＫ－３２２、ＢＹＫ－３２３、ＢＹＫ－３３０、ＢＹＫ－３３３、ＢＹＫ－３７０、ＢＹＫ－３７５、ＢＹＫ－３７８（ビックケミー・ジャパン（株）製）等が挙げられる。 As long as the effects of the present invention are not impaired, the film-forming composition of the present invention contains other components other than the triazine ring-containing polymer and the solvent, for example, a leveling agent, a surfactant, a crosslinking agent, and the like. Also good.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol Polyoxyethylene alkyl allyl ethers such as ethers; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethyleneso Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, trade name EFTOP EF301, EF303, EF352 (Mitsubishi Materials Electronics Kasei Co., Ltd. (formerly Gemco Co., Ltd.), trade names MegaFuck F171, F173, R-08, R-30, F-553, F-554 (DIC Corporation) ) Fluorosurfactant such as FLORARD FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) Agent Ganosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 ( Big Chemie Japan Co., Ltd.).
　これらの界面活性剤は、単独で使用しても、２種以上組み合わせて使用してもよい。界面活性剤の使用量は、トリアジン環含有重合体１００質量部に対して０．０００１～５質量部が好ましく、０．００１～１質量部がより好ましく、０．０１～０．５質量部がより一層好ましい。 These surfactants may be used alone or in combination of two or more. The amount of the surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. Even more preferred.
　架橋剤としては、本発明のトリアジン環含有重合体と反応し得る置換基を有する化合物であれば特に限定されるものではない。
　そのような化合物としては、メチロール基、メトキシメチル基などの架橋形成置換基を有するメラミン系化合物、置換尿素系化合物、エポキシ基またはオキセタン基などの架橋形成置換基を含有する化合物、ブロック化イソシアナートを含有する化合物、酸無水物を有する化合物、（メタ）アクリル基を有する化合物、フェノプラスト化合物等が挙げられるが、耐熱性や保存安定性の観点からエポキシ基、ブロックイソシアネート基、（メタ）アクリル基を含有する化合物が好ましい。
　また、ブロックイソシアネート基は、尿素結合で架橋し、カルボニル基を有するため屈折率が低下しないという点からも好ましい。
　なお、これらの化合物は、ポリマーの末端処理に用いる場合は少なくとも１個の架橋形成置換基を有していればよく、ポリマー同士の架橋処理に用いる場合は少なくとも２個の架橋形成置換基を有する必要がある。 The crosslinking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with the triazine ring-containing polymer of the present invention.
Examples of such compounds include melamine compounds having a crosslinkable substituent such as a methylol group and methoxymethyl group, substituted urea compounds, compounds containing a crosslinkable substituent such as an epoxy group or an oxetane group, and blocked isocyanates. A compound containing acid, a compound having an acid anhydride, a compound having a (meth) acryl group, a phenoplast compound, and the like, but from the viewpoint of heat resistance and storage stability, an epoxy group, a blocked isocyanate group, (meth) acrylic Compounds containing groups are preferred.
The blocked isocyanate group is also preferable from the viewpoint that the refractive index does not decrease because it is crosslinked by a urea bond and has a carbonyl group.
These compounds only need to have at least one cross-linking substituent when used for polymer terminal treatment, and have at least two cross-linking substituents when used for cross-linking treatment between polymers. There is a need.
　エポキシ化合物としては、エポキシ基を一分子中２個以上有し、熱硬化時の高温に曝されると、エポキシが開環し、本発明のトリアジン環含有重合体との間で付加反応により架橋反応が進行するものである。
　架橋剤の具体例としては、トリス（２，３－エポキシプロピル）イソシアヌレート、１，４－ブタンジオールジグリシジルエーテル、１，２－エポキシ－４－（エポキシエチル）シクロヘキサン、グリセロールトリグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、２，６－ジグリシジルフェニルグリシジルエーテル、１，１，３－トリス［ｐ－（２，３－エポキシプロポキシ）フェニル］プロパン、１，２－シクロヘキサンジカルボン酸ジグリシジルエステル、４，４’－メチレンビス（Ｎ，Ｎ－ジグリシジルアニリン）、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、トリメチロールエタントリグリシジルエーテル、ビスフェノール－Ａ－ジグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル等が挙げられる。 As an epoxy compound, it has two or more epoxy groups in one molecule, and when exposed to a high temperature during thermosetting, the epoxy is ring-opened and crosslinked with the triazine ring-containing polymer of the present invention by an addition reaction. The reaction proceeds.
Specific examples of the crosslinking agent include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol Diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4 '-Methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentae Examples include lithitol polyglycidyl ether.
　また、市販品として、少なくとも２個のエポキシ基を有するエポキシ樹脂である、ＹＨ－４３４、ＹＨ４３４Ｌ（東都化成（株）製）、シクロヘキセンオキサイド構造を有するエポキシ樹脂である、エポリードＧＴ－４０１、同ＧＴ－４０３、同ＧＴ－３０１、同ＧＴ－３０２、セロキサイド２０２１、同３０００（ダイセル化学工業（株）製）、ビスフェノールＡ型エポキシ樹脂である、エピコート（現、ｊＥＲ）１００１、同１００２、同１００３、同１００４、同１００７、同１００９、同１０１０、同８２８（以上、ジャパンエポキシレジン（株）製）、ビスフェノールＦ型エポキシ樹脂である、エピコート（現、ｊＥＲ）８０７（ジャパンエポキシレジン（株）製）、フェノールノボラック型エポキシ樹脂である、エピコート（現、ｊＥＲ）１５２、同１５４（以上、ジャパンエポキシレジン（株）製）、ＥＰＰＮ２０１、同２０２（以上、日本化薬（株）製）、クレゾールノボラック型エポキシ樹脂である、ＥＯＣＮ－１０２、同１０３Ｓ、同１０４Ｓ、同１０２０、同１０２５、同１０２７（以上、日本化薬（株）製）、エピコート（現、ｊＥＲ）１８０Ｓ７５（ジャパンエポキシレジン（株）製）、脂環式エポキシ樹脂である、デナコールＥＸ－２５２（ナガセケムテックス（株）製）、ＣＹ１７５、ＣＹ１７７、ＣＹ１７９（以上、ＣＩＢＡ－ＧＥＩＧＹ　Ａ．Ｇ製）、アラルダイトＣＹ－１８２、同ＣＹ－１９２、同ＣＹ－１８４（以上、ＣＩＢＡ－ＧＥＩＧＹ　Ａ．Ｇ製）、エピクロン２００、同４００（以上、ＤＩＣ（株）製）、エピコート（現、ｊＥＲ）８７１、同８７２（以上、ジャパンエポキシレジン（株）製）、ＥＤ－５６６１、ＥＤ－５６６２（以上、セラニーズコーティング（株）製）、脂肪族ポリグリシジルエーテルである、デナコールＥＸ－６１１、同ＥＸ－６１２、同ＥＸ－６１４、同ＥＸ－６２２、同ＥＸ－４１１、同ＥＸ－５１２、同ＥＸ－５２２、同ＥＸ－４２１、同ＥＸ－３１３、同ＥＸ－３１４、同ＥＸ－３２１（ナガセケムテックス（株）製）等を用いることもできる。 In addition, as commercially available products, epoxy resins having at least two epoxy groups, YH-434, YH434L (manufactured by Tohto Kasei Co., Ltd.), epoxy resins having a cyclohexene oxide structure, Epolide GT-401 and GT -403, GT-301, GT-302, Celoxide 2021, 3000 (manufactured by Daicel Chemical Industries, Ltd.), bisphenol A type epoxy resin, Epicoat (currently jER) 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (Japan Epoxy Resin Co., Ltd.), Bisphenol F type epoxy resin, Epicoat (currently jER) 807 (Japan Epoxy Resin Co., Ltd.) , Epicoat (a phenol novolac type epoxy resin) , JER) 152, 154 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPPN 201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.), cresol novolac type epoxy resin, EOCN-102, 103S, 104S, 1020, 1025, 1027 (Nippon Kayaku Co., Ltd.), Epicort (currently jER) 180S75 (Japan Epoxy Resin Co., Ltd.), Denacol EX, an alicyclic epoxy resin -252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179 (above, CIBA-GEIGY A.G), Araldite CY-182, CY-192, CY-184 (above, CIBA-GEIGY A .G), Epicron 200, 400 (above, manufactured by DIC Corporation), Epicote (currently jE) 871, 872 (above, manufactured by Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5661 (above, made by Celanese Coating), Denacol EX-611, which is an aliphatic polyglycidyl ether. EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-522, EX-421, EX-313, EX-314, EX-321 (Nagase Chemtex Co., Ltd.) can also be used.
