CN113383029A - Ester compound, resin composition, cured product, and laminated film - Google Patents
Ester compound, resin composition, cured product, and laminated film Download PDFInfo
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- CN113383029A CN113383029A CN202080007615.0A CN202080007615A CN113383029A CN 113383029 A CN113383029 A CN 113383029A CN 202080007615 A CN202080007615 A CN 202080007615A CN 113383029 A CN113383029 A CN 113383029A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4042—Imines; Imides
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Abstract
The purpose of the present invention is to provide an ester compound that can be used for a resin composition that has excellent heat resistance and dielectric properties after curing. Further, the present invention aims to provide a resin composition containing the ester compound, a cured product of the resin composition, and a laminated film using the resin composition. The present invention is an ester compound represented by the following formula (1). In the formula (1), R1And R2Each of which may be the same or different, is an aryl group which may be substituted, R3Is a 2-valent group having at least 1 arylene group which may be substituted, X is a 2-valent group having at least 1 arylene group which may be substituted, and n is an integer of 0 or more and 10 or less.
Description
Technical Field
The present invention relates to an ester compound that can be used for a resin composition having excellent heat resistance and dielectric characteristics after curing. The present invention also relates to a resin composition containing the ester compound, a cured product of the resin composition, and a laminate film using the resin composition.
Background
Curable resins such as epoxy resins, which have low shrinkage and are excellent in adhesion, insulation properties and chemical resistance, are used in many industrial products. In particular, resin compositions used for interlayer insulating materials of printed wiring boards and the like are required to have dielectric properties such as low dielectric constant and low dielectric loss tangent. As such a resin composition having excellent dielectric properties, for example, patent documents 1 and 2 disclose a resin composition containing a curable resin and a compound having a specific structure as a curing agent. However, such a resin composition has a problem that it is difficult to achieve both of heat resistance and dielectric characteristics after curing.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-186551
Patent document 2: international publication No. 2016/114286
Disclosure of Invention
Problems to be solved by the invention
An object of the present invention is to provide an ester compound that can be used for a resin composition having excellent heat resistance and dielectric characteristics after curing. Further, another object of the present invention is to provide a resin composition containing the ester compound, a cured product of the resin composition, and a laminated film using the resin composition.
Means for solving the problems
The present invention is an ester compound represented by the following formula (1).
[ chemical formula 1]
In the formula (1), R1And R2Each of which may be the same or different, is an aryl group which may be substituted, R3Is a 2-valent group having at least 1 arylene group which may be substituted, X is a 2-valent group having at least 1 arylene group which may be substituted, and n is an integer of 0 or more and 10 or less.
The present invention is described in detail below.
The present inventors have found that a resin composition excellent in heat resistance and dielectric characteristics after curing can be obtained by using an ester compound having a specific structure as a curing agent, and have completed the present invention.
The ester compound of the present invention is represented by the above formula (1).
In the above formula (1), R1And R2Each of which may be the same or different, is an aryl group which may be substituted. By having aryl groups which may be substituted as the above-mentioned R1And the above R2Accordingly, when the ester compound of the present invention is used as a curing agent, the obtained resin composition is excellent in dielectric properties such as low dielectric loss tangent.
Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group.
Examples of the substituent in the case where the aryl group is substituted include an aliphatic group and the like.
Wherein R in the above formula (1)1And R2A group represented by the following formula (2) is preferred. By making the above R1And the above R2The group represented by the following formula (2) is more excellent in dielectric properties such as low dielectric loss tangent of a cured product of the resin composition obtained when the ester compound of the present invention is used as a curing agent.
[ chemical formula 2]
In the formula (2), R4Each independently is a hydrogen atom or an aliphatic group, and is a bonding site.
In the above formula (1), R3Is a 2-valent group having at least 1 arylene group which may be substituted. By making the above R3Is a 2-valent group having at least 1 arylene group which may be substituted, and therefore, a cured product of the resin composition obtained when the ester compound of the present invention is used as a curing agent is excellent in heat resistance. In the case where n in the formula (1) is 1 or more, each R3May be the same or different.
As R in the above formula (1)3Examples of the arylene group include phenylene, naphthylene, and anthracenylene.
Examples of the substituent in the case where the arylene group is substituted include an aliphatic group and the like.
Wherein R in the above formula (1)3Preferably a group represented by the following formula (3-1), (3-2), (3-3) or (3-4), more preferably a group represented by the following formula (3-1) or (3-2). By making the above R3The ester compound of the present invention is a group represented by the following formula (3-1), (3-2), (3-3) or (3-4), and therefore, when the ester compound is used as a curing agent, the ester compound has more excellent compatibility with a curable resin, and the cured product of the obtained resin composition has more excellent heat resistance.
[ chemical formula 3]
In the formula (3-1), R5Each independently a hydrogen atom or an aliphatic group, in the formula (3-2), R6Each independently a hydrogen atom or an aliphatic group, in the formula (3-3), R7Each independently is a hydrogen atom or an aliphatic group, R8Each independently a hydrogen atom or an aliphatic group, in the formula (3-4), R9Each independently a hydrogen atom or an aliphatic group, and in the formulae (3-1), (3-2), (3-3) and (3-4), the bond site.
R in the above formula (1)3In the case of the group represented by the above formula (3-1), the group represented by the formula (3-1) is preferably a group represented by the following formula (4-1) or (4-2).
In addition, in the case of using the ester compound represented by the above formula (1) as a curing agent, the above R can be used3A compound which is a group represented by the following formula (4-1) and the above R3Is a mixture of compounds of the group represented by the following formula (4-2).
[ chemical formula 4]
In the formulae (4-1) and (4-2), it is the bonding site.
In the formula (1), n is an integer of 0 to 10 inclusive.
In the above formula (1), when n is 0, the cured product of the resin composition obtained when the ester compound of the present invention is used as a curing agent is more excellent in heat resistance.
In addition, the ester compound of the present invention is excellent in heat resistance and dielectric properties of a cured product of the resin composition obtained when used as a curing agent even when polymerized, that is, when n in the formula (1) is 1 or more. In addition, when n in the formula (1) is 1 or more, the elongation of the cured product of the obtained resin composition is also excellent.
