WO2023032723A1

WO2023032723A1 - Curable resin composition and interlayer insulating material

Info

Publication number: WO2023032723A1
Application number: PCT/JP2022/031479
Authority: WO
Inventors: 良平増井; 幸平竹田; 達史林; 悠太大當; 圭釜我; さやか脇岡
Original assignee: 積水化学工業株式会社
Priority date: 2021-09-02
Filing date: 2022-08-22
Publication date: 2023-03-09
Also published as: TW202323380A

Abstract

The present invention provides a curable resin composition excellent in terms of dielectric characteristics after curing and adhesiveness. Also provided is an interlayer insulating material obtained from the curable resin composition. This curable resin composition comprises a curable resin, a hardener, an inorganic filler, and a dispersant and has a complex viscosity, as measured at 90°C, 5% strain, and 1 rad/sec, of 8,000 Pa·s or less.

Description

Curable resin composition and interlayer insulating material

TECHNICAL FIELD The present invention relates to a curable resin composition having excellent dielectric properties and adhesiveness after curing. The present invention also relates to an interlayer insulating material using the curable resin composition.

Curable resins such as epoxy resins, which have low shrinkage and excellent adhesiveness, insulation, and chemical resistance, are used in many industrial products. In particular, dielectric properties such as a low dielectric constant and a low dielectric loss tangent are required for a curable resin composition used as an interlayer insulating material for printed wiring boards. As a curable resin composition having such excellent dielectric properties, for example, Patent Documents 1 and 2 disclose a curable resin composition containing a curable resin and a compound having a specific structure as a curing agent. ing.

JP 2017-186551 A WO2016/114286

Regarding the curable resin composition, in order to lower the dielectric loss tangent after curing, it is conceivable to add a large amount of an inorganic filler such as silica. There was a case where peeling occurred in the adherend consisting of.
An object of the present invention is to provide a curable resin composition that exhibits excellent dielectric properties and adhesion after curing. Another object of the present invention is to provide an interlayer insulating material using the curable resin composition.

The present disclosure 1 contains a curable resin, a curing agent, an inorganic filler, and a dispersant, and has a complex viscosity of 8000 Pa s or less at 90 ° C., 5% strain, and 1 rad / sec. It is a thing.
The present disclosure 2 is the curable resin composition of the present disclosure 1, wherein the inorganic filler is silica.
Present Disclosure 3 is the curable resin composition of Present Disclosure 1 or 2, wherein the content of the inorganic filler in 100 parts by weight of the total solid content of the curable resin composition is 65 parts by weight or more.
The present disclosure 4 is the curable resin composition of the present disclosure 1, 2 or 3, wherein the dispersant is a polyurethane-based dispersant.
Disclosure 5 is the curable resin composition of Disclosure 1, 2, 3 or 4, further comprising a polymer component.
The present disclosure 6 is an interlayer insulating material using the curable resin composition of the present disclosure 1, 2, 3, 4 or 5.
The present invention will be described in detail below.

The present inventors have found that the cause of peeling on the adherend when a large amount of inorganic filler is blended is that the dispersion state of the inorganic filler in the curable resin composition becomes uneven. It was thought that this was due to the fact that slight unevenness occurred on the surface of the Therefore, the present inventors have studied adjusting the melt viscosity of the curable resin composition, but the peeling of the adherend could not be sufficiently suppressed even if the melt viscosity is lowered. Therefore, the present inventors have investigated to make the complex viscosity of the curable resin composition at 90° C., 5% strain, 1 rad/sec to be a specific value or less. As a result, the inorganic filler in the resulting curable resin composition can be uniformly dispersed, and a cured product having excellent dielectric properties and adhesiveness can be obtained. This led to the completion of the present invention. rice field.

The curable resin composition of the present invention has an upper limit of complex viscosity of 8000 Pa·s at 90° C., strain of 5%, and 1 rad/sec. When the complex viscosity at 90° C., 5% strain, and 1 rad/sec is 8000 Pa s or less, the curable resin composition of the present invention has a uniform dispersion state of the inorganic filler and adhesion after curing. It will be excellent in quality. A preferable upper limit of the complex viscosity at 90° C., 5% strain, and 1 rad/sec is 7500 Pa·s, and a more preferable upper limit is 7000 Pa·s.
Although there is no particular lower limit for the complex viscosity at 90° C., 5% strain, and 1 rad/sec, the practical lower limit is 500 Pa·s.
The complex viscosity at 90° C., 5% strain, and 1 rad/sec can be measured using a rotary rheometer at a frequency of 0.01 Hz to 1 Hz and 90° C. for the curable resin composition film. can. The curable resin composition film can be obtained by applying the curable resin composition onto a base film and drying the coating. Examples of the rotational rheometer include HAAKE MARS series (manufactured by Thermo Fisher Scientific), VAR-100 (manufactured by Rheologicala), and ARES (manufactured by TA Instruments).

The curable resin composition of the present invention contains a curable resin.
Examples of the curable resins include epoxy resins, cyanate resins, phenol resins, imide resins, maleimide resins, silicone resins, acrylic resins, and fluorine resins. In particular, the curable resin preferably contains at least one selected from the group consisting of epoxy resins, cyanate resins, phenol resins, imide resins, and maleimide resins, and more preferably contains epoxy resins. The curable resins may be used alone, or two or more of them may be used in combination.

