CN113383029B - Ester compound, resin composition, cured product, and laminate film - Google Patents
Ester compound, resin composition, cured product, and laminate film Download PDFInfo
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- CN113383029B CN113383029B CN202080007615.0A CN202080007615A CN113383029B CN 113383029 B CN113383029 B CN 113383029B CN 202080007615 A CN202080007615 A CN 202080007615A CN 113383029 B CN113383029 B CN 113383029B
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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
Abstract
The purpose of the present invention is to provide an ester compound which can be used in a resin composition having excellent heat resistance and dielectric characteristics after curing. The present invention also provides a resin composition containing the ester compound, a cured product of the resin composition, and a laminate film using the resin composition. The present invention is an ester compound represented by the following formula (1). In the formula (1), R 1 And R is 2 Each of which may be the same or different, is an aryl group which may be substituted, R 3 In order to have a valence of 2 group of at least 1 arylene group which may be substituted, X is a valence of 2 group having at least 1 arylene group which may be substituted, and n is an integer of 0 to 10.
Description
Technical Field
The present invention relates to an ester compound which can be used in a resin composition excellent in 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 excellent adhesion, insulation and chemical resistance, are used in many industrial products. In particular, a resin composition used for an interlayer insulating material or the like of a printed circuit board is required to have dielectric characteristics such as a low dielectric constant and a low dielectric loss tangent. As resin compositions excellent in such dielectric characteristics, for example, patent documents 1 and 2 disclose resin compositions 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 heat resistance and dielectric characteristics after curing.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2017-186551
Patent document 2: international publication No. 2016/114286
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide an ester compound which can be used in a resin composition having excellent heat resistance and dielectric characteristics after curing. The present invention also provides a resin composition containing the ester compound, a cured product of the resin composition, and a laminate 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), R 1 And R is 2 Each of which may be the same or different, is an aryl group which may be substituted, R 3 In order to have a valence of 2 group of at least 1 arylene group which may be substituted, X is a valence of 2 group having at least 1 arylene group which may be substituted, and n is an integer of 0 to 10.
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 completed the present invention.
The ester compound of the present invention is represented by the above formula (1).
In the above formula (1), R 1 And R is 2 Each of which may be the same or different, is an aryl group which may be substituted. By having an aryl group which may be substituted as R 1 And R is as described above 2 Thus, the ester compound of the present invention gives a resin composition having excellent dielectric characteristics such as low dielectric loss tangent when used as a curing agent.
Examples of the aryl group include phenyl, naphthyl, and anthracenyl.
Examples of the substituent when the aryl group is substituted include an aliphatic group and the like.
Wherein R in the above formula (1) 1 And R is 2 The group represented by the following formula (2) is preferable. By making R as described above 1 And R is as described above 2 The resin composition obtained by using the ester compound of the present invention as a curing agent has more excellent dielectric characteristics such as low dielectric loss tangent of a cured product of the resin composition, because the resin composition is represented by the following formula (2).
[ chemical formula 2]
In the formula (2), R 4 Each independently is a hydrogen atom or an aliphatic group, and each is a bonding position.
In the above formula (1), R 3 Is a 2-valent group having at least 1 arylene group that may be substituted. By making R as described above 3 The resin composition has a 2-valent group of at least 1 arylene group which may be substituted, and thus the 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 above formula(1) When n in (1) or more, each R 3 May be the same or different.
R in the above formula (1) 3 Examples of the arylene group include phenylene, naphthylene, and anthracenylene.
Examples of the substituent when the arylene group is substituted include an aliphatic group and the like.
Wherein R in the above formula (1) 3 The group represented by the following formula (3-1), (3-2), (3-3) or (3-4) is preferable, and the group represented by the following formula (3-1) or (3-2) is more preferable. By making R as described above 3 The group represented by the following formula (3-1), (3-2), (3-3) or (3-4) is used, so that when the ester compound of the present invention is used as a curing agent, compatibility with a curable resin becomes more excellent, and heat resistance of a cured product of the obtained resin composition becomes more excellent.