From the viewpoint of compatibility with the resin component, the preferable upper limit of n in the formula (1) is 10.
In the above formula (1), X is a 2-valent group having at least 1 arylene group which may be substituted.
Examples of the arylene group contained in X in the formula (1) include a phenylene group, a naphthylene group, an anthracenylene group and the like.
Examples of the substituent in the case where the arylene group is substituted include an aliphatic group and the like. When n in the formula (1) is 2 or more, X may be the same or different.
When the above-mentioned arylene group has 2 or more, examples of X include a group represented by the following formula (5-1) or (5-2).
[ chemical formula 5]
In the formula (5-1), R10Each independently a hydrogen atom or an aliphatic group, in the formula (5-2), R11Each independently a hydrogen atom or an aliphatic group, and in the formulae (5-1) and (5-2), the bond site.
The preferable lower limit of the molecular weight of the ester compound of the present invention is 500, and the preferable upper limit is 1 ten thousand. By setting the molecular weight in this range, the ester compound of the present invention has excellent compatibility with the resin component while maintaining excellent heat resistance after curing, and the cured product of the obtained resin composition has excellent dielectric properties such as low dielectric loss tangent. The lower limit of the molecular weight of the ester compound of the present invention is more preferably 580, the upper limit is more preferably 8000, and the lower limit is more preferably 600. When more excellent heat resistance is required after curing, the molecular weight of the ester compound is preferably 5500 or less. By setting the molecular weight to 5500 or less, the heat resistance of a cured product of the obtained curable resin composition is more excellent. From the viewpoint of heat resistance after curing, a more preferable upper limit of the molecular weight of the ester compound is 5000, a more preferable upper limit is 4500, a still more preferable upper limit is 4000, a particularly preferable upper limit is 3500, and a most preferable upper limit is 3000. Further, when more excellent elongation is required after curing, the molecular weight of the ester compound is preferably 1000 or more. By making the molecular weight 1000 or more, the elongation of the cured product of the obtained curable resin composition is more excellent. From the viewpoint of elongation after curing, a more preferable lower limit of the molecular weight of the ester compound is 1200 or more, and a further preferable lower limit is 1500 or more.
In the present specification, the "molecular weight" refers to a molecular weight determined from a structural formula for a compound having a specific molecular structure (for example, in the case of a compound of formula (1) in which n is 0 only). In the present specification, the "molecular weight" may be expressed by a number average molecular weight for a compound having a wide distribution of polymerization degrees (for example, in the case of a mixture of n having a plurality of values in the formula (1)) and a compound having no specific modification site. In the present specification, the "number average molecular weight" is a value determined by measuring by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converting into polystyrene. Examples of the column used for measuring the number average molecular weight in terms of polystyrene by GPC include JAIGEL-2H-A (manufactured by Japan analytical industries, Ltd.).
In the ester compound of the present invention, examples of a method for producing a compound in which n in the formula (1) is 0 include the following methods.
That is, a compound in which n in the formula (1) is 0 can be produced by a method in which trimellitic anhydride is reacted with an aromatic diamine represented by the following formula (6), and then a hydroxyl group-containing aromatic compound represented by the following formula (7-1) and/or a hydroxyl group-containing aromatic compound represented by the following formula (7-2) are reacted with each other. Further, a compound in which n in the formula (1) is 0 can also be produced by a method in which a trimellitic anhydride halide is reacted with a hydroxyl group-containing aromatic compound represented by the following formula (7-1) and/or a hydroxyl group-containing aromatic compound represented by the following formula (7-2), and then reacted with an aromatic diamine represented by the following formula (6).
When the ester compound of the present invention is polymerized, that is, when n in the formula (1) is 1 or more, examples of the method for producing the compound include the following methods.
That is, in the method for producing a compound in which n in the formula (1) is 0, a compound in which n in the formula (1) is 1 or more can be produced by a method in which a hydroxy-containing aromatic compound represented by the following formula (8) is reacted with a hydroxy-containing aromatic compound represented by the following formula (7-1) and/or a hydroxy-containing aromatic compound represented by the following formula (7-2).
[ chemical formula 6]
H2N-R3-NH2 (6)
In the formula (6), R3Is the same as R in the above formula (1)3The same groups.
[ chemical formula 7]
R1-OH (7-1)
R2-OH (7-2)
In the formula (7-1), R1Is the same as R in the above formula (1)1The same group, formula (7-2), R2Is the same as R in the above formula (1)2The same groups.
[ chemical formula 8]
HO-X-OH(8)
In the formula (8), X is the same group as X in the formula (1).
Examples of the aromatic diamine represented by the above formula (6) include 2-methyl-4, 6-diethyl-1, 3-phenylenediamine, 2, 4-diethyl-6-methyl-1, 3-phenylenediamine, 3 ' -diaminodiphenylmethane, 3,4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylmethane, 3 ' -diaminodiphenylether, 3,4 ' -diaminodiphenylether, 4 ' -diaminodiphenylether, 1, 2-phenylenediamine, 1, 3-phenylenediamine, 1, 4-phenylenediamine, 3 ' -diaminodiphenylsulfone, 4 ' -diaminodiphenylsulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4-aminophenoxy) phenyl) sulfone, and bis (3, 3 ' -diaminodiphenylsulfone, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, bis (4- (4-aminophenoxy) phenyl) methane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (2- (4-aminophenyl) -2-propyl) benzene, 1,4- (2- (4-aminophenyl) -2-propyl) benzene, 3 '-diamino-4, 4' -dihydroxydiphenylmethane, 4 '-diamino-3, 3' -dihydroxydiphenylmethane, 3 '-diamino-4, 4' -dihydroxydiphenyl ether, 3 '-dihydroxy-4, 4' -dihydroxydiphenyl ether, 1,3 '-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (2- (4-aminophenyl) -2-propyl) benzene, 3' -dihydroxy-diphenylmethane, 3 '-dihydroxy-diphenyl ether, 3' -dihydroxy diphenyl ether, or a mixture thereof, 2, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) propane, bisaminophenylfluorene, bistoluenefluorene, 4 '-bis (4-aminophenoxy) biphenyl, 4' -diamino-3, 3 '-dihydroxydiphenyl ether, 3' -diamino-4, 4 '-dihydroxybiphenyl, 4' -diamino-2, 2 '-dihydroxybiphenyl, 4' -diamino-3, 3 '-dihydroxybiphenyl, 4' -bis (4-aminobenzamide) -3,3 '-dihydroxybiphenyl, 4' -bis (3-aminobenzamide) -3, 3' -dihydroxybiphenyl, and the like. Among them, from the viewpoint of solubility, heat resistance and availability, 2-methyl-4, 6-diethyl-1, 3-phenylenediamine, 2, 4-diethyl-6-methyl-1, 3-phenylenediamine, 1, 3-bis (3-aminophenoxy) benzene, 4' -diaminodiphenylmethane, bis (4- (4-aminophenoxy) phenyl) sulfone are preferable, and 2-methyl-4, 6-diethyl-1, 3-phenylenediamine, 2, 4-diethyl-6-methyl-1, 3-phenylenediamine and 1, 3-bis (3-aminophenoxy) benzene are more preferable.
