Compound, curable resin composition, cured product, circuit board, interlayer insulation material, and multilayer printed wiring board

Abstract

To provide a compound which is usable in a curable resin composition that is excellent in flexibility and workability before curing, and is excellent in dielectric characteristics (especially, low dielectric constant) and low linear expansion after curing, a curable resin composition containing the compound, a cured product using the curable resin composition, a circuit board, an interlayer insulation material, and a multilayer printed wiring board.SOLUTION: A compound has a structure represented by the following formula (1), and has a weight average molecular weight of 2,000 or more and 100,000 or less. In formula (1), A and B are each independently a divalent hydrocarbon group, and at least one of A and B is a group having cyclohexane. R1 to R4 are each independently a hydrogen atom, a methyl group, or an ethyl group, and n is an integer of 2 or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a compound. The present invention also relates to a curable resin composition containing the compound, a cured product obtained by using the curable resin composition, a circuit board, an interlayer insulating material, and a multilayer printed wiring board. [Background technology]

[0002] 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, curable resin compositions used as interlayer insulating materials for printed wiring boards and the like require dielectric properties such as low dielectric constant and low dielectric loss tangent. For example, Patent Documents 1 and 2 disclose curable resin compositions containing a curable resin and a compound having a specific structure as a curing agent, as curing resin compositions having such excellent dielectric properties. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2017-186551 A [Patent Document 2] International Publication No. 2016 / 114286 Summary of the Invention [Problem to be solved by the invention]

[0004] Conventional curable resin compositions have a problem in that it is difficult to achieve both flexibility and processability before curing and dielectric properties (particularly low dielectric constant) and low linear expansion after curing. The present invention aims to provide a compound that can be used in a curable resin composition that has excellent flexibility and processability before curing and excellent dielectric properties (particularly low dielectric constant) and low linear expansion after curing. The present invention also aims to provide a curable resin composition containing the compound, a cured product obtained by using the curable resin composition, a circuit board, an interlayer insulating material, and a multilayer printed wiring board. [Means for solving the problem]

[0005] Disclosure 1 relates to a compound having a structure represented by the following formula (1) and having a weight average molecular weight of 2,000 or more and 100,000 or less. Disclosure 2 is the compound of Disclosure 1 that does not have a linear aliphatic skeleton having 4 or more carbon atoms. The present disclosure 3 is a compound of the present disclosure 1 or 2, in which A in the following formula (1) is a group represented by the following formula (2-1), (2-2), or (2-3). The present disclosure 4 is a compound of the present disclosure 1 or 2, in which B in the following formula (1) is a group represented by the following formula (2-1), (2-2), or (2-3). The present disclosure 5 is a compound of the present disclosure 1 or 2, in which both A and B in the following formula (1) are each independently a group represented by the following formula (2-1), (2-2), or (2-3). The present disclosure 6 is a curable resin composition containing a curable resin and a compound of the present disclosure 1, 2, 3, 4 or 5. The present disclosure 7 is the curable resin composition according to the present disclosure 6, wherein the curable resin includes at least one selected from the group consisting of an epoxy resin, a cyanate resin, a phenol resin, an imide resin, and a maleimide resin. The present disclosure 8 is the curable resin composition of the present disclosure 6 or 7, further comprising a curing agent. Disclosure 9 is the curable resin composition of Disclosure 6, 7 or 8, further comprising an inorganic filler, wherein the inorganic filler comprises silica. The present disclosure 10 is a cured product obtained by curing the curable resin composition of the present disclosure 6, 7, 8 or 9. Disclosure 11 is a circuit board having the cured product of Disclosure 10. The twelfth aspect of the present disclosure is an interlayer insulating material obtained by using the curable resin composition according to the sixth, seventh, eighth or ninth aspect of the present disclosure. Disclosure 13 is a multilayer printed wiring board having a circuit board, a plurality of insulating layers disposed on the circuit board, and a metal layer disposed between the plurality of insulating layers, the insulating layers including a cured product of the interlayer insulating material of Disclosure 12.

[0006] [ka]

[0007] In formula (1), A and B are each independently a divalent hydrocarbon group, and at least one of A and B is a group represented by the following formula (2-1), (2-2), or (2-3). 1 ~R 4 are each independently a hydrogen atom, a methyl group, or an ethyl group, and n is an integer of 2 or greater.