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, 2,2'-diallylbisphenol A type epoxy resin, and hydrogenated bisphenol type epoxy resin. , propylene oxide-added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide 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 novolak type epoxy resin, ortho-cresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol novolak type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, Examples include rubber-modified epoxy resins and glycidyl ester compounds.

The curable resin composition of the present invention further contains a curing agent.
Examples of the curing agent include an imide skeleton in the main chain and an imide oligomer having a crosslinkable functional group at the end, an acid anhydride-based curing agent, a phenol-based curing agent, a thiol-based curing agent, an amine-based curing agent, and a cyanate-based curing agent. curing agents, active ester curing agents, and the like. Above all, the curing agent preferably contains the imide oligomer from the viewpoint of the adhesiveness and long-term heat resistance of the cured product of the curable resin composition to be obtained.

The imide oligomer is represented by the following formula (1-1) or the following formula (1-2), or the following formula (2-1) or the following formula (2-2) as a structure containing the crosslinkable functional group. It is preferred to have a structure that By having a structure represented by the following formula (1-1) or the following formula (1-2), or the following formula (2-1) or the following formula (2-2), the imide oligomer is an epoxy resin It becomes excellent in reactivity and compatibility with curable resins such as.

In formulas (1-1) and (1-2), A is an acid dianhydride residue, B is an aliphatic diamine residue or an aromatic diamine residue, and formula (1-2) Ar is an optionally substituted divalent aromatic group.

In formulas (2-1) and (2-2), A is an acid dianhydride residue, B is an aliphatic triamine residue or an aromatic triamine residue, and formula (2-2) Ar is an optionally substituted divalent aromatic group.

The acid dianhydride residue is preferably a tetravalent group represented by the following formula (3-1) or the following formula (3-2).

In formulas (3-1) and (3-2), * is a bonding position, and in formula (3-1), Z is a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a direct It is a chain or branched divalent hydrocarbon group or a divalent group having an aromatic ring. When Z is a hydrocarbon group, it may have an oxygen atom between the hydrocarbon group and each aromatic ring in formula (3-1), Z is a divalent group having an aromatic ring In some cases, an oxygen atom may be present between the divalent group having the aromatic ring and each aromatic ring in formula (3-1). The hydrogen atoms of the aromatic rings in formulas (3-1) and (3-2) may be substituted.

When Z in the above formula (3-1) is a linear or branched divalent hydrocarbon group or a divalent group having an aromatic ring, these groups are substituted good too.
Examples of substituents in the case where the linear or branched divalent hydrocarbon group or the divalent group having an aromatic ring is substituted include, for example, a halogen atom, a linear or branched chain linear alkyl groups, linear or branched alkenyl groups, alicyclic groups, aryl groups, alkoxy groups, nitro groups, cyano groups and the like.

Examples of acid dianhydrides from which the acid dianhydride residue is derived include acid dianhydrides represented by formula (9) described later.

B in the formula (1-1), the formula (1-2), the formula (2-1), or the formula (2-2) is the aliphatic diamine residue and/or the aliphatic triamine A preferable lower limit of the number of carbon atoms of the aliphatic diamine residue and the aliphatic triamine residue when they are residues is 4. Since the number of carbon atoms in the aliphatic diamine residue and the aliphatic triamine residue is 4 or more, the resulting curable resin composition has flexibility and workability before curing, and dielectric properties after curing. It will be better. A more preferable lower limit for the number of carbon atoms in the aliphatic diamine residue and the aliphatic triamine residue is 5, and a more preferable lower limit is 6.
Although there is no particular upper limit for the number of carbon atoms in the aliphatic diamine residue and the aliphatic triamine residue, the practical upper limit is 60.

Examples of the aliphatic diamine from which the aliphatic diamine residue is derived include aliphatic diamines derived from dimer acid, linear or branched aliphatic diamines, aliphatic ether diamines, and aliphatic lipids. Cyclic diamines and the like can be mentioned.
Examples of the aliphatic diamines derived from the above dimer acids include dimer diamines and hydrogenated dimer diamines.
Examples of the linear or branched aliphatic diamines include 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 1,20-eicosanediamine, 2-methyl-1,8 -octanediamine, 2-methyl-1,9-nonanediamine, 2,7-dimethyl-1,8-octanediamine and the like.
Examples of the aliphatic ether diamines include 2,2'-oxybis(ethylamine), 3,3'-oxybis(propylamine), 1,2-bis(2-aminoethoxy)ethane and the like.
Examples of the aliphatic alicyclic diamines include 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine.
Among them, the aliphatic diamine residue is preferably an aliphatic diamine residue derived from the dimer acid.

Examples of the aliphatic triamines from which the above-mentioned aliphatic triamine residues are derived include aliphatic triamines derived from trimer acid, linear or branched aliphatic triamines, aliphatic ether triamines, and aliphatic lipids. Cyclic triamines and the like can be mentioned.
Examples of aliphatic triamines derived from trimer acids include trimer triamines and hydrogenated trimer triamines.
Examples of the linear or branched aliphatic triamines include 3,3′-diamino-N-methyldipropylamine, 3,3′-diaminodipropylamine, diethylenetriamine, bis(hexamethylene)triamine, 2 , 2′-bis(methylamino)-N-methyldiethylamine and the like.
Among them, the aliphatic triamine residue is preferably an aliphatic triamine residue derived from the trimer acid.

A mixture of the dimer diamine and the trimer triamine can also be used as the aliphatic diamine and/or the aliphatic triamine.