Examples of the hydroxyl group-containing aromatic compound represented by the above formula (7-1) and the hydroxyl group-containing aromatic compound represented by the above formula (7-2) include phenol, 1-naphthol, 2-naphthol, 1-hydroxyanthracene, 2-hydroxyanthracene, 9-hydroxyanthracene, o-cresol, m-cresol, p-cresol, 2, 3-dimethylphenol, 2, 4-dimethylphenol, 2, 5-dimethylphenol, 2, 6-dimethylphenol, 3, 4-dimethylphenol, 3, 5-dimethylphenol, 4-tert-butylphenol, 4- α -cumylphenol, 1-methyl-2-naphthol, 3-methyl-2-naphthol, 6-methyl-2-naphthol, 7-methyl-2-naphthol, and the like, 1-bromo-2-naphthol, 3-bromo-2-naphthol, 6-bromo-2-naphthol, 7-bromo-2-naphthol, 1-nitro-2-naphthol, 3-nitro-2-naphthol, 6-nitro-2-naphthol, 7-nitro-2-naphthol, 1-hydroxypyrene, etc. Among them, 2-naphthol is preferable from the viewpoint of dielectric characteristics and availability.
Examples of the hydroxyl group-containing aromatic compound represented by the above formula (8) include 1, 2-dihydroxybenzene, 1, 3-dihydroxybenzene, 1, 4-dihydroxybenzene, 1, 2-dihydroxynaphthalene, 1, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, 2, 6-dihydroxyanthracene, 9, 10-dihydroxyanthracene, 4 ' -dihydroxybiphenyl, 3 ', 5,5 ' -tetramethylbiphenyl-4, 4 ' -diol, 2-bis (4-hydroxyphenyl) propane, 1 ' -methylenebis-2-naphthol, 1,4 ' -dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1,4 ' -dihydroxyanthracene, 4 ' -dihydroxybiphenyl, 3 ', 5,5 ' -tetramethylbiphenyl-4 ' -diol, 2-diol, and mixtures thereof, 1, 1' -bi-2-naphthol, and the like.
A resin composition comprising a curable resin and a curing agent, wherein the curing agent comprises the ester compound of the present invention is also one aspect of the present invention.
By containing the ester compound of the present invention, a cured product of the resin composition of the present invention is excellent in heat resistance and dielectric characteristics.
The resin composition of the present invention may contain other curing agents in addition to the ester compound of the present invention, in order to improve processability in an uncured state and the like, within a range not to impair the object of the present invention.
Examples of the other curing agent include a phenol curing agent, a thiol curing agent, an amine curing agent, an acid anhydride curing agent, a cyanate curing agent, and an active ester curing agent other than the ester compound of the present invention. Among them, active ester-based curing agents and cyanate ester-based curing agents other than the ester compound of the present invention are preferable.
When only the ester compound of the present invention is used as the curing agent, the content of the ester compound of the present invention is preferably 50 parts by weight at the lower limit and 300 parts by weight at the upper limit with respect to 100 parts by weight of the curable resin. When only the ester compound of the present invention is used as the curing agent, the resin composition obtained by setting the content of the ester compound of the present invention to the above range is more excellent in heat resistance and dielectric characteristics. A more preferable lower limit of the content of the ester compound of the present invention when only the ester compound of the present invention is used as the above curing agent is 70 parts by weight, and a more preferable upper limit is 200 parts by weight.
When the ester compound of the present invention and another curing agent are used together as the curing agent, the content of the ester compound of the present invention is preferably 5 parts by weight at the lower limit and 200 parts by weight at the upper limit with respect to 100 parts by weight of the curable resin. When the ester compound of the present invention and another curing agent are used together as the curing agent, the resin composition obtained has more excellent heat resistance and dielectric properties by setting the content of the ester compound of the present invention to the above range. When the ester compound of the present invention and another curing agent are used together as the curing agent, the lower limit of the content of the ester compound of the present invention is more preferably 10 parts by weight, and the upper limit is more preferably 150 parts by weight. When the ester compound of the present invention and another curing agent are used together as the curing agent, the total content of the ester compound of the present invention and the other curing agent is preferably 20 parts by weight at the lower limit and 200 parts by weight at the upper limit to 100 parts by weight of the curable resin.
The resin composition of the present invention contains a curable resin.
Examples of the curable resin include epoxy resins, cyanate resins, phenol resins, imide resins, maleimide resins, benzoxazine resins, silicone resins, acrylic resins, and fluororesins. Among them, the above curable resin preferably contains at least 1 selected from the group consisting of an epoxy resin, a cyanate resin, a phenol resin, an imide resin, a maleimide resin and a benzoxazine resin, and more preferably contains an epoxy resin. The curable resins may be used alone or in combination of 2 or more.