[0008] [ka]

[0009] In formula (2-1), R 5 ~R 10 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 11 , R 12 are each independently a bond or a methylene group, and * is a bonding position. When B in the above formula (1) is not a group represented by formula (2-1), (2-2), or (2-3), and A in the above formula (1) is a group represented by formula (2-1), R in the formula (2-1) 5 ~R 10 When all of are hydrogen atoms, R 1 ~R 4 At least one of R is a methyl group or an ethyl group. 13 ~R 16 are each independently a hydrogen atom or a methyl group, R 17 , R 18 are each independently a bond or an alkylene group having 1 to 3 carbon atoms, and * indicates a bonding position. 19 ~R 22 are each independently a hydrogen atom or a methyl group, and * is a bonding position.

[0010] The present invention will be described in detail below. The present inventors have found that by using a compound having a specific structure, it is possible to obtain a curable resin composition that has excellent flexibility and processability before curing, and excellent dielectric properties (particularly low dielectric constant) and low linear expansion after curing, and have completed the present invention.

[0011] The compound of the present invention has a structure represented by the above formula (1). By having the structure represented by the above formula (1), a curable resin composition obtained by using the compound of the present invention has a low dielectric constant and a low linear expansion coefficient after curing. From the viewpoint of low linear expansion, it is preferable that the compound of the present invention does not have a straight-chain aliphatic skeleton having 4 or more carbon atoms.

[0012] In the above formula (1), A and B are each independently a divalent hydrocarbon group, and at least one of A and B is a group represented by the above formula (2-1), (2-2), or (2-3). That is, in the compound of the present invention, A in the above formula (1) may be a group represented by the following formula (2-1), (2-2), or (2-3), and B in the above formula (1) may be a group represented by the above formula (2-1), (2-2), or (2-3). Among them, since the obtained curable resin composition becomes more excellent in dielectric properties (particularly low dielectric constant) and low linear expansion after curing, it is preferable that both A and B in the above formula (1) are each independently a group represented by the above formula (2-1), (2-2), or (2-3).

[0013] In the above formula (1), R 1 ~R 4 are each independently a hydrogen atom, a methyl group, or an ethyl group. When B in the above formula (1) is not a group represented by formula (2-1), (2-2), or (2-3), and A in the above formula (1) is a group represented by formula (2-1), R 5 ~R 10 When all of are hydrogen atoms, R 1 ~R 4 At least one of the groups is a methyl group or an ethyl group.

[0014] In the above formula (1), n ​​is an integer of at least 2. The above n is not particularly limited as long as the weight-average molecular weight of the compound of the present invention is within the range described below.

[0015] In the above formula (2-1), R 5 ~R 10 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 5 ~R 10 At least two of these are preferably hydrogen atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and a t-butyl group. As described above, since it is preferable that the compound of the present invention does not have a linear aliphatic skeleton having 4 or more carbon atoms, the alkyl group having 1 to 4 carbon atoms is preferably not an n-butyl group, and is more preferably a methyl group. In addition, R 7 , R 8 When one of the groups is an alkyl group having 1 to 4 carbon atoms, the other is preferably a hydrogen atom.

[0016] In the above formula (2-1), R 11 , R 12 Each of R in the above formula (2-1) is independently a bond or a methylene group. 11 , R 12 At least one of the above is preferably a bond.

[0017] Specific examples of the group represented by the above formula (2-1) include a group represented by the following formula (3-1), a group represented by the following formula (3-2), a group represented by the following formula (3-3), a group represented by the following formula (3-4), a group represented by the following formula (3-5), a group represented by the following formula (3-6), a group represented by the following formula (3-7), a group represented by the following formula (3-8), a group represented by the following formula (3-9), a group represented by the following formula (3-10), a group represented by the following formula (3-11), etc. Among these, the group represented by the following formula (3-7) is preferred.

[0018] [ka]

[0019] In the formulas (3-1) to (3-11), * indicates a bonding position.

[0020] In the above formula (2-2), R 13 ~R 16 are each independently a hydrogen atom or a methyl group. 13 ~R 16 At least one of these is preferably a methyl group. In addition, R in the above formula (2-2) 15 , R 16 When one of these is a methyl group, the other is preferably a methyl group.

[0021] In the above formula (2-2), R 17 , R 18 are each independently a bond or an alkylene group having from 1 to 3 carbon atoms. Examples of the alkylene group having from 1 to 3 carbon atoms include a methylene group, an ethylene group, and a dimethylmethylene group.