　酸無水物化合物としては、２分子のカルボン酸を脱水縮合させたカルボン酸無水物であり、熱硬化の際の高温に曝されると、無水物環が開環し、本発明のトリアジン環含有重合体との間で付加反応により架橋反応が進行するものである。
　また、酸無水物化合物の具体例としては、無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水ナジック酸、無水メチルナジック酸、無水マレイン酸、無水コハク酸、オクチル無水コハク酸、ドデセニル無水コハク酸等の分子内に１個の酸無水物基を有するもの；１，２，３，４－シクロブタンテトラカルボン酸二無水物、ピロメリット酸無水物、３，４－ジカルボキシ－１，２，３，４－テトラヒドロ－１－ナフタレンコハク酸二無水物、ビシクロ［３．３．０］オクタン－２，４，６，８－テトラカルボン酸二無水物、５－（２，５－ジオキソテトラヒドロ－３－フラニル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物、１，２，３，４－ブタンテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、２，２－ビス（３，４－ジカルボキシフェニル）ヘキサフルオロプロパン二無水物、１，３－ジメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物等の分子内に２個の酸無水物基を有するもの等が挙げられる。 The acid anhydride compound is a carboxylic acid anhydride obtained by dehydrating and condensing two molecules of carboxylic acid. When exposed to a high temperature during thermosetting, the anhydride ring is opened and the triazine ring of the present invention is contained. A crosslinking reaction proceeds with the polymer by an addition reaction.
Specific examples of the acid anhydride compound include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, maleic anhydride. Acid, succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride and the like having one acid anhydride group in the molecule; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic acid Anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid Dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2- dicarboxylic anhydride 1,2,3,4-butanetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride And those having one acid anhydride group.
　（メタ）アクリル化合物としては、（メタ）アクリル基を一分子中２個以上有し、そして熱硬化時の高温に曝されると、本発明のトリアジン環含有重合体との間で付加反応により架橋反応が進行するものである。
　（メタ）アクリル基を有する化合物としては、例えば、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、ポリエチレングリコールジアクリレート、ポリエチレングリコールジメタクリレート、エトキシ化ビスフェノールＡジアクリレート、エトキシ化ビスフェノールＡジメタクリレート、エトキシ化トリメチロールプロパントリアクリレート、エトキシ化トリメチロールプロパントリメタクリレート、エトキシ化グリセリントリアクリレート、エトキシ化グリセリントリメタクリレート、エトキシ化ペンタエリスリトールテトラアクリレート、エトキシ化ペンタエリスリトールテトラメタクリレート、エトキシ化ジペンタエリスリトールヘキサアクリレート、ポリグリセリンモノエチレンオキサイドポリアクリレート、ポリグリセリンポリエチレングリコールポリアクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、トリシクロデカンジメタノールジアクリレート、トリシクロデカンジメタノールジメタクリレート、１，６－ヘキサンジオールジアクリレート、１，６－ヘキサンジオールジメタクリレート等が挙げられる。 As a (meth) acrylic compound, it has two or more (meth) acrylic groups in one molecule, and when exposed to a high temperature during thermosetting, it undergoes an addition reaction with the triazine ring-containing polymer of the present invention. The crosslinking reaction proceeds.
Examples of the compound having a (meth) acryl group include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, and ethoxylated tri Methylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerol mono Ethylene oxide polyacrylate Polyglycerin polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, tri Examples include methylolpropane trimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and the like.
　上記（メタ）アクリル基を有する化合物は、市販品として入手が可能であり、その具体例としては、ＮＫエステルＡ－２００、同Ａ－４００、同Ａ－６００、同Ａ－１０００、同Ａ－ＴＭＰＴ、同ＵＡ－５３Ｈ、同１Ｇ、同２Ｇ、同３Ｇ、同４Ｇ、同９Ｇ、同１４Ｇ、同２３Ｇ、同ＡＢＥ－３００、同Ａ－ＢＰＥ－４、同Ａ－ＢＰＥ－６、同Ａ－ＢＰＥ－１０、同Ａ－ＢＰＥ－２０、同Ａ－ＢＰＥ－３０、同ＢＰＥ－８０Ｎ、同ＢＰＥ－１００Ｎ、同ＢＰＥ－２００、同ＢＰＥ－５００、同ＢＰＥ－９００、同ＢＰＥ－１３００Ｎ、同Ａ－ＧＬＹ－３Ｅ、同Ａ－ＧＬＹ－９Ｅ、同Ａ－ＧＬＹ－２０Ｅ、同Ａ－ＴＭＰＴ－３ＥＯ、同Ａ－ＴＭＰＴ－９ＥＯ、同ＡＴＭ－４Ｅ、同ＡＴＭ－３５Ｅ（以上、新中村化学工業（株）製）、ＫＡＹＡＲＡＤ（登録商標）ＤＰＥＡ－１２、同ＰＥＧ４００ＤＡ、同ＴＨＥ－３３０、同ＲＰ－１０４０（以上、日本化薬（株）製）、Ｍ－２１０、Ｍ－３５０（以上、東亞合成（株）製）、ＫＡＹＡＲＡＤ（登録商標）ＤＰＨＡ、同ＮＰＧＤＡ、同ＰＥＴ３０（以上、日本化薬（株）製）、ＮＫエステル　Ａ－ＤＰＨ、同Ａ－ＴＭＰＴ、同Ａ－ＤＣＰ、同Ａ－ＨＤ－Ｎ、同ＴＭＰＴ、同ＤＣＰ、同ＮＰＧ、同ＨＤ－Ｎ（以上、新中村化学工業（株）製）等が挙げられる。 The compound having the (meth) acryl group is available as a commercial product. Specific examples thereof include NK ester A-200, same A-400, same A-600, same A-1000, same A- TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A- BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE-100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A -GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO, ATM-4E, ATM-35E KAYAR) D (registered trademark) DPEA-12, PEG400DA, THE-330, RP-1040 (above, Nippon Kayaku Co., Ltd.), M-210, M-350 (above, Toagosei Co., Ltd.) , KAYARAD (registered trademark) DPHA, NPGDA, PET30 (Nippon Kayaku Co., Ltd.), NK ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT DCP, NPG, HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.).
　ブロック化イソシアネートを含有する化合物としては、イソシアネート基（－ＮＣＯ）が適当な保護基によりブロックされたブロック化イソシアネート基を一分子中２個以上有し、熱硬化時の高温に曝されると、保護基（ブロック部分）が熱解離して外れ、生じたイソシアネート基が樹脂との間で架橋反応を起こすものであり、例えば、下記式で示される基を一分子中２個以上（なお、これらの基は同一のものでも、また各々異なっているものでもよい）有する化合物が挙げられる。 As a compound containing a blocked isocyanate, when the isocyanate group (—NCO) has two or more blocked isocyanate groups blocked by an appropriate protective group in one molecule and is exposed to a high temperature during thermal curing, The protecting group (block portion) is dissociated by thermal dissociation, and the resulting isocyanate group causes a crosslinking reaction with the resin. For example, two or more groups represented by the following formula in one molecule (note these The groups may be the same or different from each other).
Figure JPOXMLDOC01-appb-C000034
 （式中、Ｒbはブロック部の有機基を表す。）
Figure JPOXMLDOC01-appb-C000034
 (In the formula, R b represents an organic group in the block part.)
　このような化合物は、例えば、一分子中２個以上のイソシアネート基を有する化合物に対して適当なブロック剤を反応させて得ることができる。
　一分子中２個以上のイソシアネート基を有する化合物としては、例えば、イソホロンジイソシアネート、１，６－ヘキサメチレンジイソシアネート、メチレンビス（４－シクロヘキシルイソシアネート）、トリメチルヘキサメチレンジイソシアネートのポリイソシアネートや、これらの二量体、三量体、および、これらとジオール類、トリオール類、ジアミン類、またはトリアミン類との反応物などが挙げられる。
　ブロック剤としては、例えば、メタノール、エタノール、イソプロパノール、ｎ－ブタノール、２－エトキシヘキサノール、２－Ｎ，Ｎ－ジメチルアミノエタノール、２－エトキシエタノール、シクロヘキサノール等のアルコール類；フェノール、ｏ－ニトロフェノール、ｐ－クロロフェノール、ｏ－、ｍ－またはｐ－クレゾール等のフェノール類；ε－カプロラクタム等のラクタム類、アセトンオキシム、メチルエチルケトンオキシム、メチルイソブチルケトンオキシム、シクロヘキサノンオキシム、アセトフェノンオキシム、ベンゾフェノンオキシム等のオキシム類；ピラゾール、３，５－ジメチルピラゾール、３－メチルピラゾール等のピラゾール類；ドデカンチオール、ベンゼンチオール等のチオール類などが挙げられる。 Such a compound can be obtained, for example, by reacting an appropriate blocking agent with a compound having two or more isocyanate groups in one molecule.