Examples of the epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol E type epoxy resins, bisphenol S type epoxy resins, 2' -diallylbisphenol A type epoxy resins, hydrogenated bisphenol type epoxy resins, propylene oxide-added bisphenol A type epoxy resins, resorcinol type epoxy resins, biphenyl type epoxy resins, thioether type epoxy resins, diphenyl ether type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resin, fluorene type epoxy resin, naphthalene ether type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenol novolac type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin, glycidyl ester compound, and the like.
The resin composition of the present invention preferably contains a curing accelerator. By containing the curing accelerator, the curing time can be shortened and the productivity can be improved.
Examples of the curing accelerator include imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphine-based curing accelerators, photobase generators, sulfonium salt-based curing accelerators, and the like. Among them, imidazole-based curing accelerators and phosphine-based curing accelerators are preferable from the viewpoint of storage stability and curability.
The curing accelerator may be used alone, or 2 or more kinds may be used in combination.
The lower limit of the content of the curing accelerator is preferably 0.01 part by weight, and the upper limit is preferably 5 parts by weight, based on 100 parts by weight of the curable resin. When the content of the curing accelerator is in this range, the curing time can be shortened without deteriorating the adhesiveness of the obtained resin composition. The lower limit of the content of the curing accelerator is more preferably 0.05 part by weight, and the upper limit is more preferably 3 parts by weight.
The resin composition of the present invention preferably contains an inorganic filler.
By containing the inorganic filler, the resin composition of the present invention is more excellent in moisture absorption reflow resistance, plating resistance and processability while maintaining excellent adhesiveness and long-term heat resistance.
The inorganic filler is preferably at least one of silica and barium sulfate. The resin composition of the present invention is more excellent in moisture absorption reflow resistance, plating resistance and processability by containing at least one of silica and barium sulfate as the inorganic filler.
Examples of the inorganic filler other than the silica and the barium sulfate include alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, carbon fiber, and inorganic ion exchanger.
The inorganic filler may be used alone, or 2 or more kinds may be used in combination.
The lower limit of the average particle diameter of the inorganic filler is preferably 50nm, and the upper limit thereof is preferably 10 μm. When the average particle diameter of the inorganic filler is in this range, the resulting resin composition is more excellent in coatability and processability. A more preferable lower limit of the average particle diameter of the inorganic filler is 100nm, and a more preferable upper limit thereof is 5 μm.
When a solvent described later is used, the content of the inorganic filler preferably has a lower limit of 10 parts by weight and an upper limit of 1000 parts by weight with respect to 100 parts by weight of the total resin composition excluding the solvent. When the content of the inorganic filler is in this range, the obtained resin composition is more excellent in moisture absorption reflow resistance, plating resistance and processability. A more preferable lower limit of the content of the inorganic filler is 20 parts by weight.
The resin composition of the present invention may contain a flow control agent for the purpose of improving coatability and shape retentivity to an adherend in a short time.
Examples of the flow control agent include fumed silica such as AEROSIL, and layered silicate.
The flow control agent can be used alone, also can be combined with more than 2.
As the flow control agent, a flow control agent having an average particle diameter of less than 100nm is preferably used.
The lower limit of the content of the flow control agent is preferably 0.1 part by weight, and the upper limit is preferably 100 parts by weight, based on 100 parts by weight of the curable resin. When the content of the flow control agent is in this range, the effects of improving the applicability to an adherend in a short time and the shape retention property are more excellent. A more preferable lower limit of the content of the flow control agent is 0.5 parts by weight, and a more preferable upper limit is 50 parts by weight.
The resin composition of the present invention may contain an organic filler for the purpose of relaxing stress, imparting toughness, and the like.
Examples of the organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanamine particles, and core-shell particles thereof. Among them, polyamide particles, polyamideimide particles, and polyimide particles are preferable.
The organic fillers may be used alone, or 2 or more of them may be used in combination.
When a solvent described later is used, the content of the organic filler is preferably up to 300 parts by weight based on 100 parts by weight of the total resin composition excluding the solvent. When the content of the organic filler is in this range, the toughness and the like of the cured product of the obtained resin composition are more excellent while maintaining excellent adhesiveness and the like. A more preferable upper limit of the content of the organic filler is 200 parts by weight.
The resin composition of the present invention may contain a flame retardant.
Examples of the flame retardant include metal hydrates such as boehmite type aluminum hydroxide, and magnesium hydroxide, halogen compounds, phosphorus compounds, and nitrogen compounds. Among them, boehmite type aluminum hydroxide is preferable.
The flame retardants mentioned above may be used alone, or 2 or more of them may be used in combination.
The lower limit of the content of the flame retardant is preferably 2 parts by weight, and the upper limit is preferably 300 parts by weight, based on 100 parts by weight of the curable resin. When the content of the flame retardant is in this range, the obtained resin composition has excellent flame retardancy while maintaining excellent adhesiveness and the like. A more preferable lower limit and a more preferable upper limit of the content of the flame retardant are 5 parts by weight and 250 parts by weight, respectively.
The resin composition of the present invention may contain a thermoplastic resin within a range not to impair the object of the present invention. By using the thermoplastic resin, the resin composition of the present invention has more excellent flow characteristics, can more easily achieve both filling properties and anti-leaching properties during thermocompression bonding, and has more excellent bending resistance after curing.
Examples of the thermoplastic resin include polyimide resins, phenoxy resins, polyamide resins, polyamideimide resins, polyvinyl acetal resins, and the like. Among them, polyimide resins and phenoxy resins are preferred in terms of heat resistance and handling properties.
The thermoplastic resin can be used alone, also can be combined with more than 2.
The lower limit of the number average molecular weight of the thermoplastic resin is preferably 2000, and the upper limit is preferably 10 ten thousand. When the number average molecular weight of the thermoplastic resin is in this range, the flow characteristics and the bending resistance after curing of the obtained resin composition are more excellent. A more preferable lower limit of the number average molecular weight of the thermoplastic resin is 5000, and a more preferable upper limit is 5 ten thousand.