[ chemical formula 3]
In the formula (3-1), R 5 Each independently is a hydrogen atom or an aliphatic group, in the formula (3-2), R 6 Each independently is a hydrogen atom or an aliphatic group, in the formula (3-3), R 7 Each independently is a hydrogen atom or an aliphatic group, R 8 Each independently is a hydrogen atom or an aliphatic group, in the formula (3-4), R 9 Each independently is a hydrogen atom or an aliphatic group, and in formulae (3-1), (3-2), (3-3) and (3-4), is a bonding position.
The R in the formula (1) 3 In the case of the group represented by the above formula (3-1), the group represented by the following formula (4-1) or (4-2) is preferable as the group represented by the above formula (3-1).
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 used 3 A compound having a group represented by the following formula (4-1) and R as described above 3 Is a mixture of compounds having a group represented by the following formula (4-2).
[ chemical formula 4]
In the formulae (4-1) and (4-2), the bond position is.
In the above formula (1), n is an integer of 0 to 10.
In the above formula (1), when n is 0, the heat resistance of 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 addition, even in the case of multimerization, that is, in the case where n in the above formula (1) is 1 or more, the ester compound of the present invention is excellent in heat resistance and dielectric characteristics of a cured product of the resin composition obtained when it is used as a curing agent. In addition, when n in the above 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 resin components and the like, the preferable upper limit of n in the above 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 above formula (1) include phenylene, naphthylene, and anthracenylene.
Examples of the substituent when the arylene group is substituted include an aliphatic group and the like. In the case where n in the above formula (1) is 2 or more, each X may be the same or different.
As the above X in the case of having 2 or more of the above arylene groups, there may be mentioned a group represented by the following formula (5-1) or (5-2).
[ chemical formula 5]
In the formula (5-1), R 10 Each independently is a hydrogen atom or an aliphatic group, in the formula (5-2), R 11 Each independently is a hydrogen atom or an aliphatic group, and in the formulae (5-1) and (5-2), each is a bonding position.
The preferred lower limit of the molecular weight of the ester compound of the present invention is 500, and the preferred upper limit is 1 ten thousand. By setting the molecular weight in this range, the ester compound of the present invention is more excellent in compatibility with the resin component while maintaining excellent heat resistance after curing, and the cured product of the obtained resin composition is more excellent in dielectric characteristics such as low dielectric loss tangent. The more preferable lower limit of the molecular weight of the ester compound of the present invention is 580, the more preferable upper limit is 8000, and the more preferable lower limit is 600. In addition, when more excellent heat resistance is required after curing, the molecular weight of the above ester compound is preferably 5500 or less. The heat resistance of the cured product of the obtained curable resin composition is further improved by setting the molecular weight to 5500 or less. From the viewpoint of heat resistance after curing, the molecular weight of the ester compound is more preferably limited to 5000, still more preferably limited to 4500, still more preferably limited to 4000, particularly preferably limited to 3500, and most preferably limited to 3000. In addition, when more excellent elongation is required after curing, the molecular weight of the above ester compound is preferably 1000 or more. By setting the molecular weight to 1000 or more, the elongation of the cured product of the obtained curable resin composition is further excellent. The lower limit of the molecular weight of the ester compound is more preferably 1200 or more, and still more preferably 1500 or more from the viewpoint of elongation after curing.
In the present specification, the "molecular weight" is a molecular weight obtained from a structural formula of a compound having a specific molecular structure (for example, a compound having n of 0 in the formula (1)). In the present specification, the "molecular weight" may be expressed by using a number average molecular weight for a compound having a wide distribution of polymerization degrees (for example, in the case of a mixture in which n has a plurality of values in the formula (1)) and a compound having an unspecified modified site. In the present specification, the "number average molecular weight" is a value obtained by measuring by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converting the obtained product 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 Japanese analytical industries Co., ltd.).
In the ester compound of the present invention, examples of the 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 is 0 in the above formula (1) can be produced by a method in which a trimellitic anhydride is reacted with an aromatic diamine represented by the following formula (6), and then a hydroxyl-containing aromatic compound represented by the following formula (7-1) and/or a hydroxyl-containing aromatic compound represented by the following formula (7-2) are reacted. Further, a compound in which n is 0 in the above formula (1) 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).