Commercially available aliphatic diamines and/or aliphatic triamines derived from the dimer acid and/or the trimer acid include, for example, aliphatic diamines and/or triamines manufactured by BASF, and fatty acids manufactured by Croda. triamines and/or aliphatic triamines.
Examples of the aliphatic diamines and/or aliphatic triamines manufactured by BASF include Versamin 551 and Versamin 552.
Examples of the aliphatic diamines and/or aliphatic triamines manufactured by Croda include Priamine 1071, Priamine 1073, Priamine 1074, and Priamine 1075.

The aromatic when B in the above formula (1-1), the above formula (1-2), the above formula (2-1), or the above formula (2-2) is the above aromatic diamine residue The diamine residue is preferably a divalent group represented by formula (4-1) or formula (4-2) below.

In formulas (4-1) and (4-2), * is a bonding position, and in formula (4-1), Y is a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a straight It is a chain or branched divalent hydrocarbon group or a divalent group having an aromatic ring. When Y is a hydrocarbon group, it may have an oxygen atom between the hydrocarbon group and each aromatic ring in formula (4-1), Y is a divalent group having an aromatic ring In some cases, an oxygen atom may be present between the divalent group having the aromatic ring and each aromatic ring in formula (4-1). The hydrogen atoms of the aromatic rings in formulas (4-1) and (4-2) may be substituted.

When Y in the above formula (4-1) is a linear or branched divalent hydrocarbon group or a divalent group having an aromatic ring, these groups are substituted good too.
Examples of substituents in the case where the linear or branched divalent hydrocarbon group or the divalent group having an aromatic ring is substituted include, for example, a halogen atom, a linear or branched chain linear alkyl groups, linear or branched alkenyl groups, alicyclic groups, aryl groups, alkoxy groups, nitro groups, cyano groups and the like.

Examples of the aromatic diamine from which the aromatic diamine residue is derived include those in which the diamine represented by formula (10) described below is an aromatic diamine.

In addition, when the imide oligomer has a siloxane skeleton in its structure, it may lower the glass transition temperature after curing, contaminate the adherend, and cause poor adhesion. , preferably an imide oligomer having no siloxane skeleton in its structure.

The imide oligomer preferably has a number average molecular weight of 5,000 or less. When the imide oligomer has a number average molecular weight of 5,000 or less, the resulting cured product of the curable resin composition is excellent in long-term heat resistance. A more preferable upper limit of the number average molecular weight of the imide oligomer is 4,000, and a more preferable upper limit is 3,000.
In particular, the number average molecular weight of the imide oligomer is preferably 900 or more and 5000 or less when it has a structure represented by the above formula (1-1) or (2-1), and the above formula (1- 2) When it has a structure represented by the above formula (2-2), it is preferably 550 or more and 4000 or less. A more preferable lower limit of the number average molecular weight is 950, and a more preferable lower limit is 1,000 in the case of having a structure represented by the above formula (1-1) or the above formula (2-1). A more preferable lower limit of the number average molecular weight is 580, and a more preferable lower limit is 600, in the case of having a structure represented by the formula (1-2) or (2-2).
In addition, the above-mentioned "number average molecular weight" in this specification is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and calculated by polystyrene conversion. Examples of the column used for measuring the polystyrene-equivalent number-average molecular weight by GPC include JAIGEL-2H-A (manufactured by Japan Analytical Industry Co., Ltd.).

Specifically, the imide oligomer is represented by the following formula (5-1), the following formula (5-2), the following formula (5-3), the following formula (5-4), or the following formula (5-5 ), or the following formula (6-1), the following formula (6-2), the following formula (6-3), the following formula (6-4), or the following formula (6-5 ) is preferably an imide oligomer represented by

In formulas (5-1) to (5-5), A is the acid dianhydride residue, and in formulas (5-1) to (5-5), A is the same. may be different. In formulas (5-1) to (5-5), B is the aliphatic diamine residue or the aromatic diamine residue, or the aliphatic triamine residue or the aromatic triamine residue, In (5-3) and formula (5-4), B may be the same or different. In formula (5-2), X is a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group, and in formula (5-4), W is a hydrogen atom, a halogen atom , or an optionally substituted monovalent hydrocarbon group. In formulas (5-3) and (5-4), n is the number of repetitions.

In formulas (6-1) to (6-5), A is the acid dianhydride residue, and in formulas (6-1) to (6-5), A is the same. may be different. In formulas (6-1) to (6-5), R is a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group, formula (6-1), formula (6 -3) and in formula (6-5), R may be the same or different. In formulas (6-2) and (6-4), W is a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group. In formulas (6-1) to (6-5), B is the aliphatic diamine residue or the aromatic diamine residue, or the aliphatic triamine residue or the aromatic triamine residue, In (6-3) and formula (6-4), B may be the same or different.

A in the above formulas (5-1) to (5-5) and the above formulas (6-1) to (6-5) is the following formula (7-1) or the following formula (7-2) It is preferably a tetravalent group represented.

In formulas (7-1) and (7-2), * is a bonding position, and in formula (7-1), Z is a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a direct It is a chain or branched divalent hydrocarbon group or a divalent group having an aromatic ring. When Z is a hydrocarbon group, it may have an oxygen atom between the hydrocarbon group and each aromatic ring in formula (7-1), Z is a divalent group having an aromatic ring In some cases, an oxygen atom may be present between the divalent group having an aromatic ring and each aromatic ring in formula (7-1). The hydrogen atoms of the aromatic rings in formulas (7-1) and (7-2) may be substituted.