The lower limit of the content of the thermoplastic resin is preferably 0.5 parts by weight and the upper limit is preferably 120 parts by weight with respect to 100 parts by weight of the curable resin. By setting the content of the thermoplastic resin to 0.5 parts by weight or more, the flow property and the bending resistance after curing of the obtained resin composition are more excellent. By setting the content of the thermoplastic resin to 120 parts by weight or less, the obtained resin composition is more excellent in adhesiveness and heat resistance. A more preferable lower limit of the content of the thermoplastic resin is 1 part by weight, and a more preferable upper limit is 80 parts by weight.
The resin composition of the present invention may contain a solvent from the viewpoint of coatability and the like.
The solvent is preferably a nonpolar solvent having a boiling point of 160 ℃ or less or an aprotic polar solvent having a boiling point of 160 ℃ or less, from the viewpoints of coatability, storage stability, and the like.
Examples of the nonpolar solvent having a boiling point of 160 ℃ or less or the aprotic polar solvent having a boiling point of 160 ℃ or less include ketone solvents, ester solvents, hydrocarbon solvents, halogen solvents, ether solvents, nitrogen-containing solvents, and the like.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of the ester-based solvent include methyl acetate, ethyl acetate, and isobutyl acetate.
Examples of the hydrocarbon solvent include benzene, toluene, n-hexane, isohexane, cyclohexane, methylcyclohexane, and n-heptane.
Examples of the halogen-based solvent include dichloromethane, chloroform, and trichloroethylene.
Examples of the ether solvent include diethyl ether, tetrahydrofuran, 1, 4-dioxane, 1, 3-dioxolane, and the like.
Examples of the nitrogen-containing solvent include acetonitrile.
Among them, from the viewpoint of handling properties, solubility of the curing agent, and the like, at least 1 kind selected from ketone solvents having a boiling point of 60 ℃ or higher, ester solvents having a boiling point of 60 ℃ or higher, and ether solvents having a boiling point of 60 ℃ or higher is preferable. Examples of such a solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, isobutyl acetate, 1, 4-dioxane, 1, 3-dioxolane, and tetrahydrofuran.
The "boiling point" refers to a value measured under a condition of 101kPa, or a value converted to 101kPa in a boiling point conversion chart or the like.
The lower limit of the content of the solvent in 100 parts by weight of the resin composition of the present invention is preferably 10 parts by weight, and the upper limit is preferably 80 parts by weight. When the content of the solvent is in this range, the resin composition of the present invention is more excellent in coating properties and the like. A more preferable lower limit of the content of the solvent is 20 parts by weight, and a more preferable upper limit is 70 parts by weight.
The resin composition of the present invention may contain a reactive diluent within a range not hindering the object of the present invention.
As the reactive diluent, a reactive diluent having 2 or more reactive functional groups in 1 molecule is preferable from the viewpoint of adhesion reliability.
The resin composition of the present invention may further contain additives such as a coupling agent, a dispersant, a storage stabilizer, a bleeding inhibitor, a flux, a leveling agent, and the like.
Examples of the method for producing the resin composition of the present invention include a method of mixing a curable resin, the ester compound of the present invention, and a solvent and the like added as needed, using a mixer.
Examples of the mixer include a homomixer, a universal mixer, a banbury mixer, and a kneader.
The resin composition of the present invention is applied to a substrate film and dried to obtain a resin composition film containing the resin composition of the present invention, and the resin composition film is cured to obtain a cured product. A cured product of the resin composition of the present invention is also one of the present invention.
The lower limit of the glass transition temperature of the cured product of the resin composition of the present invention is preferably 100 ℃ and the upper limit is preferably 250 ℃. When the glass transition temperature of the cured product is in this range, the cured product of the resin composition of the present invention has more excellent mechanical strength and long-term heat resistance. A more preferable lower limit of the glass transition temperature of the cured product is 130 ℃ and a more preferable upper limit thereof is 220 ℃.
In the present specification, the "glass transition temperature of a cured product" can be determined as the peak temperature of the tan δ curve obtained when the measurement is performed under the temperature-raising condition of the temperature-raising speed of 10 ℃/minute, the frequency of 10Hz, the distance between chucks of 24mm and-0 ℃ to 300 ℃ using a dynamic viscoelasticity measuring apparatus. Examples of the dynamic viscoelasticity measuring apparatus include a RHEOVIBRON dynamic viscoelasticity automatic measuring apparatus DDV-GP series (manufactured by A & D Co., Ltd.). The cured product for measuring the glass transition temperature can be obtained by heating the resin composition film having a thickness of about 400 μm at 190 ℃ for 30 minutes.
When a biphenyl type epoxy resin is contained as the curable resin, the linear expansion coefficient of a cured product of the resin composition of the present invention in a temperature range of 40 to 120 ℃ is preferably 5 ppm/DEG C at the lower limit and 100 ppm/DEG C at the upper limit. The cured product of the resin composition of the present invention has more excellent heat resistance. A more preferable lower limit of the above linear expansion coefficient is 10 ppm/DEG C, and a more preferable upper limit is 80 ppm/DEG C.
In the present specification, the "linear expansion coefficient" refers to a value measured by TMA method under conditions of a temperature rise rate of 10 ℃/min and a force of 50N. The cured product used for the measurement of the linear expansion coefficient can be obtained, for example, by heating the resin composition film having a thickness of about 40 μm at 190 ℃ for 30 minutes.
When a biphenyl type epoxy resin is contained as the curable resin, a preferable upper limit of the dielectric loss tangent of a cured product of the resin composition of the present invention at 23 ℃ is 15. When the dielectric loss tangent of the cured product at 23 ℃ is 15 or less, the resin composition of the present invention can be suitably used for an interlayer insulating material such as a multilayer printed wiring board. A more preferable upper limit of the dielectric loss tangent of the cured product at 23 ℃ is 10.
The "dielectric loss tangent" is a value measured at 5GHz using a dielectric constant measuring device and a network analyzer. The cured product for measuring the "dielectric loss tangent" can be obtained by heating the resin composition film having a thickness of about 40 μm to about 200 μm at 190 ℃ for 90 minutes.