In the case of polymerizing the ester compound of the present invention, that is, in the case of producing a compound having n of 1 or more in the above formula (1), the following method and the like are exemplified.
That is, in the method for producing a compound having n of 0 in the formula (1), a compound having n of 1 or more in the formula (1) can be produced by a method in which a hydroxy-containing aromatic compound represented by the formula (7-1) and/or a hydroxy-containing aromatic compound represented by the formula (7-2) is reacted with a hydroxy-containing aromatic compound represented by the formula (8).
[ chemical formula 6]
H 2 N-R 3 -NH 2 (6)
In the formula (6), R 3 Is R in the formula (1) 3 The same groups.
[ chemical formula 7]
R 1 -OH (7-1)
R 2 -OH (7-2)
In the formula (7-1), R 1 Is R in the formula (1) 1 The same groups, in the formula (7-2), R 2 Is R in the formula (1) 2 The same groups.
[ chemical formula 8]
HO-X-OH(8)
In the formula (8), X is the same group as X in the above formula (1).
As the aromatic diamine represented by the above formula (6), examples thereof include 2-methyl-4, 6-diethyl-1, 3-phenylenediamine, 2, 4-diethyl-6-methyl-1, 3-phenylenediamine, 3 '-diaminodiphenylmethane, 3,4' -diaminodiphenylmethane, 4 '-diaminodiphenylmethane, and 3,3' -diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, 1, 2-phenylenediamine, 1, 3-phenylenediamine, 1, 4-phenylenediamine, 3 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, and bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 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, 3,3' -diamino-4, 4' -dihydroxydiphenylmethane, 4' -diamino-3, 3' -dihydroxydiphenylmethane, 3' -diamino-4, 4' -dihydroxydiphenyl ether, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) propane, diaminophenylfluorene, ditolyl-fluorene, 4' -bis (4-aminophenoxy) biphenyl 4,4' -diamino-3, 3' -dihydroxydiphenyl ether, 3' -diamino-4, 4' -dihydroxydiphenyl, 4' -diamino-2, 2' -dihydroxydiphenyl, 4' -diamino-3, 3' -dihydroxydiphenyl, 4' -bis (4-aminobenzamide) -3,3' -dihydroxydiphenyl, 4' -bis (3-aminobenzamide) -3,3' -dihydroxydiphenyl, and the like. Among them, 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, more preferably 2-methyl-4, 6-diethyl-1, 3-phenylenediamine, 2, 4-diethyl-6-methyl-1, 3-phenylenediamine, 1, 3-bis (3-aminophenoxy) benzene are preferable from the viewpoints of solubility, heat resistance and availability.
Examples of the hydroxyl-containing aromatic compound represented by the above formula (7-1) and the hydroxyl-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, 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-hydroxy-pyrene and the like. Among them, 2-naphthol is preferable from the viewpoint of dielectric characteristics and availability.
Examples of the hydroxyl-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 '-tetramethylbiphenyl-4, 4' -diol, 2-bis (4-hydroxyphenyl) propane, 1 '-methylenebis-2-naphthol, and 1,1' -bi-2-naphthol.
The resin composition containing a curable resin and a curing agent, wherein the curing agent contains the ester compound of the present invention, is also one of the present invention.
By containing the ester compound of the present invention, the 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 a curing agent in addition to the ester compound of the present invention in a range that does not hinder the object of the present invention, in order to improve processability in an uncured state, etc.
Examples of the other curing agent include phenol curing agents, thiol curing agents, amine curing agents, acid anhydride curing agents, cyanate curing agents, and active ester curing agents other than the ester compounds of the present invention. Among them, other active ester-based curing agents and cyanate-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, and more preferably 300 parts by weight, based on 100 parts by weight of the curable resin. 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 in this range, whereby the heat resistance and dielectric characteristics of the obtained resin composition are further excellent. The 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-mentioned curing agent is 70 parts by weight, and the more preferable upper limit is 200 parts by weight.