B in the above formulas (5-1) to (5-5) and the above formulas (6-1) to (6-5) is the following formula (8-1) or the following formula (8-2) It is preferably a divalent group represented.

In formulas (8-1) and (8-2), * is a bonding position, and in formula (8-1), Y is a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a straight It is a chain or branched divalent hydrocarbon group or a divalent group having an aromatic ring. When Y is a hydrocarbon group, it may have an oxygen atom between the hydrocarbon group and each aromatic ring in formula (8-1), Y is a divalent group having an aromatic ring In some cases, an oxygen atom may be present between the divalent group having an aromatic ring and each aromatic ring in formula (8-1). The hydrogen atoms of the aromatic rings in formulas (8-1) and (8-2) may be substituted.

As a method for producing an imide oligomer having a structure represented by the above formula (1-1), for example, an acid dianhydride represented by the following formula (9) and a diamine represented by the following formula (10) and the like. Also, by using an aliphatic triamine or an aromatic triamine instead of the diamine represented by the following formula (10), an imide oligomer having a structure represented by the above formula (2-1) can be produced.

In formula (9), A is the same tetravalent group as A in formula (1-1) above.

In formula (10), B is the same divalent group as B in formula (1-1) above, and R ¹ to R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group. .

A specific example of the method for reacting the acid dianhydride represented by the above formula (9) with the diamine represented by the above formula (10) is shown below.
First, the diamine represented by the above formula (10) is dissolved in advance in a solvent (for example, N-methylpyrrolidone, etc.) in which the amic acid oligomer obtained by the reaction is soluble, and the resulting solution is added with the above formula (9). An acid dianhydride represented by is added and reacted to obtain an amic acid oligomer solution. Next, the solvent is removed by heating, pressure reduction, or the like, and the mixture is heated at about 200° C. or higher for 1 hour or longer to react the amic acid oligomer. By adjusting the molar ratio of the acid dianhydride represented by the above formula (9) and the diamine represented by the above formula (10), and the imidization conditions, it has a desired number average molecular weight, and both An imide oligomer having a structure represented by the above formula (1-1) at the end can be obtained.
Further, by replacing a part of the acid dianhydride represented by the above formula (9) with the acid anhydride represented by the following formula (11), it has a desired number average molecular weight and one end has the above An imide oligomer having a structure represented by the formula (1-1) and having a structure derived from an acid anhydride represented by the following formula (11) at the other end can be obtained. In this case, the acid dianhydride represented by the above formula (9) and the acid anhydride represented by the following formula (11) may be added simultaneously or separately.
Furthermore, by replacing part of the diamine represented by the above formula (10) with a monoamine represented by the following formula (12), it has a desired number average molecular weight, and one end has the above formula (1-1) ) and having at the other end a structure derived from a monoamine represented by the following formula (12). In this case, the diamine represented by the above formula (10) and the monoamine represented by the following formula (12) may be added simultaneously or separately.

In formula (11), Ar is an optionally substituted divalent aromatic group.

In formula (12), Ar is an optionally substituted monovalent aromatic group, and R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent hydrocarbon group.

As a method for producing an imide oligomer having a structure represented by the above formula (1-2), for example, an acid dianhydride represented by the above formula (9) and a diamine represented by the above formula (10) Examples thereof include a method of reacting with a phenolic hydroxyl group-containing monoamine represented by the following formula (13). Further, by using an aliphatic triamine or an aromatic triamine instead of the diamine represented by the above formula (10), an imide oligomer having a structure represented by the above formula (2-2) can be produced.

In formula (13), Ar is an optionally substituted divalent aromatic group, and R ⁷ and R ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group.

Specific examples of the method for reacting the acid dianhydride represented by the above formula (9), the diamine represented by the above formula (10), and the phenolic hydroxyl group-containing monoamine represented by the above formula (13) are shown below. show.
First, a phenolic hydroxyl group-containing monoamine represented by the above formula (13) and a diamine represented by the above formula (10) are mixed in advance with a solvent in which the amic acid oligomer obtained by the reaction is soluble (for example, N-methylpyrrolidone, etc.) ), and the acid dianhydride represented by the above formula (9) is added to the obtained solution and reacted to obtain an amic acid oligomer solution. Next, the solvent is removed by heating, pressure reduction, or the like, and the mixture is heated at about 200° C. or higher for 1 hour or longer to react the amic acid oligomer. The molar ratio of the acid dianhydride represented by the above formula (9), the diamine represented by the above formula (10) and the phenolic hydroxyl group-containing monoamine represented by the above formula (13), and the imidization conditions By adjusting, it is possible to obtain an imide oligomer having a desired number average molecular weight and a structure represented by the above formula (1-2) at both ends.
Further, by replacing part of the phenolic hydroxyl group-containing monoamine represented by the above formula (13) with the monoamine represented by the above formula (12), it has a desired number average molecular weight, and one end has the above formula An imide oligomer having a structure represented by (1-2) and having a structure derived from a monoamine represented by the above formula (12) at the other end can be obtained. In this case, the phenolic hydroxyl group-containing monoamine represented by the above formula (13) and the monoamine represented by the above formula (12) may be added simultaneously or separately.