The resin composition of the present invention can be used in a wide range of applications, and is particularly suitable for electronic material applications requiring high heat resistance. For example, the resin composition can be used for chip adhesives (ダイアタッチ) in applications to control units (ECUs) for aviation and vehicles, and power devices using SiC and GaN. Further, the resin composition can be used for, for example, an adhesive for power overlay packaging (Japanese patent: パワーオーバーレイパッケージ), an adhesive for printed wiring boards, an adhesive for coverlays of flexible printed circuit boards, a copper-clad laminate, an adhesive for semiconductor bonding, an interlayer insulating material, a prepreg, an encapsulant for LEDs, an adhesive for structural materials, and the like.
Among them, the resin composition of the present invention can be suitably used for a laminate film because the cured product has a low dielectric constant, a low dielectric loss tangent and excellent dielectric characteristics. A laminate film using the resin composition of the present invention is also one aspect of the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, an ester compound that can be used for a resin composition excellent in heat resistance and dielectric characteristics after curing can be provided. The present invention also provides a resin composition containing the ester compound, a cured product of the resin composition, and a laminated film using the resin composition.
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Synthesis example 1 (preparation of ester Compound A)
Using a vessel equipped with a stirrer, a reflux condenser, and a dean-stark water separator, 21.1 parts by weight of trimellitic anhydride acid chloride was dissolved in 200 parts by weight of N-methyl-2-pyrrolidone. To the resulting solution, 14.4 parts by weight of 2-naphthol and 10.1 parts by weight of triethylamine were added, and the mixture was stirred at 25 ℃ for 4 hours to react.
To the obtained reaction solution, 14.6 parts by weight of 1, 3-bis (3-aminophenoxy) benzene was added, and the mixture was stirred at 25 ℃ for 4 hours to effect a reaction. After 200 parts by weight of toluene was added to the resulting solution, reflux was carried out at 150 ℃ for 4 hours until water was not produced any more. After the reaction was completed, the solution from which toluene was removed by an evaporator was added dropwise to 800 parts by weight of pure water, and the precipitate was separated by filtration and then dried under vacuum to obtain ester compound a.
By the way of illustration1H-NMR, GPC and FT-IR analyses confirmed that the ester compound A was represented by the formula (1) (R)1、R2Is a group (R) represented by the above formula (2)4All hydrogen atoms), R3Is a group (R) represented by the above formula (3-2)6All hydrogen atoms), n is 0).
Synthesis example 2 (preparation of ester Compound B)
An ester compound B was obtained in the same manner as in synthesis example 1, except that 14.4 parts by weight of 2-naphthol was changed to 9.4 parts by weight of phenol.
By the way of illustration1H-NMR, GPC and FT-IR analyses confirmed that the ester compound B was represented by the formula (1) (R)1、R2Is phenyl, R3Is a group (R) represented by the above formula (3-2)6All hydrogen atoms), n is 0).
Synthesis example 3 (preparation of ester Compound C)
An ester compound C was obtained in the same manner as in synthesis example 1 except that 14.6 parts by weight of 1, 3-bis (3-aminophenoxy) benzene was changed to 8.9 parts by weight of a mixture of 2-methyl-4, 6-diethyl-1, 3-phenylenediamine and 2, 4-diethyl-6-methyl-1, 3-phenylenediamine ("Ethacure 100", manufactured by Mitsui Fine Chemicals).
By the way of illustration1H-NMR, GPC and FT-IR analyses confirmed that the ester compound C was represented by the formula (1) (R)1、R2Is a group (R) represented by the above formula (2)4All hydrogen atoms), R3Is a group represented by the above-mentioned formulae (4-1) and (4-2), and n is 0).
Synthesis example 4 (preparation of ester Compound D)
An ester compound D was obtained in the same manner as in synthesis example 1, except that 14.6 parts by weight of 1, 3-bis (3-aminophenoxy) benzene was changed to 9.9 parts by weight of 4, 4' -diaminodiphenylmethane.
By the way of illustration1H-NMR, GPC and FT-IR analyses confirmed that the ester compound D was represented by the formula (1) (R)1、R2Is a group (R) represented by the above formula (2)4All hydrogen atoms), R3Is a group (R) represented by the above formula (3-3)7All being hydrogen atoms, R8All hydrogen atoms), n is 0).
Synthesis example 5 (preparation of ester Compound E)
An ester compound E was obtained in the same manner as in synthesis example 1, except that 14.6 parts by weight of 1, 3-bis (3-aminophenoxy) benzene was changed to 21.6 parts by weight of bis (4- (4-aminophenoxy) phenyl) sulfone.
By the way of illustration1H-NMR, GPC and FT-IR analyses confirmed that the ester compound E was composed ofThe formula (1) represents (R)1、R2Is a group (R) represented by the above formula (2)4All hydrogen atoms), R3Is a group (R) represented by the above formula (3-4)9All hydrogen atoms), n is 0).
Synthesis example 6 (preparation of ester Compound F)
Using a vessel equipped with a stirrer, a reflux condenser, and a dean-stark water separator, 21.1 parts by weight of trimellitic anhydride acid chloride, 7.2 parts by weight of 2-naphthol, and 2.8 parts by weight of 1, 3-dihydroxybenzene were dissolved in 130 parts by weight of N-methyl-2-pyrrolidone. To the resulting solution, 11.1 parts by weight of triethylamine was added, and the mixture was stirred at 25 ℃ for 2 hours to effect a reaction.
To the obtained reaction solution, 8.9 parts by weight of a mixture of 2-methyl-4, 6-diethyl-1, 3-phenylenediamine and 2, 4-diethyl-6-methyl-1, 3-phenylenediamine ("Ethacure 100", manufactured by Mitsui Fine Chemicals) was added, and the mixture was stirred at 25 ℃ for 2 hours to effect a reaction. After 50 parts by weight of toluene was added to the resulting solution, reflux was carried out at 170 ℃ overnight until water was not produced any more. After the reaction, the reaction mixture was added dropwise to 800 parts by weight of methanol, and after separating the precipitate by filtration, the mixture was vacuum-dried to obtain an ester compound F.