The content of the ester compound of the present invention in the case of using the ester compound of the present invention and other curing agents together as the curing agent is preferably 5 parts by weight, and more preferably 200 parts by weight, based on 100 parts by weight of the curable resin. When the ester compound of the present invention and another curing agent are used in combination as the curing agent, the content of the ester compound of the present invention is in this range, whereby the heat resistance and dielectric characteristics of the obtained resin composition are further excellent. When the ester compound of the present invention and other curing agents are used as the curing agents, 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 the other curing agent are used 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, and the upper limit is preferably 200 parts by weight, based on 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, phenolic resins, imide resins, maleimide resins, benzoxazine resins, silicone resins, acrylic resins, and fluorine resins. Among them, the curable resin preferably contains at least 1 selected from the group consisting of epoxy resins, cyanate resins, phenolic resins, imide resins, maleimide resins, and benzoxazine resins, and more preferably contains an epoxy resin. The curable resin may be used alone or in combination of 2 or more.
Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2' -diallyl bisphenol a type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol a type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, naphthylene ether type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin, and glycidyl ester compound.
The resin composition of the present invention preferably contains a curing accelerator. By containing the above-mentioned curing accelerator, the curing time can be shortened and 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 viewpoints of storage stability and curability.
The curing accelerators may be used alone or in combination of 2 or more.
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 within this range, the effect of shortening the curing time is more excellent without deteriorating the adhesion of the obtained resin composition. The lower limit of the content of the above-mentioned curing accelerator is more preferably 0.05 parts 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 resistance to reflow by moisture absorption, plating and processability while maintaining excellent adhesion and long-term heat resistance.
The inorganic filler is preferably at least one of silica and barium sulfate. By containing at least one of silica and barium sulfate as the inorganic filler, the resin composition of the present invention is more excellent in resistance to reflow under moisture, plating resistance, and processability.
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 in combination of 2 or more.
The average particle diameter of the inorganic filler is preferably 50nm in lower limit and 10 μm in upper limit. When the average particle diameter of the inorganic filler is within this range, the resulting resin composition is more excellent in coatability and processability. The average particle diameter of the inorganic filler is more preferably limited to 100nm at a lower limit and 5 μm at an upper limit.
When the solvent described later is used, the content of the inorganic filler is preferably 10 parts by weight, and the upper limit is preferably 1000 parts by weight, based on 100 parts by weight of the total resin composition excluding the solvent. When the content of the inorganic filler is within this range, the resin composition obtained is more excellent in resistance to reflow due to moisture absorption, plating resistance and processability. The 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 regulator for the purpose of improving the coatability and shape retention properties of an adherend in a short period of time.
Examples of the flow regulator include fumed silica such as AEROSIL and a layered silicate.
The above-mentioned flow regulators may be used alone or in combination of 2 or more.
The flow control agent preferably has an average particle diameter of less than 100 nm.
The content of the flow regulator is preferably limited to 0.1 part by weight, and the content of the flow regulator is preferably limited to 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 effect of improving the coatability and shape retention properties of the adherend in a short period of time is more excellent. The more preferable lower limit of the content of the above flow regulator is 0.5 parts by weight, and the 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 filler may be used alone or in combination of 2 or more.
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 further excellent while maintaining excellent adhesion and the like. The 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, aluminum hydroxide and magnesium hydroxide, halogen-based compounds, phosphorus-based compounds and nitrogen compounds. Among them, boehmite type aluminum hydroxide is preferable.
The above flame retardants may be used alone or in combination of 2 or more.
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, relative to 100 parts by weight of the curable resin. When the content of the flame retardant is within this range, the obtained resin composition is excellent in flame retardancy while maintaining excellent adhesion and the like. The lower limit of the content of the above flame retardant is more preferably 5 parts by weight, and the upper limit is more preferably 250 parts by weight.
The resin composition of the present invention may contain a thermoplastic resin within a range that does not hinder the object of the present invention. By using the thermoplastic resin, the resin composition of the present invention is more excellent in flow characteristics, is more easily compatible with both of the filling property and the leaching resistance at the time of thermocompression bonding, and is more excellent in bending resistance after curing.