[0022] Specific examples of the group represented by the above formula (2-2) include a group represented by the following formula (4-1), a group represented by the following formula (4-2), a group represented by the following formula (4-3), a group represented by the following formula (4-4), a group represented by the following formula (4-5), a group represented by the following formula (4-6), etc. Among these, a group represented by the following formula (4-4) is preferred.

[0023] [ka]

[0024] In the formulas (4-1) to (4-6), * indicates a bonding position.

[0025] In the above formula (2-3), R 19 ~R 22 are each independently a hydrogen atom or a methyl group.19 ~R 22 At least one of these is preferably a methyl group.

[0026] Specific examples of the group represented by the above formula (2-3) include groups represented by the following formula (5).

[0027] [ka]

[0028] In formula (5), * indicates a bond position.

[0029] The lower limit of the weight average molecular weight of the compound of the present invention is 2000, and the upper limit is 100,000. When the compound of the present invention is used in a curable resin composition, the resulting curable resin composition has excellent flexibility and processability before curing. The preferred lower limit of the weight average molecular weight of the compound of the present invention is 3000, and the preferred upper limit is 50,000, and the more preferred lower limit is 5000, and the more preferred upper limit is 30,000. In this specification, the "weight average molecular weight" is a value obtained by measuring using tetrahydrofuran as a solvent by gel permeation chromatography (GPC) and converting the weight average molecular weight into polystyrene equivalent. Examples of columns used in measuring the weight average molecular weight converted into polystyrene equivalent by GPC include JAIGEL-2H-A (manufactured by Japan Analytical Industry Co., Ltd.).

[0030] The method for producing the compound of the present invention may, for example, be a method of reacting a bisphenol compound having a group derived from A in the above formula (1), a diamine compound having a group derived from B in the above formula (1), and paraformaldehyde. The weight average molecular weight of the resulting compound can be adjusted by adjusting the molar ratio of the bisphenol compound having a group derived from A in the above formula (1) and the diamine compound having a group derived from B in the above formula (1) and the reaction conditions. The molar ratio of the bisphenol compound having a group derived from A in the above formula (1) and the diamine compound having a group derived from B in the above formula (1) (bisphenol compound having a group derived from A in the above formula (1) : diamine compound having a group derived from B in the above formula (1)) is preferably 40:60 to 60:40.

[0031] At least one of the bisphenol compound having a group derived from A in the above formula (1) and the diamine compound having a group derived from B in the above formula (1) has a group represented by the above formula (2-1), (2-2), or (2-3). In the case where the bisphenol compound having the group from which A in the above formula (1) is derived has a group represented by the above formula (2-1), R 5 ~R 10 are all hydrogen atoms, at least one of the hydrogen atoms at the ortho-position of the phenol skeleton is substituted with a methyl group or an ethyl group.

[0032] Among the bisphenol compounds having a group from which A in the above formula (1) is derived, examples of the bisphenol compounds having a group represented by the above formula (2-1), (2-2), or (2-3) include 4,4'-(3,3,5-trimethylcyclohexylidene)bis(phenol), 4,4'-(3,3-dimethylcyclohexylidene)bis(phenol), 4,4'-(3,5-dimethylcyclohexylidene)bis(phenol), 4,4'-((3S,4R)-3,4-dimethylcyclohexylidene)bis(phenol), 4,4'-(3,3,5-trimethylcyclohexylidene)bis(2-methylphenol), 4,4'-(3-methylcyclohexylidene)bis(phenol), 4,4'-(1 ,3-dimethyl-cyclohexanediyl)bis(phenol), 4,4'-(1,3-dimethyl-cyclohexanediyl)bis(2-methylphenol), 4,4'-(3-(1,1-dimethylethyl)cyclohexylidene)bis(phenol), 4,4'-((3,3,5,5-tetramethylcyclohexyl)methylene)bis(phenol), 4,4'-(4-methylcyclohexylidene)bis(phenol), 4,4'-cyclohexylidenebis(2-ethylphenol), 4-(1-(3-(4-hydroxyphenyl)-3-methylcyclohexyl)-1-methylethyl)phenol, 4,4'-(3-methylcyclohexylidene)bis(2,6-dimethylphenol), and the like. Other examples of the bisphenol compounds having a group from which A in the above formula (1) is derived include 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 4,4'-dihydroxydiphenyl sulfone, 2-hydroxyphenyl ether, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, and cyclohexylidene bisphenol.