Examples of the acid dianhydride represented by the above formula (9) include pyromellitic anhydride, 3,3'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride. acid anhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-bis(2,3-dicarboxylphenoxy)diphenyl ether dianhydride, p-phenylene Bis(trimellitate anhydride), 2,3,3',4'-biphenyltetracarboxylic acid dianhydride and the like can be mentioned.
Among them, aromatic acid dianhydrides having a melting point of 240° C. or less are preferable as the acid dianhydrides used as raw materials for the imide oligomers, since they are excellent in solubility and heat resistance, and have a melting point of 220° C. The following aromatic acid dianhydrides are more preferred, and aromatic acid dianhydrides having a melting point of 200°C or less are more preferred, and 3,4'-oxydiphthalic dianhydride (melting point 180°C), 4,4'-(4,4'-Isopropylidenediphenoxy)diphthalic anhydride (melting point 190°C) is particularly preferred.
In this specification, the "melting point" means a value measured as an endothermic peak temperature when the temperature is raised at 10°C/min using a differential scanning calorimeter. Examples of the differential scanning calorimeter include EXTEAR DSC6100 (manufactured by SII Nano Technology Co., Ltd.).

Among the diamines represented by the above formula (10), aromatic diamines include, for example, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′- Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl 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, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, 1,4-bis( 2-(4-aminophenyl)-2-propyl)benzene, 3,3′-diamino-4,4′-dihydroxyphenylmethane, 4,4′-diamino-3,3′-dihydroxyphenylmethane, 3,3 '-diamino-4,4'-dihydroxyphenyl ether, bisaminophenylfluorene, bistoluidinefluorene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxyphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl and the like. Among them, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, 1,4 -bis(2-(4-aminophenyl)-2-propyl)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis( 4-Aminophenoxy)benzene is preferred, and 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, 1,4-bis(2-(2-( 4-aminophenyl)-2-propyl)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene is more preferred.

Examples of acid anhydrides represented by the above formula (11) include phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 1,2-naphthalic anhydride, and 2,3-naphthalic anhydride. acid anhydride, 1,8-naphthalic anhydride, 2,3-anthracenedicarboxylic anhydride, 4-tert-butyl phthalic anhydride, 4-ethynyl phthalic anhydride, 4-phenylethynyl phthalic anhydride, 4-fluorophthalic anhydride, 4-chlorophthalic anhydride, 4-bromophthalic anhydride, 3,4-dichlorophthalic anhydride and the like.

Monoamines represented by the above formula (12) include, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 2,4-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, 1-aminopyrene, 3- Chloroaniline, o-anisidine, m-anisidine, p-anisidine, 1-amino-2-methylnaphthalene, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 3,4-dimethyl aniline, 4-ethylaniline, 4-ethynylaniline, 4-isopropylaniline, 4-(methylthio)aniline, N,N-dimethyl-1,4-phenylenediamine and the like.

Examples of the phenolic hydroxyl group-containing monoamine represented by the above formula (13) include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4-amino-2 ,3-xylenol, 4-amino-2,5-xylenol, 4-amino-2,6-xylenol, 4-amino-1-naphthol, 5-amino-2-naphthol, 6-amino-1-naphthol, 4 -amino-2,6-diphenylphenol and the like. Among them, 4-amino-o-cresol and 5-amino-o-cresol are preferred because they are excellent in availability and storage stability and provide a high glass transition temperature after curing.

When the imide oligomer is produced by the production method described above, the imide oligomer is a plurality of imide oligomers having a structure represented by the above formula (1-1) or a structure represented by the above formula (1-2). and a mixture of each raw material (imide oligomer composition). When an aliphatic triamine or an aromatic triamine is used in place of the diamine represented by the formula (10), the imide oligomer is a plurality of imide oligomers having a structure represented by the formula (2-1). Alternatively, it can be obtained as one contained in a mixture (imide oligomer composition) of a plurality of kinds of imide oligomers having a structure represented by the above formula (2-2) and each raw material. When the imide oligomer composition has an imidization rate of 70% or more, it can provide a cured product having excellent mechanical strength at high temperatures and long-term heat resistance when used as a curing agent.
A preferred lower limit for the imidization rate of the imide oligomer composition is 75%, and a more preferred lower limit is 80%. Although there is no particular upper limit for the imidization rate of the imide oligomer composition, the practical upper limit is 98%.
The above-mentioned "imidation rate" is measured by a total reflection measurement method (ATR method) using a Fourier transform infrared spectrophotometer (FT-IR), and is derived from the carbonyl group of amic acid at 1660 cm ^-1 It can be derived from the peak absorbance area in the vicinity by the following formula. Examples of the Fourier transform infrared spectrophotometer include UMA600 (manufactured by Agilent Technologies). The "peak absorbance area of the amic acid oligomer" in the following formula is obtained by removing the solvent by evaporation or the like without performing the imidization step after reacting the acid dianhydride with a diamine or a phenolic hydroxyl group-containing monoamine. is the absorbance area of the amic acid oligomer obtained by
Imidation rate (%) = 100 × (1-(peak absorbance area after imidization)/(peak absorbance area of amic acid oligomer))

From the viewpoint of solubility in the curable resin composition, it is preferable that 3 g or more of the imide oligomer composition dissolve in 10 g of tetrahydrofuran at 25°C.

The preferable lower limit of the content of the curing agent in the total 100 parts by weight of the curable resin and the curing agent (further curing accelerator when containing the curing accelerator described later) is 20 parts by weight, and the preferable upper limit is 80 parts. weight part. When the content of the curing agent is within this range, the resulting curable resin composition is more excellent in curability and storage stability. A more preferable lower limit to the content of the curing agent is 25 parts by weight, and a more preferable upper limit is 75 parts by weight.