Examples of the thermoplastic resin include polyimide resins, phenoxy resins, polyamide resins, polyamideimide resins, and polyvinyl acetal resins. Among them, polyimide resins and phenoxy resins are preferable from the viewpoints of heat resistance and handling properties.
The thermoplastic resin may be used alone or in combination of 2 or more.
The thermoplastic resin has a preferable lower limit of 2000 and a preferable upper limit of 10 ten thousand in number average molecular weight. When the number average molecular weight of the thermoplastic resin is in this range, the resin composition obtained is more excellent in flow characteristics and flex resistance after curing. The number average molecular weight of the thermoplastic resin is more preferably limited to 5000, and the upper limit is more preferably 5 ten thousand.
The content of the thermoplastic resin is preferably limited to 0.5 parts by weight, and the content of the thermoplastic resin is preferably limited to 120 parts by weight, based on 100 parts by weight of the curable resin. When the content of the thermoplastic resin is 0.5 parts by weight or more, the resulting resin composition is more excellent in flow characteristics and flex resistance after curing. The thermoplastic resin is contained in an amount of 120 parts by weight or less, whereby the resulting resin composition is more excellent in adhesion and heat resistance. The more preferable lower limit of the content of the thermoplastic resin is 1 part by weight, and the 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, etc.
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, and nitrogen-containing solvents.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of the ester solvents 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 methylene chloride, chloroform, and trichloroethylene.
Examples of the ether solvent include diethyl ether, tetrahydrofuran, 1, 4-dioxane, and 1, 3-dioxolane.
Examples of the nitrogen-containing solvent include acetonitrile.
Among them, from the viewpoints of handleability, solubility of the above-mentioned curing agent, and the like, at least 1 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 solvents include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, isobutyl acetate, 1, 4-dioxane, 1, 3-dioxolane, tetrahydrofuran, and the like.
The "boiling point" refers to a value measured under the condition of 101kPa, or a value converted to 101kPa in a boiling point conversion chart or the like.
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 within this range, the resin composition of the present invention is more excellent in coating properties and the like. The lower limit of the content of the above solvent is more preferably 20 parts by weight, and the upper limit is more preferably 70 parts by weight.
The resin composition of the present invention may contain a reactive diluent within a range that does not hinder 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, an anti-bleeding agent, 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, if necessary, using a mixer.
Examples of the mixer include a homogenizing and dispersing machine, a universal mixer, a Banbury mixer, and a kneader.
The resin composition of the present invention can be 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 can be cured to obtain a cured product. The 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 ℃. By setting the glass transition temperature of the cured product to this range, the cured product of the resin composition of the present invention is more excellent in mechanical strength and long-term heat resistance. The lower limit of the glass transition temperature of the cured product is more preferably 130℃and the upper limit is more preferably 220 ℃.
In the present specification, the "glass transition temperature of a cured product" may be obtained as a peak temperature of a tan δ curve obtained when the measurement is performed under a heating condition of a heating rate of 10 ℃/min, a frequency of 10Hz, a distance between chucks of 24mm, and a temperature of-0 ℃ to 300 ℃ using a dynamic viscoelasticity measurement apparatus. Examples of the dynamic viscoelasticity measuring device include the RHEOVIBRON dynamic viscoelasticity automatic measuring device DDV-GP series (manufactured by A & D Co., ltd.). The cured product of 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 lower limit of the linear expansion coefficient of the cured product of the resin composition of the present invention in the temperature range of 40 to 120℃is preferably 5ppm/℃and the upper limit is preferably 100ppm/℃. The cured product of the resin composition of the present invention is more excellent in 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 term "linear expansion coefficient" means a value measured by the 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.
In the case of containing a biphenyl type epoxy resin as the curable resin, the upper limit of the dielectric tangent at 23℃of the cured product of the resin composition of the present invention is preferably 15. The resin composition of the present invention can be suitably used for an interlayer insulating material such as a multilayer printed wiring board by setting the dielectric loss tangent of the cured product at 23 ℃ to 15 or less. The upper limit of the dielectric loss tangent of the cured product at 23℃is more preferably 10.