Examples of the compound having two or more isocyanate groups in one molecule include, for example, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), polyisocyanate of trimethylhexamethylene diisocyanate, and dimers thereof. , Trimers, and reaction products of these with diols, triols, diamines, or triamines.
Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol; phenol, o-nitrophenol , P-chlorophenol, phenols such as o-, m- or p-cresol; lactams such as ε-caprolactam, oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime And pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole; thiols such as dodecanethiol and benzenethiol.
　ブロック化イソシアネートを含有する化合物は、市販品としても入手が可能であり、その具体例としては、Ｂ－８３０、Ｂ－８１５Ｎ、Ｂ－８４２Ｎ、Ｂ－８７０Ｎ、Ｂ－８７４Ｎ、Ｂ－８８２Ｎ、Ｂ－７００５、Ｂ－７０３０、Ｂ－７０７５、Ｂ－５０１０（以上、三井化学ポリウレタン（株）製）、デュラネート（登録商標）１７Ｂ－６０ＰＸ、同ＴＰＡ－Ｂ８０Ｅ、同ＭＦ－Ｂ６０Ｘ、同ＭＦ－Ｋ６０Ｘ、同Ｅ４０２－Ｂ８０Ｔ（以上、旭化成ケミカルズ（株）製）、カレンズＭＯＩ－ＢＭ（登録商標）（以上、昭和電工（株）製）等が挙げられる。 A compound containing a blocked isocyanate is also available as a commercial product. Specific examples thereof include B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B -7005, B-7030, B-7075, B-5010 (Mitsui Chemicals Polyurethane Co., Ltd.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (above, manufactured by Asahi Kasei Chemicals Corporation), Karenz MOI-BM (registered trademark) (above, manufactured by Showa Denko Co., Ltd.), and the like.
　アミノプラスト化合物としては、メトキシメチレン基を一分子中２個以上有し、そして熱硬化時の高温に曝されると、本発明のトリアジン環含有重合体との間で脱メタノール縮合反応により架橋反応が進行するものである。
　メラミン系化合物としては、例えば、ヘキサメトキシメチルメラミン　ＣＹＭＥＬ（登録商標）３０３、テトラブトキシメチルグリコールウリル　同１１７０、テトラメトキシメチルベンゾグアナミン　同１１２３（以上、日本サイテックインダストリーズ（株）製）等のサイメルシリーズ、メチル化メラミン樹脂であるニカラック（登録商標）ＭＷ－３０ＨＭ、同ＭＷ－３９０、同ＭＷ－１００ＬＭ、同ＭＸ－７５０ＬＭ、メチル化尿素樹脂である同ＭＸ－２７０、同ＭＸ－２８０、同ＭＸ－２９０（以上、（株）三和ケミカル製）等のニカラックシリーズ等が挙げられる。
　オキセタン化合物としては、オキセタニル基を一分子中２個以上有し、そして熱硬化時の高温に曝されると、本発明のトリアジン環含有重合体との間で付加反応により架橋反応が進行するものである。
　オキセタン基を有する化合物としては、例えば、オキセタン基を含有するＯＸＴ－２２１、ＯＸ－ＳＱ－Ｈ、ＯＸ－ＳＣ（以上、東亜合成（株）製）等が挙げられる。 As an aminoplast compound, it has two or more methoxymethylene groups in one molecule, and when exposed to a high temperature during thermosetting, it undergoes a crosslinking reaction by a demethanol condensation reaction with the triazine ring-containing polymer of the present invention. Is something that progresses.
Examples of the melamine-based compound include Cymel series such as hexamethoxymethylmelamine CYMEL (registered trademark) 303, tetrabutoxymethylglycoluril 1170, tetramethoxymethylbenzoguanamine 1123 (above, manufactured by Nihon Cytec Industries, Ltd.), Nicalac (registered trademark) MW-30HM, MW-390, MW-100LM, MX-750LM, which are methylated melamine resins, MX-270, MX-280, MX-290, which are methylated urea resins. (Nicarak series, etc., manufactured by Sanwa Chemical Co., Ltd.).
The oxetane compound has two or more oxetanyl groups in one molecule and undergoes a crosslinking reaction by an addition reaction with the triazine ring-containing polymer of the present invention when exposed to a high temperature during thermosetting. It is.
Examples of the compound having an oxetane group include OX-221-containing oxetane group, OX-SQ-H, and OX-SC (manufactured by Toagosei Co., Ltd.).
　フェノプラスト化合物としては、ヒドロキシメチレン基を一分子中２個以上有し、そして熱硬化時の高温に曝されると、本発明のトリアジン環含有重合体との間で脱水縮合反応により架橋反応が進行するものである。
　フェノプラスト化合物としては、例えば、２，６－ジヒドロキシメチル－４－メチルフェノール、２，４－ジヒドロキシメチル－６－メチルフェノール、ビス（２－ヒドロキシ－３－ヒドロキシメチル－５－メチルフェニル）メタン、ビス（４－ヒドロキシ－３－ヒドロキシメチル－５－メチルフェニル）メタン、２，２－ビス（４－ヒドロキシ－３，５－ジヒドロキシメチルフェニル）プロパン、ビス（３－ホルミル－４－ヒドロキシフェニル）メタン、ビス（４－ヒドロキシ－２，５－ジメチルフェニル）ホルミルメタン、α，α－ビス（４－ヒドロキシ－２，５－ジメチルフェニル）－４－ホルミルトルエン等が挙げられる。
　フェノプラスト化合物は、市販品としても入手が可能であり、その具体例としては、２６ＤＭＰＣ、４６ＤＭＯＣ、ＤＭ－ＢＩＰＣ－Ｆ、ＤＭ－ＢＩＯＣ－Ｆ、ＴＭ－ＢＩＰ－Ａ、ＢＩＳＡ－Ｆ、ＢＩ２５Ｘ－ＤＦ、ＢＩ２５Ｘ－ＴＰＡ（以上、旭有機材工業（株）製）等が挙げられる。 The phenoplast compound has two or more hydroxymethylene groups in one molecule and undergoes a crosslinking reaction by dehydration condensation reaction with the triazine ring-containing polymer of the present invention when exposed to a high temperature during thermosetting. It is a progression.
Examples of the phenoplast compound include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, Bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane, bis (3-formyl-4-hydroxyphenyl) methane Bis (4-hydroxy-2,5-dimethylphenyl) formylmethane, α, α-bis (4-hydroxy-2,5-dimethylphenyl) -4-formyltoluene and the like.
The phenoplast compound is also available as a commercial product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF. BI25X-TPA (above, manufactured by Asahi Organic Materials Co., Ltd.).
　これらの架橋剤は単独で使用しても、２種以上組み合わせて使用してもよい。架橋剤の使用量は、トリアジン環含有重合体１００質量部に対して、１～１００質量部が好ましいが、溶剤耐性を考慮すると、その下限は、好ましくは１０質量部、より好ましくは２０質量部であり、さらには、屈折率をコントロールすることを考慮すると、その上限は好ましくは５０質量部、より好ましくは３０質量部である。
　架橋剤を用いることで、架橋剤とトリアジン環含有重合体が有する反応性の末端置換基とが反応し、膜密度の向上、耐熱性の向上、熱緩和能力の向上などの効果を発現できる場合がある。
　なお、上記その他の成分は、本発明の組成物を調製する際の任意の工程で添加することができる。 These crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent used is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer, but considering the solvent resistance, the lower limit is preferably 10 parts by mass, more preferably 20 parts by mass. Furthermore, in consideration of controlling the refractive index, the upper limit is preferably 50 parts by mass, more preferably 30 parts by mass.
When the crosslinking agent and the reactive terminal substituent of the triazine ring-containing polymer react with each other, and effects such as improved film density, improved heat resistance, and improved thermal relaxation ability can be achieved There is.
In addition, the said other component can be added at the arbitrary processes at the time of preparing the composition of this invention.
　本発明の膜形成用組成物は、基材に塗布し、その後、必要に応じて加熱することで所望の膜を形成することができる。
　組成物の塗布方法は任意であり、例えば、スピンコート法、ディップ法、フローコート法、インクジェット法、スプレー法、バーコート法、グラビアコート法、スリットコート法、ロールコート法、転写印刷法、刷毛塗り、ブレードコート法、エアーナイフコート法等の方法を採用できる。 The film-forming composition of the present invention can be applied to a substrate and then heated as necessary to form a desired film.
The coating method of the composition is arbitrary, for example, spin coating method, dip method, flow coating method, ink jet method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer printing method, brush Methods such as coating, blade coating, and air knife coating can be employed.