[0033] Among the diamine compounds having a group from which B in the above formula (1) is derived, examples of the diamine compounds having a group represented by the above formula (2-1), (2-2), or (2-3) include isophoronediamine, 3-amino-1,5,5-trimethylcyclohexaneethanamine, 3-amino-5,5-dimethylcyclohexanemethanamine, 1-amino-3,3,5-trimethylcyclohexanemethanamine, 1-amino-3,3,5,5-tetramethylcyclohexanemethanamine, 1-amino-3,3-dimethylcyclohexanemethanamine, and 1,5,5-trimethyl-1,3-cyclohexanedimethanamine. Other examples of the diamine compounds having a group from which B in the above formula (1) is derived include 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'-diaminodiphenylsulfone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis(4-(4-aminophenoxy)phenyl)methane, 2,3'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylether ... ,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, bistruidine fluorene, 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.

[0034] The reaction of the bisphenol compound having a group from which A in the above formula (1) is derived, the diamine compound having a group from which B in the above formula (1) is derived, and the above paraformaldehyde can be carried out in a solvent or without a solvent. When the reaction is carried out in a solvent, examples of the reaction solvent to be used include aromatic non-polar solvents and halogenated solvents. Examples of the aromatic non-polar solvent include benzene, toluene, xylene, pseudocumene, and mesitylene. Examples of the halogen solvent include chloroform and dichloromethane. Among these, toluene and xylene are preferred, and toluene is more preferred, since they have a small impact on the environment and the human body, are highly versatile, and are inexpensive. The above solvents may be used alone or in combination of two or more kinds.

[0035] When the aromatic non-polar solvent is used as the reaction solvent, alcohols may be used in combination with the aromatic non-polar solvent. The alcohols are not particularly limited, but alcohols having a boiling point lower than that of the aromatic non-polar solvent are preferred. Examples of such alcohols include alcohols having a carbon number of not more than 4. Among these, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, and isobutanol are preferred. These alcohols may be used alone or in combination of two or more kinds.

[0036] During the reaction, the reaction solvent may be refluxed. In the reaction between the bisphenol compound having a group from which A in the above formula (1) is derived, the diamine compound having a group from which B in the above formula (1) is derived, and the above paraformaldehyde, water is generated in the reaction system. The water, like alcohols, has the effect of suppressing the progress of the synthesis reaction of the compound by solvation. When a solvent that forms an azeotrope with water is used as the synthesis solvent, the water generated during the reaction may be distilled out of the system by azeotropy in order to efficiently proceed with the reaction. In that case, the water generated during the reaction can be distilled out by using, for example, a pressure-equipped dropping funnel with a stopcock, a Dimroth condenser, a Dean-Stark apparatus, or the like.

[0037] In the reaction of a bisphenol compound having a group from which A in the above formula (1) is derived, a diamine compound having a group from which B in the above formula (1) is derived, and paraformaldehyde, it is preferable to carry out a heating treatment during synthesis. Examples of the heating treatment include a method in which a temperature regulator such as an oil bath is used to raise the temperature to a predetermined level and then the temperature is kept constant. The predetermined temperature during the heating treatment is not particularly limited, but it is preferable to adjust the reaction solution temperature to 50°C to 150°C. By setting the reaction solution temperature at 50°C or higher, the compound synthesis reaction can be prevented from slowing down, and the synthesis efficiency can be improved. By setting the reaction solution temperature at 150°C or lower, gelation of the reaction solution during the synthesis reaction can be suppressed.

[0038] The duration of the heating treatment is not particularly limited, but it is preferable to continue heating for about 1 to 10 hours after the start of heating. By continuing the heating treatment for 1 hour or more, the synthesis reaction can be sufficiently advanced and the synthesis yield can be improved. By continuing the heating treatment for 10 hours or less, gelation of the reaction solution and insolubilization of the compound, which is the synthesis product, can be suppressed.

[0039] After the above heating treatment is completed, the reaction medium may be allowed to cool by being released from contact with a temperature regulator such as an oil bath, or may be cooled using a refrigerant or the like. After cooling, examples of the method for extracting the compound from the reaction solution include poor solvent reprecipitation, concentration and solidification (solvent distillation under reduced pressure), and spray drying.

[0040] The present invention also includes a curable resin composition containing a curable resin and the compound of the present invention. The curable resin composition of the present invention contains the compound of the present invention, and therefore has excellent flexibility and processability before curing, and has excellent dielectric properties (particularly low dielectric constant) and low linear expansion after curing.