The "dielectric loss tangent" is a value measured at 5GHz using a dielectric constant measuring device and a network analyzer. The cured product of 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 variety of applications, and is particularly suitable for use in electronic materials requiring high heat resistance. For example, the adhesive can be used for aviation, vehicle-mounted Electric Control Units (ECU) applications, chip adhesives for power device applications using SiC or GaN, and the like. Further, the present invention can be used for, for example, an adhesive for power coating packaging (japanese: case), an adhesive for printed wiring boards, an adhesive for coverlay of flexible printed circuit boards, a copper-clad laminate, an adhesive for bonding semiconductors, an interlayer insulating material, a prepreg, a sealing agent for LEDs, an adhesive for structural materials, and the like.
Among these, the resin composition of the present invention is excellent in dielectric characteristics because the cured product has a low dielectric constant and a low dielectric loss tangent, and therefore can be suitably used for a laminate film. The laminate film obtained by using the resin composition of the present invention is also one of the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, an ester compound which can be used in a resin composition excellent in heat resistance and dielectric characteristics after curing can be provided. Further, according to the present invention, a resin composition containing the ester compound, a cured product of the resin composition, and a laminate film using the resin composition can be provided.
Detailed Description
Hereinafter, 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 further added, and the mixture was stirred at 25℃for 4 hours to react.
14.6 parts by weight of 1, 3-bis (3-aminophenoxy) benzene was added to the obtained reaction mixture, and the mixture was stirred at 25℃for 4 hours to react. After 200 parts by weight of toluene was added to the resulting solution, reflux was performed at 150℃for 4 hours until water was no longer produced. After completion of the reaction, 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 the precipitate was separated by filtration and dried in vacuo to obtain an ester compound a.
By the way, by 1 H-NMR, GPC and FT-IR analysis confirmed that the ester compound A was represented by the above formula (1) (R 1 、R 2 Is a group (R) represented by the above formula (2) 4 All hydrogen atoms), R 3 Is a group (R) represented by the above formula (3-2) 6 All 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, by 1 H-NMR, GPC and FT-IR analysis confirmed that the ester compound B was represented by the above formula (1) (R 1 、R 2 Is phenyl, R 3 Is a group (R) represented by the above formula (3-2) 6 All 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 (manufactured by Mitsui Fine Chemicals corporation, "Ethacure 100").
By the way, by 1 H-NMR, GPC and FT-IR analysis confirmed that the ester compound C was represented by the above formula (1) (R 1 、R 2 Is a group (R) represented by the above formula (2) 4 All hydrogen atoms), R 3 Is a group represented by the above formula (4-1) or (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, by 1 H-NMR, GPC and FT-IR analysis confirmed that the ester compound D was represented by the above formula (1) (R 1 、R 2 Is a group (R) represented by the above formula (2) 4 All hydrogen atoms), R 3 Is a group (R) represented by the above formula (3-3) 7 All being hydrogen atoms, R 8 All 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, by 1 H-NMR, GPC and FT-IR analysis confirmed that the ester compound E was represented by the above formula (1) (R 1 、R 2 Is a group (R) represented by the above formula (2) 4 All hydrogen atoms), R 3 Is a group (R) represented by the above formula (3-4) 9 All 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 react.
To the obtained reaction mixture was added 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 (manufactured by Mitsui Fine Chemicals Co., ltd., "Ethacure 100"), and the mixture was stirred at 25℃for 2 hours to react. After 50 parts by weight of toluene was added to the resulting solution, reflux was performed at 170℃overnight until water was no longer produced. After the completion of the reaction, the mixture was added dropwise to 800 parts by weight of methanol, and the precipitate was separated by filtration and dried under vacuum to obtain an ester compound F.