　また、基材としては、シリコン、インジウム錫酸化物（ＩＴＯ）が成膜されたガラス、インジウム亜鉛酸化物（ＩＺＯ）が成膜されたガラス、ポリエチレンテレフタレート（ＰＥＴ）、プラスチック、ガラス、石英、セラミックス等からなる基材等が挙げられ、可撓性を有するフレキシブル基材を用いることもできる。
　焼成温度は、溶媒を蒸発させる目的では特に限定されず、例えば４０～４００℃で行うことができる。これらの場合、より高い均一製膜性を発現させたり、基材上で反応を進行させたりする目的で２段階以上の温度変化をつけてもよい。
　焼成方法としては、特に限定されるものではなく、例えば、ホットプレートやオーブンを用いて、大気、窒素等の不活性ガス、真空中等の適切な雰囲気下で蒸発させればよい。
　焼成温度および焼成時間は、目的とする電子デバイスのプロセス工程に適合した条件を選択すればよく、得られる膜の物性値が電子デバイスの要求特性に適合するような焼成条件を選択すればよい。 As the base material, silicon, glass with indium tin oxide (ITO) formed, glass with indium zinc oxide (IZO) formed, polyethylene terephthalate (PET), plastic, glass, quartz, ceramics A flexible substrate having flexibility can be used.
The firing temperature is not particularly limited for the purpose of evaporating the solvent, and can be performed at 40 to 400 ° C., for example. In these cases, the temperature may be changed in two or more steps for the purpose of expressing a higher uniform film forming property or allowing the reaction to proceed on the substrate.
The baking method is not particularly limited, and for example, it may be evaporated using a hot plate or an oven in an appropriate atmosphere such as air, an inert gas such as nitrogen, or in a vacuum.
The firing temperature and firing time may be selected in accordance with the process steps of the target electronic device, and the firing conditions may be selected so that the physical properties of the obtained film meet the required characteristics of the electronic device.
　このようにして得られた本発明の組成物からなる膜は、高耐熱性、高透明性、高屈折率、高溶解性、および低体積収縮を達成できるため、液晶ディスプレイ、有機エレクトロルミネッセンス（ＥＬ）ディスプレイ、光半導体（ＬＥＤ）素子、固体撮像素子、有機薄膜太陽電池、色素増感太陽電池、有機薄膜トランジスタ（ＴＦＴ）などの電子デバイスを作製する際の一部材として好適に利用できる。 The film made of the composition of the present invention thus obtained can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage, so that it can be used for liquid crystal displays, organic electroluminescence (EL ) It can be suitably used as a member for producing electronic devices such as displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin film solar cells, dye-sensitized solar cells, and organic thin film transistors (TFTs).
　なお、本発明の組成物には、必要に応じてその他の樹脂（熱可塑性樹脂または熱硬化性樹脂）を配合してもよい。
　樹脂の具体例としては、特に限定されるものではない。熱可塑性樹脂としては、例えば、ＰＥ（ポリエチレン）、ＰＰ（ポリプロピレン）、ＥＶＡ（エチレン－酢酸ビニル共重合体）、ＥＥＡ（エチレン－アクリル酸エチル共重合体）等のポリオレフィン系樹脂；ＰＳ（ポリスチレン）、ＨＩＰＳ（ハイインパクトポリスチレン）、ＡＳ（アクリロニトリル－スチレン共重合体）、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン共重合体）、ＭＳ（メタクリル酸メチル－スチレン共重合体）等のポリスチレン系樹脂；ポリカーボネート樹脂；塩化ビニル樹脂；ポリアミド樹脂；ポリイミド樹脂；ＰＭＭＡ（ポリメチルメタクリレート）等の（メタ）アクリル樹脂；ＰＥＴ（ポリエチレンテレフタレート）、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ＰＬＡ（ポリ乳酸）、ポリ－３－ヒドロキシ酪酸、ポリカプロラクトン、ポリブチレンサクシネート、ポリエチレンサクシネート／アジペート等のポリエステル樹脂；ポリフェニレンエーテル樹脂；変性ポリフェニレンエーテル樹脂；ポリアセタール樹脂；ポリスルホン樹脂；ポリフェニレンサルファイド樹脂；ポリビニルアルコール樹脂；ポリグルコール酸；変性でんぷん；酢酸セルロース、三酢酸セルロース；キチン、キトサン；リグニンなどが挙げられ、熱硬化性樹脂としては、例えば、フェノール樹脂、尿素樹脂、メラミン樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂などが挙げられる。
　これらの樹脂は、単独で用いても、２種以上組み合わせて用いてもよく、その使用量は、上記トリアジン環含有重合体１００質量部に対して、１～１０，０００質量部が好ましく、より好ましくは１～１，０００質量部である。 In addition, you may mix | blend other resin (thermoplastic resin or thermosetting resin) with the composition of this invention as needed.
Specific examples of the resin are not particularly limited. Examples of the thermoplastic resin include polyolefin resins such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer); PS (polystyrene) Polystyrene resins such as HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer); polycarbonate resin; Polyvinyl resin; Polyamide resin; (Meth) acrylic resin such as PMMA (polymethyl methacrylate); PET (polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate Polyester resin such as PLA (polylactic acid), poly-3-hydroxybutyric acid, polycaprolactone, polybutylene succinate, polyethylene succinate / adipate; polyphenylene ether resin; modified polyphenylene ether resin; polyacetal resin; polysulfone resin; Polyvinyl alcohol resin; polyglycolic acid; modified starch; cellulose acetate, cellulose triacetate; chitin, chitosan; lignin and the like. Examples of thermosetting resins include phenol resin, urea resin, melamine resin, unsaturated polyester resin. , Polyurethane resin, epoxy resin and the like.
These resins may be used alone or in combination of two or more, and the amount used is preferably 1 to 10,000 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. The amount is preferably 1 to 1,000 parts by mass.
　例えば、（メタ）アクリル樹脂との組成物は、（メタ）アクリレート化合物を組成物に配合し、（メタ）アクリレート化合物を重合させて得ることができる。
　（メタ）アクリレート化合物の例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリオキシエチル（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、トリシクロデカニルジ（メタ）アクリレート、トリメチロールプロパントリオキシプロピル（メタ）アクリレート、トリス－２－ヒドロキシエチルイソシアヌレートトリ（メタ）アクリレート、トリス－２－ヒドロキシエチルイソシアヌレートジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、グリセリンメタクリレートアクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリメタクリレート、（メタ）アクリル酸アリル、（メタ）アクリル酸ビニル、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、ウレタン（メタ）アクリレート等が挙げられる。 For example, a composition with a (meth) acrylic resin can be obtained by blending a (meth) acrylate compound into the composition and polymerizing the (meth) acrylate compound.
Examples of (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri Oxyethyl (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, tricyclodecanyl di (meth) acrylate, trimethylolpropane trioxypropyl (meth) Chlorate, tris-2-hydroxyethyl isocyanurate tri (meth) acrylate, tris-2-hydroxyethyl isocyanurate di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, Glycerin methacrylate acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane trimethacrylate, allyl (meth) acrylate, vinyl (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, etc. Is mentioned.
　これらの（メタ）アクリレート化合物の重合は、光ラジカル開始剤や熱ラジカル開始剤の存在下、光照射または加熱して行うことができる。
　光ラジカル重合開始剤としては、例えば、アセトフェノン類、ベンゾフェノン類、ミヒラーのベンゾイルベンゾエート、アミロキシムエステル、テトラメチルチウラムモノサルファイドおよびチオキサントン類等が挙げられる。
　特に、光開裂型の光ラジカル重合開始剤が好ましい。光開裂型の光ラジカル重合開始剤については、最新ＵＶ硬化技術（１５９頁、発行人：高薄一弘、発行所：（株）技術情報協会、１９９１年発行）に記載されている。
　市販の光ラジカル重合開始剤としては、例えば、チバ・ジャパン（株）製　商品名：　イルガキュア　１８４、３６９、６５１、５００、８１９、９０７、７８４、２９５９、ＣＧＩ１７００、ＣＧＩ１７５０、ＣＧＩ１８５０、ＣＧ２４－６１、ダロキュア　１１１６、１１７３、ＢＡＳＦ社製　商品名：ルシリン　ＴＰＯ、ＵＣＢ社製　商品名：ユベクリル　Ｐ３６、フラテツリ・ランベルティ社製　商品名：エザキュアー　ＫＩＰ１５０、ＫＩＰ６５ＬＴ、ＫＩＰ１００Ｆ、ＫＴ３７、ＫＴ５５、ＫＴＯ４６、ＫＩＰ７５／Ｂ等が挙げられる。 Polymerization of these (meth) acrylate compounds can be carried out by light irradiation or heating in the presence of a photo radical initiator or a heat radical initiator.
Examples of the photo radical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.
In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (p. 159, publisher: Kazuhiro Takahisa, publisher: Technical Information Association, Inc., published in 1991).