The curable resin composition of the present invention contains an inorganic filler.
By containing the inorganic filler, the curable resin composition of the present invention provides a cured product with excellent dielectric properties.

Examples of the inorganic filler include silica, alumina, boron nitride, magnesium oxide, and boehmite. Among them, silica is preferable.

A preferable lower limit of the average particle size of the inorganic filler is 0.2 μm, and a preferable upper limit thereof is 5 μm. When the average particle size of the inorganic filler is within this range, it becomes more excellent in dispersibility in the curable resin composition without deteriorating the coatability, etc., and the dielectric properties and adhesiveness of the cured product are improved. It becomes excellent by the effect of compatibility. A more preferable lower limit of the average particle size of the inorganic filler is 0.5 μm, and a more preferable upper limit thereof is 2 μm.
The average particle size of the inorganic filler can be measured by dispersing the inorganic filler in a solvent (water, organic solvent, etc.) using a particle size distribution analyzer. Examples of the particle size distribution analyzer include NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

A preferable lower limit of the content of the inorganic filler in 100 parts by weight of the solid content of the curable resin composition is 65 parts by weight. When the content of the inorganic filler is 65 parts by weight or more, the resulting curable resin composition is more excellent in dielectric properties after curing. A more preferable lower limit for the content of the inorganic filler is 70 parts by weight.
Further, from the viewpoint of coatability and adhesiveness, the upper limit of the content of the inorganic filler in 100 parts by weight of the total solid content of the curable resin composition is preferably 73 parts by weight, and a more preferred upper limit is 71 parts by weight. be.
In addition, in the present specification, the above-mentioned "entire solid content of the curable resin composition" means the entire components other than the solvent when the curable resin composition contains a solvent described later.

The curable resin composition of the present invention contains a dispersant.
By containing the dispersant, the curable resin composition of the present invention can uniformly disperse the inorganic filler, and the cured product has excellent adhesiveness.

Examples of the dispersant include polyurethane-based dispersants, fatty acid-based dispersants, polyamino-based dispersants, and polyacrylate-based dispersants. Among these, polyurethane-based dispersants are preferred because they make it particularly easy to set the complex viscosity at 90° C., 5% strain, and 1 rad/sec within the above range.

A preferable lower limit of the content of the dispersing agent in 100 parts by weight of the total solid content of the curable resin composition is 0.05 parts by weight, and a preferable upper limit thereof is 1.0 parts by weight. When the content of the dispersant is within this range, the resulting curable resin composition is more excellent in the effect of achieving both dielectric properties and adhesiveness after curing. A more preferred lower limit to the content of the dispersant is 0.1 parts by weight, and a more preferred upper limit is 0.7 parts by weight.

The curable 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, phosphorus-based curing accelerators, photobase generators, sulfonium salt-based curing accelerators, and the like. . Of these, imidazole-based curing accelerators are preferred because of their excellent storage stability. The curing accelerators may be used alone, or two or more of them may be used in combination.

The content of the curing accelerator has a preferable lower limit of 0.01 parts by weight and a preferable upper limit of 10 parts by weight based on a total of 100 parts by weight of the curable resin, the curing agent and the curing accelerator. When the content of the curing accelerator is within this range, the effect of shortening the curing time while maintaining excellent adhesiveness and the like is enhanced. A more preferred lower limit to the content of the curing accelerator is 0.05 parts by weight, and a more preferred upper limit is 5 parts by weight.

The curable 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 preferred.

The preferred upper limit of the content of the organic filler is 300 parts by weight with respect to a total of 100 parts by weight of the curable resin and the curing agent (and the curing accelerator when the curing accelerator is contained). be. When the content of the organic filler is within this range, the obtained cured product is superior in toughness and the like 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 curable resin composition of the present invention may contain a polymer component as long as the object of the present invention is not impaired. The polymer component serves as a film-forming component.

A preferable lower limit of the number average molecular weight of the polymer component is 3,000, and a preferable upper limit thereof is 100,000. When the number average molecular weight of the polymer component is within this range, the resulting curable resin composition will be superior in flexibility and workability before curing and in heat resistance after curing. A more preferable lower limit of the number average molecular weight of the polymer component is 5,000, and a more preferable upper limit thereof is 80,000.

Examples of the polymer component include polyimide, phenoxy resin, polyamide, polyamideimide, polymaleimide, cyanate resin, benzoxazine resin, acrylic resin, urethane resin, and polyester. Among these, from the viewpoint of heat resistance, polyimide, polyamide, polyamideimide, and polymaleimide are preferable, and polyimide is more preferable.

The preferable lower limit of the content of the polymer component is 0.5 parts by weight with respect to a total of 100 parts by weight of the curable resin and the curing agent (and the curing accelerator when the curing accelerator is contained). , the preferred upper limit is 20 parts by weight. When the content of the polymer component is within this range, the resulting cured product of the curable resin composition is more excellent in heat resistance. A more preferable lower limit of the content of the polymer component is 1 part by weight, and a more preferable upper limit is 10 parts by weight.

The curable resin composition of the present invention may contain a flame retardant as long as the object of the present invention is not impaired.
Examples of the flame retardant include boehmite-type aluminum hydroxide, aluminum hydroxide, metal hydrates such as magnesium hydroxide, halogen-based compounds, phosphorus-based compounds, and nitrogen compounds. Among them, boehmite-type aluminum hydroxide is preferable.