By the way of illustration1H-NMR and GPC confirmed that the ester compound F was represented by the formula (1) (R)1、R2Is a group (R) represented by the above formula (2)4All hydrogen atoms), R3Is a group represented by the above formulae (4-1) and (4-2), X is a 1, 3-phenylene group, and n is 0 or more and 10 or less). The number average molecular weight of the ester compound F determined from the GPC result was 1784.
Synthesis example 7 (preparation of ester Compound G)
An ester compound G was obtained in the same manner as in synthesis example 6, except that 2.8 parts by weight of 1, 3-dihydroxybenzene was changed to 4.7 parts by weight of 4, 4' -dihydroxybiphenyl.
By the way of illustration1H-NMR and GPC confirmed that the ester compound G was represented by the formula (1) (R)1、R2Is a group (R) represented by the above formula (2)4All hydrogen atoms), R3Are represented by the above formulae (4-1) and (4-2)X is a group (R) represented by the above formula (5-1)10All are hydrogen atoms), and n is 0 or more and 10 or less). The number average molecular weight of the ester compound G determined from the GPC result was 2175.
Synthesis example 8 (preparation of ester Compound H)
An ester compound H was obtained in the same manner as in synthesis example 6, except that 2.8 parts by weight of 1, 3-dihydroxybenzene was changed to 7.5 parts by weight of 1, 1' -methylenebis-2-naphthol.
By the way of illustration1H-NMR and GPC confirmed that the ester compound H was represented by the formula (1) (R)1、R2Is a group (R) represented by the above formula (2)4All hydrogen atoms), R3Is a group represented by the above formula (4-1) or (4-2), and X is a group (R) represented by the above formula (5-2)11All are hydrogen atoms, and n is 0 or more and 10 or less)). The number average molecular weight of the ester compound H determined from the GPC result was 1687.
Synthesis example 9 (preparation of ester Compound I)
Using a vessel equipped with a stirrer, a reflux condenser, and a dean-stark water separator, 21.8 parts by weight of 3-aminophenol was dissolved in 100 parts by weight of N-methyl-2-pyrrolidone. To the resulting solution, 52.0 parts by weight of 2, 2-bis (4- (2, 3-dicarboxyphenoxy) phenyl) propane was added, and the mixture was stirred at 25 ℃ for 4 hours to effect a reaction. After adding 100 parts by weight of toluene to the resulting solution, reflux was carried out at 150 ℃ for 4 hours until water was not produced any more. After the reaction was completed, the solution obtained by removing toluene from the obtained solution by using an evaporator was added dropwise to 800 parts by weight of pure water, and precipitates were separated by filtration.
70.3 parts by weight of the precipitate thus obtained and 20.2 parts by weight of triethylamine were further dissolved in 200 parts by weight of N-methyl-2-pyrrolidone. To the resulting solution, 28.1 parts by weight of benzoyl chloride was added, and the mixture was stirred at 25 ℃ for 4 hours to effect a reaction. After the reaction was completed, the obtained solution was added dropwise to 800 parts by weight of pure water, and after separating precipitates by filtration, vacuum drying was performed to obtain ester compound I.
By the way of illustration1H-NMR, GPC and FT-IR analysis confirmed that the ester compound I was not represented by the above formula (1).
(examples 1 to 8, comparative examples 1 and 2)
Methyl ethyl ketone was added as a solvent to each of the materials at the mixing ratios shown in table 1, and the mixture was stirred at 1200rpm for 4 hours with a stirrer to obtain a resin composition. The compositions in table 1 show solid components other than the solvent.
The obtained resin composition was coated on a release-treated surface of a PET film having a thickness of 25 μm using an applicator. XG284 (manufactured by Toray corporation) was used as a PET film. Then, the film was dried in a gill oven at 100 ℃ for 5 minutes to volatilize the solvent, thereby obtaining an uncured laminate film having a PET film and a resin composition layer having a thickness of 40 μm on the PET film.
< evaluation >
The uncured laminated films obtained in examples and comparative examples were evaluated as follows. The results are shown in Table 1.
(coefficient of linear expansion)
Each of the uncured laminated films obtained in examples and comparative examples was heated at 190 ℃ for 90 minutes, and then the base PET film was peeled off to obtain a cured product. The linear expansion coefficient of the obtained cured product was measured in a temperature range of 25 ℃ to 150 ℃ under a condition of a temperature rise rate of 10 ℃/min and a force of 50N using a TMA apparatus. TMA7100 (manufactured by Hitachi High-TechScience) was used as the TMA device.
(dielectric loss tangent)
Each of the uncured laminated films obtained in examples and comparative examples was heated at 190 ℃ for 90 minutes, and then the base PET film was peeled off to obtain a cured product. The obtained cured product was cut into a size of 2mm in width and 100mm in length. The cut cured product was measured for dielectric loss tangent by the cavity resonance method at 23 ℃ and a frequency of 5GHz using a cavity resonance perturbation dielectric constant measuring apparatus and a network analyzer. CP521 (manufactured by Kanto electronics application and development Co., Ltd.) was used as a device for measuring dielectric constant by cavity resonance perturbation method, and N5224A PNA (manufactured by KEYSIGHTTECHNOLOGIES Co., Ltd.) was used as a network analyzer.
(elongation at maximum breaking Point)
Each of the uncured laminated films obtained in examples and comparative examples was heated at 200 ℃ for 3 hours, and then the base PET film was peeled off to obtain a cured product. The obtained cured product was cut into a size of 10mm in width and 100mm in length. The cut cured product was subjected to a tensile test using a tensile tester under conditions of a chuck-to-chuck distance of 60mm, a tensile speed of 5 mm/min and an initial tension of 0.35N to measure the maximum breaking point elongation. UCT-500 (manufactured by ORIENTEC) was used as a tensile tester.
[ Table 1]
Industrial applicability
According to the present invention, an ester compound that can be used for a resin composition excellent in heat resistance and dielectric characteristics after curing can be provided. The present invention also provides a resin composition containing the ester compound, a cured product of the resin composition, and a laminated film using the resin composition.