By the way, by 1 H-NMR and GPC confirmed that the ester compound F was represented by the above formula (1) (R 1 、R 2 Is a group (R) represented by the above formula (2) 4 All hydrogen atoms), R 3 X is a 1, 3-phenylene group, and n is 0 to 10 inclusive, which are groups represented by the above formulas (4-1) and (4-2). The number average molecular weight of the ester compound F obtained 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, by 1 H-NMR and GPC confirmed that the ester compound G was represented by the above formula (1) (R 1 、R 2 Is a group (R) represented by the above formula (2) 4 All hydrogen atoms), R 3 X is a group represented by the above formula (4-1) or (4-2) and X is a group (R) represented by the above formula (5-1) 10 All hydrogen atoms), n is 0 or more and 10 or less). The number average molecular weight of the ester compound G obtained from the result of GPC 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, by 1 H-NMR and GPC confirmed that the ester compound H was represented by the above formula (1) (R 1 、R 2 Is a group (R) represented by the above formula (2) 4 All hydrogen atoms), R 3 X is 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) 11 All hydrogen atoms, n is 0 to 10 inclusive)). The number average molecular weight of the ester compound H obtained from the GPC result was 1687.
Synthesis example 9 (preparation of ester Compound I)
21.8 parts by weight of 3-aminophenol were dissolved in 100 parts by weight of N-methyl-2-pyrrolidone using a vessel equipped with a stirrer, reflux condenser, dean-Stark separator. To the resulting solution was added 52.0 parts by weight of 2, 2-bis (4- (2, 3-dicarboxyphenoxy) phenyl) propane, and the mixture was stirred at 25℃for 4 hours to react. After 100 parts by weight of toluene was added to the resulting solution, reflux was performed at 150℃for 4 hours until water was no longer produced. After the completion of the reaction, the solution from which toluene was removed from the obtained solution by using an evaporator was added dropwise to 800 parts by weight of pure water, and the precipitate was separated by filtration.
Further, 70.3 parts by weight of the obtained precipitate and 20.2 parts by weight of triethylamine were dissolved in 200 parts by weight of N-methyl-2-pyrrolidone. To the resulting solution was added 28.1 parts by weight of benzoyl chloride, and the mixture was stirred at 25℃for 4 hours to react. After the completion of the reaction, the obtained solution was added dropwise to 800 parts by weight of pure water, and the precipitate was separated by filtration and then dried in vacuo to obtain an ester compound I.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the ester compound I was not represented by the above-mentioned formula (1).
Examples 1 to 8 and comparative examples 1 and 2
Methyl ethyl ketone was added as a solvent to each of the materials in the compounding ratios shown in table 1, and the mixture was stirred at 1200rpm for 4 hours using a stirrer, to obtain a resin composition. The compositions of 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. Mu.m, using an applicator. XG284 (manufactured by Toray Co., ltd.) was used as the 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)
After each of the uncured laminated films obtained in examples and comparative examples was heated at 190 ℃ for 90 minutes, the base PET film was peeled off to obtain a cured product. The obtained cured product was measured for linear expansion coefficient in a temperature range of 25℃to 150℃under a condition of a heating rate of 10℃per minute and a force of 50N using a TMA apparatus. As a TMA device, TMA7100 (manufactured by Hitachi High-Techscience Co., ltd.) was used.
(dielectric loss tangent)
After each of the uncured laminated films obtained in examples and comparative examples was heated at 190 ℃ for 90 minutes, the base PET film was peeled off to obtain a cured product. The resulting cured product was cut into a size of 2mm wide and 100mm long. The cut cured product was subjected to a cavity-perturbing method using a dielectric constant measuring device and a network analyzer, and the dielectric loss tangent was measured at 23℃and a frequency of 5GHz by the cavity-perturbing method. CP521 (manufactured by kanto electronic applications development) was used as a dielectric constant measuring device by the cavity perturbation method, and N5224A PNA (manufactured by keyighttechenologies) was used as a network analyzer.
(elongation at maximum breaking point)
After each of the uncured laminated films obtained in examples and comparative examples was heated at 200 ℃ for 3 hours, the base PET film was peeled off to obtain a cured product. The resulting cured product was cut into a size of 10mm wide and 100mm long. For the cut cured product, the maximum breaking point elongation was measured using a tensile tester under conditions of 60mm distance between chucks, a tensile speed of 5 mm/min, and an initial tension of 0.35N. As a tensile tester, UCT-500 (manufactured by ORIENTEC Co.) was used.