Examples of commercially available radical photopolymerization initiators are, for example, trade names: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG24-61, Darocur, manufactured by Ciba Japan 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Ubekrill P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, etc. It is done.
　光重合開始剤は、（メタ）アクリレート化合物１００質量部に対して、０．１～１５質量部の範囲で使用することが好ましく、より好ましくは１～１０質量部の範囲である。
　重合に用いる溶剤は、上記膜形成用組成物で例示した溶剤と同様のものが挙げられる。 The photopolymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylate compound.
Examples of the solvent used for the polymerization include the same solvents as those exemplified above for the film-forming composition.
　以下、実施例および比較例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。なお、実施例で用いた各測定装置は以下のとおりである。
［1Ｈ－ＮＭＲ］
　装置：Ｖａｒｉａｎ　ＮＭＲ　Ｓｙｓｔｅｍ　４００ＮＢ（４００ＭＨｚ）
　　　　ＪＥＯＬ－ＥＣＡ７００（７００ＭＨｚ）
　測定溶媒：ＤＭＳＯ－ｄ６
　基準物質：テトラメチルシラン（ＴＭＳ）（δ０．０ｐｐｍ）
［ＧＰＣ］
　装置：東ソー（株）製　ＨＬＣ－８２００　ＧＰＣ
　カラム：Ｓｈｏｄｅｘ　ＫＦ－８０４Ｌ＋ＫＦ－８０５Ｌ
　カラム温度：４０℃
　溶媒：テトラヒドロフラン（以下、ＴＨＦ）
　検出器：ＵＶ（２５４ｎｍ）
　検量線：標準ポリスチレン
［エリプソメーター］
　装置：ジェー・エー・ウーラム・ジャパン製　多入射角分光エリプソメーターＶＡＳＥ
［示差熱天秤（ＴＧ－ＤＴＡ）］
　装置：（株）リガク製　ＴＧ－８１２０
　昇温速度：１０℃／分
　測定温度：２５℃－７５０℃ EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, each measuring apparatus used in the Example is as follows.
[ 1 H-NMR]
Apparatus: Varian NMR System 400NB (400MHz)
JEOL-ECA700 (700MHz)
Measuring solvent: DMSO-d6
Reference substance: Tetramethylsilane (TMS) (δ0.0ppm)
[GPC]
Equipment: HLC-8200 GPC manufactured by Tosoh Corporation
Column: Shodex KF-804L + KF-805L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran (hereinafter THF)
Detector: UV (254 nm)
Calibration curve: Standard polystyrene [Ellipsometer]
Apparatus: Multi-angle-of-incidence spectroscopic ellipsometer VASE manufactured by JA Woollam Japan
[Differential thermal balance (TG-DTA)]
Equipment: TG-8120, manufactured by Rigaku Corporation
Temperature increase rate: 10 ° C / min Measurement temperature: 25 ° C-750 ° C
［実施例１］高分子化合物［１］の合成（ジアミン単一重合）
Figure JPOXMLDOC01-appb-C000035
 （式中、Ｍｅはメチル基を意味する。） [Example 1] Synthesis of polymer compound [1] (diamine single polymerization)
Figure JPOXMLDOC01-appb-C000035
 (In the formula, Me means a methyl group.)
　２００ｍＬ四口フラスコに、２，２－ビス（３－アミノ－４－メチルフェニル）ヘキサフルオロプロパン（４．３２ｇ、１１．９３ｍｍｏｌ、セントラル硝子（株）製）を入れ、ジメチルアセトアミド（以下、ＤＭＡｃ）３２ｍＬに溶解して、オイルバスで１００℃に加熱した。その後、ＤＭＡｃ３２ｍＬに溶解した２，４，６－トリクロロ－１，３，５－トリアジン（２．００ｇ、１０．９ｍｍｏｌ、東京化成工業（株）製）を加えて重合を開始した。
　５０分後、アニリン（３．０３ｇ、３２．５ｍｍｏｌ、純正化学（株）製）を加え、３０分間撹拌して重合を停止した。室温まで放冷後、２８％アンモニア水溶液（１．９８ｇ）を水２４０ｍＬおよびメタノール８０ｍＬに溶解した混合溶液中に再沈殿させた。沈殿物をろ過し、ＴＨＦ３５ｍＬに再溶解させ、イオン交換水２５０ｍＬに再沈殿した。得られた沈殿物をろ過し、減圧乾燥機で１２０℃、６時間乾燥し、目的とする高分子化合物［１］５．１１ｇを得た。1Ｈ－ＮＭＲスペクトルの測定結果を図１に示す。得られた高分子化合物［１］は式（１）で表される構造単位を有する化合物である。高分子化合物［１］のＧＰＣによるポリスチレン換算で測定される重量平均分子量Ｍｗは８，９００、多分散度Ｍｗ／Ｍｎは４．９２であった。また、ＴＧ－ＤＴＡによる５％重量減少温度は、３３９℃であった。 In a 200 mL four-necked flask, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane (4.32 g, 11.93 mmol, manufactured by Central Glass Co., Ltd.) was placed, and dimethylacetamide (hereinafter referred to as DMAc). It melt | dissolved in 32 mL and heated to 100 degreeC with the oil bath. Thereafter, 2,4,6-trichloro-1,3,5-triazine (2.00 g, 10.9 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in DMAC (32 mL) was added to initiate polymerization.
After 50 minutes, aniline (3.03 g, 32.5 mmol, manufactured by Junsei Chemical Co., Ltd.) was added and stirred for 30 minutes to stop the polymerization. After cooling to room temperature, a 28% aqueous ammonia solution (1.98 g) was reprecipitated in a mixed solution in 240 mL of water and 80 mL of methanol. The precipitate was filtered, redissolved in 35 mL of THF, and reprecipitated in 250 mL of ion exchange water. The obtained precipitate was filtered and dried with a vacuum dryer at 120 ° C. for 6 hours to obtain 5.11 g of the target polymer [1]. The measurement result of 1 H-NMR spectrum is shown in FIG. The obtained polymer compound [1] is a compound having a structural unit represented by the formula (1). The weight average molecular weight Mw measured by polystyrene conversion by GPC of the high molecular compound [1] was 8,900, and the polydispersity Mw / Mn was 4.92. The 5% weight reduction temperature by TG-DTA was 339 ° C.
［実施例２］高分子化合物［２］の合成（ジアミン共重合１）
Figure JPOXMLDOC01-appb-C000036
 [Example 2] Synthesis of polymer compound [2] (diamine copolymer 1)
Figure JPOXMLDOC01-appb-C000036
　２００ｍＬ四口フラスコに、２，２－ビス（３－アミノ－４－メチルフェニル）ヘキサフルオロプロパン（５．４０ｇ、１４．９１ｍｍｏｌ、セントラル硝子（株）製）、ｐ－フェニレンジアミン（１．７６ｇ、１６．２７ｍｍｏｌ、東京化成工業（株）製）を入れ、ＤＭＡｃ５２ｍＬに溶解して、オイルバスで１００℃に加熱した。その後、ＤＭＡｃ５２ｍＬに溶解した２，４，６－トリクロロ－１，３，５－トリアジン（５．００ｇ、１０．９ｍｍｏｌ、東京化成工業（株）製）を加えて重合を開始した。
　５０分後、アニリン（７．５８ｇ、８１．３ｍｍｏｌ、純正化学（株）製）を加え、３０分間撹拌して重合を停止した。室温まで放冷後、２８％アンモニア水溶液（４．９４ｇ）を水４９０ｍＬおよびメタノール１６５ｍＬに溶解した混合溶液中に再沈殿させた。沈殿物をろ過し、ＴＨＦ７８ｍＬに再溶解させ、イオン交換水５６０ｍＬに再沈殿した。得られた沈殿物をろ過し、減圧乾燥機で１２０℃、６時間乾燥し、目的とする高分子化合物［１］１０．４ｇを得た。1Ｈ－ＮＭＲスペクトルの測定結果を図２に示す。得られた高分子化合物［１］は式（２）で表される構造単位を有する化合物である。高分子化合物［２］のＧＰＣによるポリスチレン換算で測定される重量平均分子量Ｍｗは４，６００、多分散度Ｍｗ／Ｍｎは２．２７であった。また、ＴＧ－ＤＴＡによる５％重量減少温度は、４０５℃であった。 In a 200 mL four-necked flask, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane (5.40 g, 14.91 mmol, manufactured by Central Glass Co., Ltd.), p-phenylenediamine (1.76 g, 16.27 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, dissolved in 52 mL of DMAc, and heated to 100 ° C. in an oil bath. Thereafter, 2,4,6-trichloro-1,3,5-triazine (5.00 g, 10.9 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 52 mL of DMAc was added to initiate polymerization.