[0041] In 100 parts by mass of the components excluding the inorganic filler and the solvent in the curable resin composition of the present invention, the preferred lower limit of the content of the compound of the present invention is 5 parts by mass, and the preferred upper limit is 40 parts by mass. When the content of the compound of the present invention is within this range, the obtained curable resin composition is more excellent in flexibility and processability before curing, and in dielectric properties (particularly low dielectric constant) and low linear expansion after curing. The more preferred lower limit of the content of the compound of the present invention is 10 parts by mass, and the more preferred upper limit is 30 parts by mass.

[0042] Examples of the curable resin include epoxy resin, cyanate resin, phenol resin, imide resin, maleimide resin, silicone resin, acrylic resin, and fluororesin. Among them, the curable resin preferably contains at least one selected from the group consisting of epoxy resin, cyanate resin, phenol resin, imide resin, and maleimide resin, and more preferably contains epoxy resin. The curable resin may be used alone or in combination of two or more.

[0043] 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'-diallyl bisphenol A type epoxy resin, 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 novolac type epoxy resin, ortho-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthalene phenol novolac type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin, and glycidyl ester compound.

[0044] The curable resin composition of the present invention preferably further contains a curing agent. Examples of the curing agent include phenol-based curing agents, thiol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, cyanate-based curing agents, active ester-based curing agents, etc. Among these, phenol-based curing agents and active ester-based curing agents are preferred.

[0045] The preferred lower limit of the content of the curing agent in 100 parts by mass of the components excluding the inorganic filler and the solvent in the curable resin composition of the present invention is 10 parts by mass, and the preferred upper limit is 70 parts by mass. By the content of the curing agent being within this range, the obtained curable resin composition has better curability and storage stability. The more preferred lower limit of the content of the curing agent is 20 parts by mass, and the more preferred upper limit is 60 parts by mass.

[0046] 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.

[0047] 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, etc. Among these, imidazole-based curing accelerators are preferred from the viewpoints of curability and storage stability. The above curing accelerators may be used alone or in combination of two or more kinds.

[0048] The preferred lower limit of the content of the curing accelerator in 100 parts by mass of the components excluding the inorganic filler and the solvent in the curable resin composition of the present invention is 0.01 parts by mass. By having the content of the curing accelerator be 0.01 parts by mass or more, the effect of shortening the curing time is more excellent. The more preferred lower limit of the content of the curing accelerator is 0.02 parts by mass. From the viewpoint of adhesion and the like, the upper limit of the content of the curing accelerator is preferably 3 parts by mass, and more preferably 2 parts by mass.

[0049] The curable resin composition of the present invention preferably contains an inorganic filler. By containing the inorganic filler, the curable resin composition of the present invention becomes more excellent in moisture absorption reflow resistance and plating resistance while maintaining excellent adhesiveness and the like.

[0050] Examples of the inorganic filler include silica, talc, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, boron nitride, etc. Among them, the inorganic filler is preferably silica or alumina, and more preferably silica. By using the silica, the thermal expansion coefficient of the cured product of the obtained curable resin composition is further reduced, the surface roughness of the surface of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased. The silica is preferably spherical in shape. The silica may be hollow silica.

[0051] The inorganic fillers may be used alone or in combination of two or more kinds.

[0052] The inorganic filler has a preferred lower limit of 10 nm and a preferred upper limit of 4 μm for the average particle size. When the inorganic filler has an average particle size in this range, the curable resin composition obtained has better coatability. The inorganic filler has a more preferred upper limit of 3 μm for the average particle size.

[0053] The preferred lower limit of the content of the inorganic filler in 100 parts by mass of the components excluding the solvent in the curable resin composition of the present invention is 20 parts by mass, and the preferred upper limit is 90 parts by mass. By the content of the inorganic filler being within this range, the thermal dimensional stability can be improved, and the warping of the cured product of the obtained curable resin composition can be effectively suppressed. In addition, when the content of the inorganic filler is 20 parts by mass or more and 90 parts by mass or less, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Furthermore, when the content of the inorganic filler is within this range, it is possible to lower the thermal expansion coefficient of the cured product and at the same time improve the smear removability. The more preferred lower limit of the content of the inorganic filler is 30 parts by mass, and the more preferred upper limit is 80 parts by mass.

[0054] The curable resin composition of the present invention may contain a flow control agent for the purposes of improving the coatability onto an adherend in a short period of time and the shape retention. Examples of the flow regulator include fumed silica such as Aerosil, layered silicates, and the like. The flow control agents may be used alone or in combination of two or more kinds. The flow control agent preferably has an average particle size of less than 100 nm.