TABLE 1
Industrial applicability
According to the present invention, an ester compound which can be used in a resin composition excellent in heat resistance and dielectric characteristics after curing can be provided. Further, according to the present invention, a resin composition containing the ester compound, a cured product of the resin composition, and a laminate film using the resin composition can be provided.
Claims (12)
1. An ester compound represented by the following formula (1),
in the formula (1), R 1 And R is 2 Each identical or different, is a group of the formula (2), R 3 For 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, n is an integer of 0 or more and 10 or less,
in the formula (2), R 4 Each independently is a hydrogen atom or an aliphatic group, and each is a bonding position.
2. The ester compound according to claim 1, wherein R in the formula (1) 3 Is a group represented by any one of the following formulas (3-1), (3-2), (3-3) or (3-4),
in the formula (3-1), R 5 Each independently is a hydrogen atom or an aliphatic group, in the formula (3-2), R 6 Each independently is a hydrogen atom or an aliphatic group, in the formula (3-3), R 7 Each independently is a hydrogen atom or an aliphatic group, R 8 Each independently is a hydrogen atom or an aliphatic group, in the formula (3-4), R 9 Each independently is a hydrogen atom or an aliphatic group, and in formulae (3-1), (3-2), (3-3) and (3-4), is a bonding position.
3. The ester compound according to claim 1 or 2, wherein the molecular weight is 1 ten thousand or less.
4. A resin composition comprising a curable resin and a curing agent,
the curing agent comprises the ester compound of claim 1,2 or 3.
5. The resin composition according to claim 4, wherein the curable resin comprises an epoxy resin.
6. A resin composition comprising a curable resin and a curing agent,
the curing agent comprises an ester compound represented by the following formula (1),
in the formula (1), R 1 And R is 2 Each identical or different, is optionally substituted aryl, R 3 For 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.
7. The resin composition according to claim 6, wherein R in the formula (1) 3 Is a group represented by any one of the following formulas (3-1), (3-2), (3-3) or (3-4),
in the formula (3-1), R 5 Each independently is a hydrogen atom or an aliphatic group, in the formula (3-2), R 6 Each independently is a hydrogen atom or an aliphatic group, in the formula (3-3), R 7 Each independently is a hydrogen atom or an aliphatic group, R 8 Each independently is a hydrogen atom or an aliphatic group, in the formula (3-4), R 9 Each independently is a hydrogen atom or an aliphatic group, and in formulae (3-1), (3-2), (3-3) and (3-4), is a bonding position.
8. The resin composition according to claim 6 or 7, wherein the molecular weight of the ester compound is 1 ten thousand or less.
9. The resin composition according to claim 6 or 7, wherein the curable resin comprises an epoxy resin.
10. The resin composition of claim 8, wherein the curable resin comprises an epoxy resin.
11. A cured product of the resin composition according to claim 4, 5, 6, 7 or 8.
12. A laminated film comprising the resin composition according to claim 4, 5, 6, 7 or 8.
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| 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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| JPS504063A (en) * | 1973-05-17 | 1975-01-16 | ||
| US3951977A (en) * | 1970-09-16 | 1976-04-20 | Standard Oil Company | 4-High molecular weight alkyl-substituted carbophenoxy phthalic acid-containing compounds |
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| JPS534063A (en) * | 1976-07-02 | 1978-01-14 | Idemitsu Petrochemical Co | Method for purification of polystyrene |
| JPS5952890A (en) * | 1982-09-20 | 1984-03-27 | Hitachi Ltd | Pulse gas laser device |
| JPS6253327A (en) * | 1985-08-31 | 1987-03-09 | Res Dev Corp Of Japan | Curable composition |
| US4841057A (en) * | 1987-01-13 | 1989-06-20 | Mitsubishi Chemical Industries Limited | Cyclic imido anthraquinone compounds |
| 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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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| TW202037588A (en) | 2020-10-16 |
| KR20210113159A (en) | 2021-09-15 |
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| JP7467330B2 (en) | 2024-04-15 |
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