After 50 minutes, aniline (7.58 g, 81.3 mmol, manufactured by Junsei Chemical Co., Ltd.) was added and the mixture was stirred for 30 minutes to stop the polymerization. After cooling to room temperature, a 28% aqueous ammonia solution (4.94 g) was reprecipitated in a mixed solution dissolved in 490 mL of water and 165 mL of methanol. The precipitate was filtered, redissolved in 78 mL of THF, and reprecipitated in 560 mL of ion exchange water. The obtained precipitate was filtered and dried in a vacuum dryer at 120 ° C. for 6 hours to obtain 10.4 g of the target polymer [1]. The measurement result of 1 H-NMR spectrum is shown in FIG. The obtained polymer compound [1] is a compound having a structural unit represented by the formula (2). The weight average molecular weight Mw measured by polystyrene conversion by GPC of the high molecular compound [2] was 4,600, and the polydispersity Mw / Mn was 2.27. The 5% weight reduction temperature by TG-DTA was 405 ° C.
［実施例３］高分子化合物［３］の合成（ジアミン共重合２）
Figure JPOXMLDOC01-appb-C000037
 [Example 3] Synthesis of polymer compound [3] (diamine copolymer 2)
Figure JPOXMLDOC01-appb-C000037
　２００ｍＬ四口フラスコに、２，２－ビス（３－アミノ－４－メチルフェニル）ヘキサフルオロプロパン（２．７２ｇ、７．５１ｍｍｏｌ、セントラル硝子（株）製）、ｐ－フェニレンジアミン（２．６４ｇ、２４．４０ｍｍｏｌ、東京化成工業（株）製）を入れ、ＤＭＡｃ３９ｍＬに溶解して、オイルバスで１００℃に加熱した。その後、ＤＭＡｃ３９ｍＬに溶解した２，４，６－トリクロロ－１，３，５－トリアジン（５．００ｇ、１０．９ｍｍｏｌ、東京化成工業（株）製）を加えて重合を開始した。
　５０分後、アニリン（７．５８ｇ、８１．３ｍｍｏｌ、純正化学（株）製）を加え、３０分間撹拌して重合を停止した。室温まで放冷後、２８％アンモニア水溶液（４．９４ｇ）を水４９０ｍＬおよびメタノール１６５ｍＬに溶解した混合溶液中に再沈殿させた。沈殿物をろ過し、ＴＨＦ７８ｍＬに再溶解させ、イオン交換水５６０ｍＬに再沈殿した。得られた沈殿物をろ過し、減圧乾燥機で１２０℃、６時間乾燥し、目的とする高分子化合物［３］８．１ｇを得た。1Ｈ－ＮＭＲスペクトルの測定結果を図３に示す。得られた高分子化合物［３］は式（２）で表される構造単位を有する化合物である。高分子化合物［３］のＧＰＣによるポリスチレン換算で測定される重量平均分子量Ｍｗは６，２００、多分散度Ｍｗ／Ｍｎは３．６０であった。また、ＴＧ－ＤＴＡによる５％重量減少温度は、４１７℃であった。 In a 200 mL four-necked flask, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane (2.72 g, 7.51 mmol, manufactured by Central Glass Co., Ltd.), p-phenylenediamine (2.64 g, 24.40 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, dissolved in 39 mL of DMAc, and heated to 100 ° C. in an oil bath. Thereafter, 2,4,6-trichloro-1,3,5-triazine (5.00 g, 10.9 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 39 mL of DMAc was added to initiate polymerization.
After 50 minutes, aniline (7.58 g, 81.3 mmol, manufactured by Junsei Chemical Co., Ltd.) was added and the mixture was stirred for 30 minutes to stop the polymerization. After cooling to room temperature, a 28% aqueous ammonia solution (4.94 g) was reprecipitated in a mixed solution dissolved in 490 mL of water and 165 mL of methanol. The precipitate was filtered, redissolved in 78 mL of THF, and reprecipitated in 560 mL of ion exchange water. The resulting precipitate was filtered and dried in a vacuum dryer at 120 ° C. for 6 hours to obtain 8.1 g of the intended polymer compound [3]. The measurement result of 1 H-NMR spectrum is shown in FIG. The obtained polymer compound [3] is a compound having a structural unit represented by the formula (2). The weight average molecular weight Mw measured in terms of polystyrene by GPC of the polymer compound [3] was 6,200, and the polydispersity Mw / Mn was 3.60. The 5% weight loss temperature by TG-DTA was 417 ° C.
［実施例４］高分子化合物［４］の合成（ジアミン単一重合２）
Figure JPOXMLDOC01-appb-C000038
 [Example 4] Synthesis of polymer compound [4] (diamine single polymerization 2)
Figure JPOXMLDOC01-appb-C000038
　２００ｍＬ四口フラスコに、３，５－ジアミノベンゾトリフルオリド（５．７３ｇ、３２．５ｍｍｏｌ、Ｐ＆Ｍ社製）を入れ、ＤＭＡｃ６４ｍＬに溶解して、オイルバスで１００℃に加熱した。その後、ＤＭＡｃ６４ｍＬに溶解した２，４，６－トリクロロ－１，３，５－トリアジン（５．００ｇ、２７．１ｍｍｏｌ、東京化成工業（株）製）を加えて重合を開始した。
　５０分後、アニリン（７．５８ｇ、８１．３ｍｍｏｌ、純正化学（株）製）を加え、３０分間撹拌して重合を停止した。室温まで放冷後、２８％アンモニア水溶液（４．９４ｇ）を水４００ｍＬおよびメタノール１３４ｍＬに溶解した混合溶液中に再沈殿させた。沈殿物をろ過し、ＴＨＦ５４ｍＬに再溶解させ、イオン交換水４３０ｍＬに再沈殿した。得られた沈殿物をろ過し、減圧乾燥機で１２０℃、６時間乾燥し、目的とする高分子化合物［４］７．５４ｇを得た。1Ｈ－ＮＭＲスペクトルの測定結果を図４に示す。得られた高分子化合物［４］は式（１）で表される構造単位を有する化合物である。高分子化合物［４］のＧＰＣによるポリスチレン換算で測定される重量平均分子量Ｍｗは１，１００、多分散度Ｍｗ／Ｍｎは１．４３であった。また、ＴＧ－ＤＴＡによる５％重量減少温度は、３５８℃であった。 In a 200 mL four-necked flask, 3,5-diaminobenzotrifluoride (5.73 g, 32.5 mmol, manufactured by P & M) was added, dissolved in DMAc 64 mL, and heated to 100 ° C. in an oil bath. Thereafter, 2,4,6-trichloro-1,3,5-triazine (5.00 g, 27.1 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 64 mL of DMAc was added to initiate polymerization.
After 50 minutes, aniline (7.58 g, 81.3 mmol, manufactured by Junsei Chemical Co., Ltd.) was added and the mixture was stirred for 30 minutes to stop the polymerization. After cooling to room temperature, a 28% aqueous ammonia solution (4.94 g) was reprecipitated in a mixed solution in 400 mL of water and 134 mL of methanol. The precipitate was filtered, redissolved in 54 mL of THF, and reprecipitated in 430 mL of ion exchange water. The obtained precipitate was filtered and dried with a vacuum dryer at 120 ° C. for 6 hours to obtain 7.54 g of the intended polymer compound [4]. The measurement result of 1 H-NMR spectrum is shown in FIG. The obtained polymer compound [4] is a compound having a structural unit represented by the formula (1). The weight average molecular weight Mw measured by polystyrene conversion by GPC of the high molecular compound [4] was 1,100, and the polydispersity Mw / Mn was 1.43. The 5% weight loss temperature by TG-DTA was 358 ° C.