The content of the flame retardant is preferably 200 parts by weight with respect to a total of 100 parts by weight of the curable resin and the curing agent (and the curing accelerator when the curing accelerator is contained). . When the content of the flame retardant is within this range, the resulting curable resin composition has excellent flame retardancy while maintaining excellent adhesion and the like. A more preferable upper limit of the content of the flame retardant is 150 parts by weight.

The curable resin composition may contain a solvent from the viewpoint of coatability and the like.
As the solvent, a solvent having a boiling point of less than 200° C. is preferable from the viewpoint of coatability, storage stability, and the like.
Examples of the solvent having a boiling point of less than 200° C. include alcohol-based solvents, ketone-based solvents, ester-based solvents, hydrocarbon-based solvents, halogen-based solvents, ether-based solvents, and nitrogen-containing solvents.
Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol, tertiary butyl alcohol, and 2-ethylhexanol.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and diacetone alcohol.
Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, methoxybutyl acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, butyl lactate and the like.
Examples of the hydrocarbon solvent include benzene, toluene, xylene, normal hexane, isohexane, cyclohexane, methylcyclohexane, ethylcyclohexane, isooctane, normal decane, normal heptane, and the like.
Examples of the halogen-based solvent include dichloromethane, chloroform, and trichlorethylene.
Examples of the ether solvent include diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate. , propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol monotertiary butyl ether, propylene glycol monomethyl ether propionate, 3-methoxybutanol, diethylene glycol dimethyl ether, anisole, 4-methylanisole and the like. be done.
Examples of the nitrogen-containing solvent include acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide and the like.
Among them, from the viewpoint of handleability and solubility of imide oligomers, ketone solvents with a boiling point of 60 ° C. or higher and lower than 200 ° C., ester solvents with a boiling point of 60 ° C. or higher and lower than 200 ° C., and boiling points of 60 ° C. or higher and 200 ° C. At least one selected from the group consisting of ether-based solvents having a temperature of less than °C is preferred. Examples of such solvents include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, cyclohexanone, methylcyclohexanone, diethylene glycol dimethyl ether, and anisole.
The "boiling point" means a value measured under conditions of 101 kPa, or a value converted to 101 kPa using a boiling point conversion chart or the like.

A preferable lower limit of the content of the solvent in 100 parts by weight of the curable resin composition containing the solvent is 20 parts by weight, and a preferable upper limit thereof is 90 parts by weight. When the content of the solvent is within this range, the resulting curable resin composition is more excellent in coatability and the like. A more preferable lower limit for the content of the solvent is 30 parts by weight, and a more preferable upper limit is 80 parts by weight.

The curable resin composition of the present invention may contain a reactive diluent as long as the object of the present invention is not impaired.
From the viewpoint of adhesion reliability, the reactive diluent is preferably a reactive diluent having two or more reactive functional groups in one molecule.

The curable resin composition of the present invention may further contain additives such as coupling agents, storage stabilizers, anti-bleeding agents, fluxing agents and leveling agents.

The method for producing the curable resin composition of the present invention includes, for example, a method of mixing a curable resin, a curing agent, an inorganic filler, a dispersant, a polymer component, etc. using a mixer. is mentioned. Examples of the mixer include a homodisper, a universal mixer, a Banbury mixer, a kneader, and the like.

A curable resin composition film comprising the curable resin composition of the present invention can be obtained by applying the curable resin composition of the present invention onto a substrate film and drying the curable resin composition. A cured product can be obtained by curing the product film.

In the curable resin composition of the present invention, the preferable upper limit of dielectric loss tangent at 23° C. of the cured product is 0.0045. Since the cured product has a dielectric loss tangent within this range at 23° C., the curable resin composition of the present invention can be suitably used as an interlayer insulating material for multilayer printed wiring boards and the like. A more preferable upper limit of the dielectric loss tangent at 23° C. of the cured product is 0.0040, and a more preferable upper limit is 0.0035.
The above-mentioned "dielectric loss tangent" is a value measured under conditions of 1.0 GHz 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 curable resin composition film having a thickness of 40 to 200 μm at 190° C. for 90 minutes.

The curable resin composition of the present invention can be used in a wide variety of applications. For example, adhesives for printed wiring boards, adhesives for coverlays of flexible printed circuit boards, copper-clad laminates, adhesives for bonding semiconductors, interlayer insulating materials, prepregs, sealants for LEDs, adhesives for structural materials, etc. can be used.
In particular, the curable resin composition of the present invention can be suitably used as an interlayer insulating material such as a multilayer printed wiring board because the cured product thereof has a low dielectric constant and a low dielectric loss tangent and is excellent in dielectric properties. An interlayer insulating material using the curable resin composition of the present invention is also one aspect of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which is excellent in the dielectric property and adhesiveness after hardening can be provided. Further, according to the present invention, it is possible to provide an interlayer insulating material using the curable resin composition.

EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples.

(Synthesis Example 1 (Preparation of imide oligomer composition))
104 parts by weight of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 parts by weight of N-methylpyrrolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "NMP") dissolved in parts. To the obtained solution, a solution obtained by diluting 28 parts by weight of Priamine 1074 (manufactured by Croda), which is a dimer diamine, diluted with 100 parts by weight of N-methylpyrrolidone, is added, and the mixture is stirred at 25° C. for 2 hours to react to form an amic acid oligomer solution. got After removing N-methylpyrrolidone from the obtained amic acid oligomer solution under reduced pressure, the solution was heated at 300° C. for 2 hours to obtain an imide oligomer composition (imidization rate: 93%).
The obtained imide oligomer composition was confirmed by ¹ H-NMR, GPC, and FT-IR analysis as an aliphatic diamine residue having a structure represented by the above formula (5-1) or (5-3). It was confirmed that a group-containing imide oligomer (A is a 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride residue, B is a dimer diamine residue). Moreover, the weight average molecular weight of the imide oligomer composition was 2,200.