Claims (8)
1. An ester compound represented by the following formula (1),
in the formula (1), R1And R2Each, the same or different, is an optionally substituted aryl group, R3Is a 2-valent group having at least 1 optionally substituted arylene group, X is a 2-valent group having at least 1 optionally substituted arylene group, and n is an integer of 0 or more and 10 or less.
2. The ester compound according to claim 1, wherein R in the formula (1)1And R2Is a group represented by the following formula (2),
in the formula (2), R4Each independently is a hydrogen atom or an aliphatic group, and is a bonding site.
3. The ester compound according to claim 1 or 2, wherein R in the formula (1)3Is a group represented by any one of the following formulae (3-1), (3-2), (3-3) or (3-4),
in the formula (3-1), R5Each independently a hydrogen atom or an aliphatic group, in the formula (3-2), R6Each independently a hydrogen atom or an aliphatic group, in the formula (3-3), R7Each independently is a hydrogen atom or an aliphatic group, R8Each independently a hydrogen atom or an aliphatic group, in the formula (3-4), R9Each independently a hydrogen atom or an aliphatic group, and in the formulae (3-1), (3-2), (3-3) and (3-4), the bond site.
4. The ester compound according to claim 1,2 or 3, wherein the molecular weight is 1 ten thousand or less.
5. A resin composition comprising a curable resin and a curing agent,
the curing agent comprises the ester compound of claim 1,2, 3 or 4.
6. The resin composition according to claim 5, wherein the curable resin comprises an epoxy resin.
7. A cured product of the resin composition according to claim 5 or 6.
8. A laminate film comprising the resin composition according to claim 5 or 6.
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| JP2019002678 | 2019-01-10 | ||
| JP2019-002678 | 2019-01-10 | ||
| PCT/JP2020/000448 WO2020145346A1 (en) | 2019-01-10 | 2020-01-09 | Ester compound, resin composition, cured product, and build-up film |
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| JP (2) | JP7467330B2 (en) |
| KR (1) | KR20210113159A (en) |
| CN (1) | CN113383029B (en) |
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| WO (1) | WO2020145346A1 (en) |
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| CN114524938A (en) * | 2021-10-28 | 2022-05-24 | 江苏三月科技股份有限公司 | Polymer, photosensitive resin composition, cured film prepared from same and electronic element |
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| CA1276016C (en) | 1987-01-13 | 1990-11-06 | Konoe Miura | Anthraquinone compounds and polarizing film containing the same |
| JPH04180920A (en) * | 1990-11-15 | 1992-06-29 | Teijin Ltd | Copolyester |
| JPH04182920A (en) * | 1990-11-16 | 1992-06-30 | Konica Corp | Magnetic recording medium |
| US5268487A (en) * | 1993-04-07 | 1993-12-07 | National Science Council | Diimide dicarboxylic acid |
| JP3829354B2 (en) * | 1996-04-01 | 2006-10-04 | 日立化成工業株式会社 | Aromatic polyamideimide, process for producing the same and varnish containing the same |
| JP4543314B2 (en) * | 2003-09-01 | 2010-09-15 | 東洋紡績株式会社 | Polyamideimide resin, resin composition, and metal-clad laminate using the same |
| JP4182920B2 (en) | 2004-06-03 | 2008-11-19 | ブラザー工業株式会社 | Inkjet printer |
| JP2006335843A (en) | 2005-06-01 | 2006-12-14 | Kaneka Corp | Thermosetting resin composition and application thereof |
| TWI522099B (en) | 2014-06-04 | 2016-02-21 | 中國醫藥大學 | Pharmaceutical formulation for treating pancreatic cancer and uses of the same |
| KR20160114286A (en) | 2015-03-24 | 2016-10-05 | 길기영 | Tunnel internal traffic information providing device through the interlocking of the tunnel monitoring cameras and vehicle navigation |
| KR102211591B1 (en) | 2016-03-30 | 2021-02-02 | 아라까와 가가꾸 고교 가부시끼가이샤 | Polyimide, polyimide-based adhesive, film-shaped adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper clad laminate and printed wiring board, and multi-layer board and manufacturing method thereof |
| CN106433125B (en) * | 2016-08-31 | 2019-04-16 | 成都正威新材料研发有限公司 | A kind of high-performance thermoplastic polyimides PP Pipe Compound and its manufacturing method |
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2020
- 2020-01-09 KR KR1020217013923A patent/KR20210113159A/en not_active Application Discontinuation
- 2020-01-09 CN CN202080007615.0A patent/CN113383029B/en active Active
- 2020-01-09 WO PCT/JP2020/000448 patent/WO2020145346A1/en active Application Filing
- 2020-01-09 JP JP2020504427A patent/JP7467330B2/en active Active
- 2020-01-10 TW TW109100901A patent/TWI826633B/en active
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| US3951977A (en) * | 1970-09-16 | 1976-04-20 | Standard Oil Company | 4-High molecular weight alkyl-substituted carbophenoxy phthalic acid-containing compounds |
| JPS504063A (en) * | 1973-05-17 | 1975-01-16 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114524938A (en) * | 2021-10-28 | 2022-05-24 | 江苏三月科技股份有限公司 | Polymer, photosensitive resin composition, cured film prepared from same and electronic element |
| CN114524938B (en) * | 2021-10-28 | 2024-02-09 | 江苏三月科技股份有限公司 | Polymer, photosensitive resin composition, cured film prepared from polymer and photosensitive resin composition, and electronic element |
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| Publication number | Publication date |
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| CN113383029B (en) | 2023-10-24 |
| TWI826633B (en) | 2023-12-21 |
| WO2020145346A1 (en) | 2020-07-16 |
| JP2024086771A (en) | 2024-06-28 |
| JPWO2020145346A1 (en) | 2021-11-18 |
| KR20210113159A (en) | 2021-09-15 |
| TW202037588A (en) | 2020-10-16 |
| JP7467330B2 (en) | 2024-04-15 |
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