［実施例５］高分子化合物［５］の合成（ジアミン共重合３）
Figure JPOXMLDOC01-appb-C000039
 [Example 5] Synthesis of polymer compound [5] (diamine copolymer 3)
Figure JPOXMLDOC01-appb-C000039
　２００ｍＬ四口フラスコに、３，５－ジアミノベンゾトリフルオリド（５．７３ｇ、３２．５ｍｍｏｌ、Ｐ＆Ｍ社製）、ｍ－フェニレンジアミン（３．５２ｇ、３２．５ｍｍｏｌ、ＤｕＰｏｎｔ社製）を入れ、ＤＭＡｃ９４ｍＬに溶解して、オイルバスで１００℃に加熱した。その後、ＤＭＡｃ９４ｍＬに溶解した２，４，６－トリクロロ－１，３，５－トリアジン（１０．０ｇ、５４．２ｍｍｏｌ、東京化成工業（株）製）を加えて重合を開始した。
　５０分後、アニリン（１５．１５ｇ、１６２．７ｍｍｏｌ、純正化学（株）製）を加え、３０分間撹拌して重合を停止した。室温まで放冷後、２８％アンモニア水溶液（９．８８ｇ）を水５９０ｍＬおよびメタノール１９７ｍＬに溶解した混合溶液中に再沈殿させた。沈殿物をろ過し、ＴＨＦ９６ｍＬに再溶解させ、イオン交換水７７０ｍＬに再沈殿した。得られた沈殿物をろ過し、減圧乾燥機で１２０℃、６時間乾燥し、目的とする高分子化合物［５］１４．２ｇを得た。1Ｈ－ＮＭＲスペクトルの測定結果を図５に示す。得られた高分子化合物［５］は式（５）で表される構造単位を有する化合物である。高分子化合物［５］のＧＰＣによるポリスチレン換算で測定される重量平均分子量Ｍｗは１，５００、多分散度Ｍｗ／Ｍｎは１．４０であった。また、ＴＧ－ＤＴＡによる５％重量減少温度は、３５２℃であった。 In a 200 mL four-necked flask, 3,5-diaminobenzotrifluoride (5.73 g, 32.5 mmol, manufactured by P & M) and m-phenylenediamine (3.52 g, 32.5 mmol, manufactured by DuPont) were added, and DMAc was added to 94 mL. Dissolved and heated to 100 ° C. in an oil bath. Thereafter, 2,4,6-trichloro-1,3,5-triazine (10.0 g, 54.2 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 94 mL of DMAc was added to initiate polymerization.
After 50 minutes, aniline (15.15 g, 162.7 mmol, manufactured by Junsei Chemical Co., Ltd.) was added and stirred for 30 minutes to stop the polymerization. After cooling to room temperature, a 28% aqueous ammonia solution (9.88 g) was reprecipitated in a mixed solution in 590 mL of water and 197 mL of methanol. The precipitate was filtered, redissolved in 96 mL of THF, and reprecipitated in 770 mL of ion exchange water. The obtained precipitate was filtered and dried in a vacuum dryer at 120 ° C. for 6 hours to obtain 14.2 g of the target polymer [5]. The measurement result of 1 H-NMR spectrum is shown in FIG. The obtained polymer compound [5] is a compound having a structural unit represented by the formula (5). The weight average molecular weight Mw measured by polystyrene conversion by GPC of the high molecular compound [5] was 1,500, and the polydispersity Mw / Mn was 1.40. The 5% weight reduction temperature by TG-DTA was 352 ° C.
　上記実施例１～５で得られた高分子化合物１．０ｇを、シクロヘキサノン９．０ｇに溶解し、薄黄色透明溶液を得た。得られたポリマーワニスをシリコン基板上にスピンコーターを用いて３００ｒｐｍで５秒間、１，５００ｒｐｍで３０秒間スピンコートし、１５０℃で５分間焼成して溶媒を除去し薄膜を得た。得られた薄膜の屈折率を分光エリプソメトリーにより測定した。結果を表１に示す。 1.0 g of the polymer compound obtained in Examples 1 to 5 was dissolved in 9.0 g of cyclohexanone to obtain a light yellow transparent solution. The obtained polymer varnish was spin-coated on a silicon substrate using a spin coater at 300 rpm for 5 seconds and 1,500 rpm for 30 seconds, and baked at 150 ° C. for 5 minutes to remove the solvent and obtain a thin film. The refractive index of the obtained thin film was measured by spectroscopic ellipsometry. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
　表１に示されるように、実施例１～５で得られた各高分子化合物は、１．６を超える高い屈折率を有していることがわかる。
　また、実施例２と３の結果から、ｐ－フェニレンジアミンの使用比率を高めると、屈折率が高まっており、共重合比率を変化させることで、得られるハイパーブランチポリマーの屈折率が調整可能であることがわかる。なお、後述するように、フェニレンジアミン構造の含有比率が増えても各種有機溶媒に対する溶解性が低下することはない。 As shown in Table 1, it can be seen that each of the polymer compounds obtained in Examples 1 to 5 has a high refractive index exceeding 1.6.
Further, from the results of Examples 2 and 3, the refractive index increases when the use ratio of p-phenylenediamine is increased, and the refractive index of the obtained hyperbranched polymer can be adjusted by changing the copolymerization ratio. I know that there is. As will be described later, the solubility in various organic solvents does not decrease even if the content ratio of the phenylenediamine structure increases.
［比較例１］高分子化合物［６］の合成
Figure JPOXMLDOC01-appb-C000041
 [Comparative Example 1] Synthesis of polymer compound [6]
Figure JPOXMLDOC01-appb-C000041
　実施例１と同様の手法で、ｐ－フェニレンジアミン（７．４９ｇ、０．０６９ｍｏｌ、Ａｌｄｒｉｃｈ製）、２，４，６－トリクロロ－１，３，５－トリアジン（１８．５４ｇ、０．１ｍｏｌ、東京化成工業（株）製）、アニリン（２８．３０ｇ、０．３ｍｏｌ、純正化学（株）製）を用いて合成を行った。再溶解をＮ，Ｎ－ジメチルホルムアミド２６０ｍＬにより行い、再沈殿させて目的の高分子化合物［６］４９．７８ｇを得た。高分子化合物［６］の1Ｈ－ＮＭＲスペクトルの測定結果を図６に示す。高分子化合物［６］のＧＰＣによるポリスチレン換算で測定される重量平均分子量Ｍｗは２，３００、多分散度Ｍｗ／Ｍｎは１．７５であった。なお、ＧＰＣ測定は、下記の条件にて行った。
［ＧＰＣ］
装置：東ソー（株）製　ＨＬＣ－８２００　ＧＰＣ
カラム：Ｓｈｏｄｅｘ　ＯＨｐａｋ　ＳＢ－８０３ＨＱ＋ＳＢ－８０４ＨＱ
カラム温度：４０℃
溶媒：ジメチルホルムアミド
検出器：ＵＶ（２５４ｎｍ）
検量線：標準ポリスチレン In the same manner as in Example 1, p-phenylenediamine (7.49 g, 0.069 mol, manufactured by Aldrich), 2,4,6-trichloro-1,3,5-triazine (18.54 g, 0.1 mol, Synthesis was carried out using Tokyo Chemical Industry Co., Ltd.) and aniline (28.30 g, 0.3 mol, Junsei Chemical Co., Ltd.). Redissolution was performed with 260 mL of N, N-dimethylformamide and reprecipitation to obtain 49.78 g of the target polymer [6]. The measurement result of the 1 H-NMR spectrum of the polymer compound [6] is shown in FIG. The weight average molecular weight Mw measured by polystyrene conversion by GPC of the high molecular compound [6] was 2,300, and the polydispersity Mw / Mn was 1.75. The GPC measurement was performed under the following conditions.
[GPC]
Equipment: HLC-8200 GPC manufactured by Tosoh Corporation
Column: Shodex OHpak SB-803HQ + SB-804HQ
Column temperature: 40 ° C
Solvent: Dimethylformamide Detector: UV (254 nm)
Calibration curve: Standard polystyrene
　上記実施例１～５および比較例１で得られた各高分子化合物について、表１に示す各溶媒に対する溶解性を検討し、以下の基準にて評価した。なお、溶液は、１０質量％高分子化合物となるように調製し、溶解性は、２５℃で１時間後に目視で確認した。
○：透明な溶液となり、良好に溶解
×：沈殿物があり、不溶 The respective polymer compounds obtained in Examples 1 to 5 and Comparative Example 1 were examined for solubility in the respective solvents shown in Table 1, and evaluated according to the following criteria. In addition, the solution was prepared so that it might become a 10 mass% high molecular compound, and solubility was visually confirmed after 1 hour at 25 degreeC.
○: Transparent solution, good dissolution ×: Precipitates, insoluble
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000042
　表２に示されるように、フッ素原子を含むジアミン化合物を用いた本発明の高分子化合物は、ｐ－フェニレンジアミンを用いた比較例の高分子化合物に比べ、有機溶媒に対する溶解性が良好であり、特に、電子デバイス分野で汎用されている、シクロヘキサノン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセテート等にも良く溶けることがわかる。 As shown in Table 2, the polymer compound of the present invention using a diamine compound containing a fluorine atom has better solubility in an organic solvent than the polymer compound of a comparative example using p-phenylenediamine. In particular, it can be seen that it is well soluble in cyclohexanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, etc., which are widely used in the field of electronic devices.