(Synthesis Example 2 (Preparation of polyimide resin solution))
54.6 weight of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a reaction vessel equipped with a stirrer, a water divider, and a nitrogen gas inlet tube. and 200 parts by weight of cyclohexanone were charged and dissolved. A mixed solution of 56.1 parts by weight of Priamine 1074 (manufactured by Croda), which is a dimer diamine, and 55.0 parts by weight of cyclohexanone was added dropwise to the resulting solution, followed by imidization reaction at 150° C. for 8 hours. A polyimide resin solution was obtained. The polyimide resin solution obtained had a solid concentration of 30% by weight and a number average molecular weight of 25,000.

(Examples 1 to 7, Comparative Examples 1 to 4)
According to the compounding ratio shown in Table 1, each material was stirred and mixed to prepare curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4.
Each obtained curable resin composition was coated on a substrate PET film so as to have a thickness of about 20 μm, and dried to prepare a curable resin composition film on the substrate PET film. The PET film was peeled off from the obtained curable resin composition film, and laminated with a laminator to a thickness of 500 μm to obtain a laminate. Using a rotary rheometer, the obtained laminate was heated to 90° C. at a frequency of 0.01 Hz to 1.0 Hz, and the complex viscosity at 90° C., 5% strain, and 1 rad/sec was measured. Also, the laminate obtained in the same manner was heated from 40° C. to 120° C. at a frequency of 1.0 Hz, a strain of 21%, and the melt viscosity at 90° C. was measured using a rotary rheometer. ARES (manufactured by TA Instruments) was used as the rotational rheometer. Table 1 shows the measurement results of the complex viscosity and the melt viscosity.

<Evaluation>
Each curable resin composition obtained in Examples and Comparative Examples was evaluated as follows. Table 1 shows the results.

(dielectric properties)
Each curable resin composition obtained in Examples and Comparative Examples was coated on a base PET film and dried to form a base PET film and a cured film having a thickness of 40 μm on the base PET film. An uncured laminated film having a flexible resin composition layer was obtained. The obtained uncured laminated film was cut into a size of 2 mm in width and 80 mm in length. The substrate PET film was peeled off from the curable resin composition layer of the cut uncured laminated film, and five curable resin composition layers were laminated using a laminator to obtain a laminate having a thickness of about 200 μm. The resulting laminate was heated at 190° C. for 90 minutes to obtain a cured product. For the obtained cured body, a cavity resonance perturbation method permittivity measuring device CP521 (manufactured by Kanto Denshi Applied Development Co., Ltd.) and a network analyzer N5224A PNA (manufactured by Keysight Technologies) were used to measure the frequency at 23 ° C. by the cavity resonance method. Dielectric loss tangent was measured at 1.0 GHz.
"◎" when the dielectric loss tangent was 0.0035 or less, "○" when the dielectric loss tangent was over 0.0035 and 0.0040 or less, and when the dielectric loss tangent was over 0.0040 and 0.0045 or less The dielectric properties were evaluated as “Δ” when there was a dielectric loss tangent, and as “×” when the dielectric loss tangent exceeded 0.0045.

(Adhesion to copper foil)
Each curable resin composition obtained in Examples and Comparative Examples was coated on a polyimide substrate ("Kapton 100H" manufactured by Toray DuPont Co., Ltd., thickness 25 μm) so as to have a thickness of about 20 μm, By drying, a laminate having a curable resin composition film on the polyimide substrate was obtained. The resulting laminate was cut to a width of 1 cm, and a 35 μm thick copper foil (manufactured by Fukuda Metal Foil and Powder Co., Ltd., a glossy surface of electrolytic copper foil, “CF-T8G-UN-35 ”) was laminated and heat-pressed under the conditions of 190° C., 3 MPa, and 1 hour to cure the curable resin composition layer and obtain a test piece. A test piece within 24 hours after preparation was subjected to a 90° peel test at a peel rate of 50 mm/min at 25° C. using a tensile tester ("UCT-500" manufactured by ORIENTEC) to measure the peel strength.
"◎" when the initial adhesive strength was 5 N / cm or more, "○" when it was 4 N / cm or more and less than 5 N / cm, and "△" when it was 3 N / cm or more and less than 4 N / cm. , and the adhesiveness to the copper foil was evaluated as "x" when it was less than 3 N/cm.

Claims

containing a curable resin, a curing agent, an inorganic filler, and a dispersant;
A curable resin composition having a complex viscosity of 8000 Pa·s or less at 90°C, 5% strain and 1 rad/sec.
2. The curable resin composition according to claim 1, wherein said inorganic filler is silica.
3. The curable resin composition according to claim 1, wherein the content of said inorganic filler is 65 parts by weight or more in 100 parts by weight of the total solid content of said curable resin composition.
4. The curable resin composition according to claim 1, 2 or 3, wherein the dispersant is a polyurethane-based dispersant.
5. The curable resin composition according to claim 1, 2, 3 or 4, further comprising a polymer component.
An interlayer insulating material using the curable resin composition according to claim 1, 2, 3, 4 or 5.