WO2012057104A1 - Polymère contenant un cycle triazine et composition filmogène contenant ledit polymère - Google Patents

Polymère contenant un cycle triazine et composition filmogène contenant ledit polymère 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
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carbon atoms
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PCT/JP2011/074482
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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/ja
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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.

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Abstract

L'invention concerne un polymère qui contient une structure d'unité de répétition ayant un cycle de triazine comme structure d'unité de répétition représenté par la formule (21) qui est capable de présenter une résistance élevée à la chaleur, une transparence élevée, un indice de réfraction élevé, une solubilité élevée et un faible rétrécissement volumétrique par lui-même, et est approprié pour l'utilisation comme composant d'une composition filmogène.
PCT/JP2011/074482 2010-10-28 2011-10-25 Polymère contenant un cycle triazine et composition filmogène contenant ledit polymère WO2012057104A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015072474A1 (fr) * 2013-11-13 2015-05-21 日産化学工業株式会社 Élément électroluminescent organique
WO2016199630A1 (fr) * 2015-06-09 2016-12-15 日産化学工業株式会社 Composition de formation de film pour revêtement à jet d'encre
WO2017110810A1 (fr) * 2015-12-21 2017-06-29 日産化学工業株式会社 Polymère contenant un cycle triazine, et composition filmogène contenant ledit polymère
KR20180022711A (ko) * 2015-06-03 2018-03-06 닛산 가가쿠 고교 가부시키 가이샤 트라이아진환 함유 중합체 및 그것을 포함하는 막 형성용 조성물
WO2018097000A1 (fr) * 2016-11-22 2018-05-31 出光興産株式会社 Polymère comprenant un cycle triazine, et composition mettant en œuvre celui-ci

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS323145B1 (fr) * 1954-10-12 1957-05-27
JPH07113009A (ja) * 1993-10-18 1995-05-02 Alps Electric Co Ltd 溶媒可溶性芳香族ポリアミンおよびその製造方法
JPH10287745A (ja) * 1997-04-16 1998-10-27 Otsuka Chem Co Ltd 含弗素樹脂
JP2001503077A (ja) * 1996-09-16 2001-03-06 バイエル・アクチエンゲゼルシヤフト トリアジン重合体そして電界発光装置におけるそれの使用
WO2010128661A1 (fr) * 2009-05-07 2010-11-11 日産化学工業株式会社 Polymère contenant un cycle triazine et composition filmogène comprenant celui-ci

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS323145B1 (fr) * 1954-10-12 1957-05-27
JPH07113009A (ja) * 1993-10-18 1995-05-02 Alps Electric Co Ltd 溶媒可溶性芳香族ポリアミンおよびその製造方法
JP2001503077A (ja) * 1996-09-16 2001-03-06 バイエル・アクチエンゲゼルシヤフト トリアジン重合体そして電界発光装置におけるそれの使用
JPH10287745A (ja) * 1997-04-16 1998-10-27 Otsuka Chem Co Ltd 含弗素樹脂
WO2010128661A1 (fr) * 2009-05-07 2010-11-11 日産化学工業株式会社 Polymère contenant un cycle triazine et composition filmogène comprenant celui-ci

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MAHAPATRA, S.S. ET AL.: "Effect of structure and concentration of polymer, metal ion and pH of the medium on the fluorescence characteristics of hyper branched polyamines", JOURNAL OF LUMINESCENCE, vol. 128, no. 12, 2008, pages 1917 - 1921 *
ZHANG, W. ET AL.: "Structure-Activity Relationships in Dendrimers Based on Triazines: Gelation Depends on Choice of Linking and Surface Groups", MACROMOLECULES, vol. 35, no. 24, 2002, pages 9015 - 9021, XP055085420, DOI: doi:10.1021/ma021101f *

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