Claims (17)

  1. 　下記式（１）または式（２）で表される繰り返し単位構造を含むことを特徴とするトリアジン環含有重合体。
    Figure JPOXMLDOC01-appb-C000001
     ｛式中、Ｒ、Ｒ’、Ｒ”およびＲ'''は、互いに独立して、水素原子、アルキル基、アルコキシ基、アリール基、またはアラルキル基を表し、Ａｒ1は、式（３）～（８）で示される群から選ばれる少なくとも１種を表し、
    Figure JPOXMLDOC01-appb-C000002
     〔式中、Ｘ1およびＸ2は、互いに独立して、フルオロ基、または炭素数１～１０のフルオロアルキル基を表し、Ｒ1～Ｒ61は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホン基、炭素数１～１０の分岐構造を有していてもよいアルキル基、または炭素数１～１０の分岐構造を有していてもよいアルコキシ基を表し、Ｗ1およびＷ2は、互いに独立して、Ｏ、Ｓ、ＣＨ2、またはＳＯ2を表す。〕
    　Ａｒ2は、式（９）～（１９）で示される群から選ばれる少なくとも１種を表す。
    Figure JPOXMLDOC01-appb-C000003
     〔式中、Ｒ62～Ｒ141は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホン基、炭素数１～１０の分岐構造を有していてもよいアルキル基、または炭素数１～１０の分岐構造を有していてもよいアルコキシ基を表し、Ｗ3およびＷ4は、互いに独立して、単結合、ＣＲ142Ｒ143（Ｒ142およびＲ143は、互いに独立して、水素原子または炭素数１～１０の分岐構造を有していてもよいアルキル基（ただし、これらは一緒になって環を形成していてもよい。）を表す。）、Ｃ＝Ｏ、Ｏ、Ｓ、ＳＯ、ＳＯ2、またはＮＲ144（Ｒ144は、水素原子または炭素数１～１０の分岐構造を有していてもよいアルキル基を表す。）を表し、Ｙ1およびＹ2は、互いに独立して、単結合、炭素数１～１０の分岐構造を有していてもよいアルキレン基、または式（２０）
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒ145～Ｒ148は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホン基、炭素数１～１０の分岐構造を有していてもよいアルキル基、または炭素数１～１０の分岐構造を有していてもよいアルコキシ基を表し、Ｙ3およびＹ4は、互いに独立して、単結合または炭素数１～１０の分岐構造を有していてもよいアルキレン基を表す。）で示される基を表す。〕｝     A triazine ring-containing polymer comprising a repeating unit structure represented by the following formula (1) or formula (2):
    Figure JPOXMLDOC01-appb-C000001
     {Wherein R, R ′, R ″ and R ′ ″ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and Ar 1 represents a group represented by the formula (3) to Represents at least one selected from the group represented by (8),
    Figure JPOXMLDOC01-appb-C000002
     [Wherein, X 1 and X 2 each independently represent a fluoro group or a fluoroalkyl group having 1 to 10 carbon atoms, and R 1 to R 61 each independently represent a hydrogen atom, a halogen atom, W 1 and W 2 represent a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkoxy group which may have a branched structure having 1 to 10 carbon atoms. Independently represent O, S, CH 2 , or SO 2 . ]
    Ar 2 represents at least one selected from the group represented by formulas (9) to (19).
    Figure JPOXMLDOC01-appb-C000003
     [Wherein R 62 to R 141 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group optionally having a branched structure of 1 to 10 carbon atoms, or 1 carbon atom. Represents an alkoxy group which may have a branched structure of ˜10, W 3 and W 4 are each independently a single bond, CR 142 R 143 (R 142 and R 143 are each independently hydrogen, An atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms (however, they may be combined to form a ring), C═O, O, S , SO, SO 2 , or NR 144 (R 144 represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms), and Y 1 and Y 2 are independent of each other. And an alkyle which may have a single bond and a branched structure having 1 to 10 carbon atoms. Group or formula (20)
    Figure JPOXMLDOC01-appb-C000004
     (Wherein R 145 to R 148 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group optionally having a branched structure having 1 to 10 carbon atoms, or 1 carbon atom) Represents an alkoxy group which may have a branched structure of ˜10, and Y 3 and Y 4 each independently represent an alkylene group which may have a single bond or a branched structure of 1 to 10 carbon atoms. Represents a group represented by: ]}
  2. 　前記Ａｒ1が、式（３）および式（４）から選ばれる少なくとも１種である請求項１記載のトリアジン環含有重合体。 The triazine ring-containing polymer according to claim 1, wherein Ar 1 is at least one selected from formulas (3) and (4).
  3. 　前記Ａｒ1が、式（３′）および式（４′）から選ばれる少なくとも１種である請求項１記載のトリアジン環含有重合体。
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｒ1～Ｒ11は前記と同じ。）     The triazine ring-containing polymer according to claim 1, wherein Ar 1 is at least one selected from formula (3 ') and formula (4').
    Figure JPOXMLDOC01-appb-C000005
     (Wherein R 1 to R 11 are the same as described above.)
  4. 　前記Ａｒ2が、式（９）で示される基である請求項１～３のいずれか１項記載のトリアジン環含有重合体。 The triazine ring-containing polymer according to any one of claims 1 to 3, wherein Ar 2 is a group represented by the formula (9).
  5. 　前記Ｘ1およびＸ2が、炭素数１～１０のパーフルオロアルキル基である請求項１または２記載のトリアジン環含有重合体。 The triazine ring-containing polymer according to claim 1 or 2, wherein X 1 and X 2 are perfluoroalkyl groups having 1 to 10 carbon atoms.
  6. 　前記繰り返し単位構造が、式（２１）で示される請求項１記載のトリアジン環含有重合体。
    Figure JPOXMLDOC01-appb-C000006
         The triazine ring-containing polymer according to claim 1, wherein the repeating unit structure is represented by the formula (21).
    Figure JPOXMLDOC01-appb-C000006
  7. 　前記繰り返し単位構造が、式（２２）で示される請求項１記載のトリアジン環含有重合体。
    Figure JPOXMLDOC01-appb-C000007
         The triazine ring-containing polymer according to claim 1, wherein the repeating unit structure is represented by the formula (22).
    Figure JPOXMLDOC01-appb-C000007
  8. 　前記繰り返し単位構造が、式（２３）で示される請求項１記載のトリアジン環含有重合体。
    Figure JPOXMLDOC01-appb-C000008
         The triazine ring-containing polymer according to claim 1, wherein the repeating unit structure is represented by the formula (23).
    Figure JPOXMLDOC01-appb-C000008
  9. 　前記繰り返し単位構造が、式（２４）で示される請求項１記載のトリアジン環含有重合体。
    Figure JPOXMLDOC01-appb-C000009
         The triazine ring-containing polymer according to claim 1, wherein the repeating unit structure is represented by the formula (24).
    Figure JPOXMLDOC01-appb-C000009
  10. 　少なくとも１つの末端が、アルキル基、アラルキル基、アリール基、アルキルアミノ基、アルコキシシリル基含有アルキルアミノ基、アラルキルアミノ基、アリールアミノ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、またはエステル基でキャップされている請求項１～９のいずれか１項記載のトリアジン環含有重合体。 At least one terminal is an alkyl group, aralkyl group, aryl group, alkylamino group, alkoxysilyl group-containing alkylamino group, aralkylamino group, arylamino group, alkoxy group, aralkyloxy group, aryloxy group, or ester group. The triazine ring-containing polymer according to any one of claims 1 to 9, which is capped.
  11. 　少なくとも１つのトリアジン環末端を有し、このトリアジン環末端が、アルキル基、アラルキル基、アリール基、アルキルアミノ基、アルコキシシリル基含有アルキルアミノ基、アラルキルアミノ基、アリールアミノ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、またはエステル基でキャップされている請求項１０記載のトリアジン環含有重合体。 Having at least one triazine ring end, and the triazine ring end is an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, an alkoxy group, an aralkyloxy group The triazine ring-containing polymer according to claim 10, which is capped with a group, an aryloxy group, or an ester group.
  12. 　請求項１～１１のいずれか１項記載のトリアジン環含有重合体を含む膜形成用組成物。 A film-forming composition comprising the triazine ring-containing polymer according to any one of claims 1 to 11.
  13. 　請求項１～１１のいずれか１項記載のトリアジン環含有重合体を含む膜。 A film comprising the triazine ring-containing polymer according to any one of claims 1 to 11.
  14. 　基材と、この基材上に形成された請求項１３記載の膜とを備える電子デバイス。 An electronic device comprising a base material and the film according to claim 13 formed on the base material.
  15. 　基材と、この基材上に形成された請求項１３記載の膜とを備える光学部材。 An optical member comprising a base material and the film according to claim 13 formed on the base material.
  16. 　請求項１３記載の膜を少なくとも１層備える、電荷結合素子または相補性金属酸化膜半導体からなる固体撮像素子。 A solid-state imaging device comprising at least one layer of the film according to claim 13 and made of a charge coupled device or a complementary metal oxide semiconductor.
  17. 　請求項１３記載の膜をカラーフィルター上の平坦化層として備える固体撮像素子。 A solid-state imaging device comprising the film according to claim 13 as a planarizing layer on a color filter.
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