[0055] The curable resin composition of the present invention may contain an organic filler for the purposes of stress relief, 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 these, polyamide particles, polyamideimide particles, and polyimide particles are preferred. The organic fillers may be used alone or in combination of two or more kinds.

[0056] The curable resin composition of the present invention may contain a flame retardant. Examples of the flame retardant include boehmite-type aluminum hydroxide, metal hydrates such as aluminum hydroxide and magnesium hydroxide, halogen-based compounds, phosphorus-based compounds, nitrogen compounds, etc. Among these, boehmite-type aluminum hydroxide is preferred. The flame retardants may be used alone or in combination of two or more kinds.

[0057] The curable resin composition of the present invention may contain a thermoplastic resin within a range that does not impair the object of the present invention. By using the thermoplastic resin, the curable resin composition of the present invention has excellent flow properties, and is more easily able to achieve both filling properties and exudation prevention properties during thermocompression bonding, and has excellent flex resistance after curing.

[0058] Examples of the thermoplastic resin include polyimide resin, phenoxy resin, polyamide resin, polyamideimide resin, polyvinyl acetal resin, etc. Among these, phenoxy resin is preferred from the viewpoints of heat resistance and handling properties. The above thermoplastic resins may be used alone or in combination of two or more kinds.

[0059] The preferred lower limit of the weight average molecular weight of the thermoplastic resin is 3000, and the preferred upper limit is 100,000. When the weight average molecular weight of the thermoplastic resin is within this range, the resulting curable resin composition has better flow properties and bending resistance after curing. The more preferred lower limit of the weight average molecular weight of the thermoplastic resin is 5000, and the more preferred upper limit is 50,000.

[0060] The curable resin composition of the present invention may contain a solvent from the viewpoint of coatability and the like. As the above-mentioned solvent, from the viewpoints of coatability, storage stability, and the like, a nonpolar solvent having a boiling point of 160° C. or less or an aprotic polar solvent having a boiling point of 160° C. or less is preferred. Examples of the nonpolar solvents having a boiling point of 160° C. or lower or the aprotic polar solvents having a boiling point of 160° C. or lower 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 solvent include methyl acetate, ethyl acetate, and isobutyl acetate. Examples of the hydrocarbon solvent include benzene, toluene, normal hexane, isohexane, cyclohexane, methylcyclohexane, normal heptane, and the like. Examples of the halogen-based solvent include dichloromethane, chloroform, and trichloroethylene. Examples of the ether solvent include diethyl ether, tetrahydrofuran, 1,4-dioxane, and 1,3-dioxolane. The nitrogen-containing solvent includes, for example, acetonitrile. Among these, from the viewpoints of ease of handling and solubility of the curing agent, it is preferable to use at least one solvent selected from the group consisting of ketone solvents having a boiling point of 60° C. or higher, ester solvents having a boiling point of 60° C. or higher, and ether solvents having a boiling point of 60° C. or higher. Examples of such solvents include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, isobutyl acetate, 1,4-dioxane, 1,3-dioxolane, and tetrahydrofuran. The above "boiling point" refers to a value measured under a condition of 101 kPa, or a value converted to 101 kPa using a boiling point conversion chart or the like.

[0061] The curable resin composition of the present invention may contain a reactive diluent within a range that does not impair the object of the present invention. From the viewpoint of adhesive reliability, the reactive diluent is preferably one having two or more reactive functional groups in one molecule.

[0062] The curable resin composition of the present invention may further contain additives such as a coupling agent, a dispersant, a storage stabilizer, a bleeding inhibitor, a fluxing agent, and a leveling agent.

[0063] Examples of a method for producing the curable resin composition of the present invention include a method in which a curable resin, the compound of the present invention, a curing agent, and a solvent added as necessary are mixed using a mixer such as a homodisper, a universal mixer, a Banbury mixer, or a kneader.

[0064] The curable resin composition of the present invention can be applied onto a substrate film and dried to obtain a curable resin composition film made of the curable resin composition of the present invention, and the curable resin composition film can be cured to obtain a cured product. A cured product obtained by curing the curable resin composition of the present invention also constitutes the present invention.

[0065] The curable resin composition of the present invention has a preferred upper limit of the dielectric constant at 23° C. after curing of 3.1. Since the dielectric constant at 23° C. after curing is in this range, the curable resin composition of the present invention can be suitably used as an interlayer insulating material for multilayer printed wiring boards, etc. The more preferred upper limit of the dielectric constant at 23° C. after curing is 2.9. The dielectric constant at 23° C. after curing is preferably as low as possible, and there is no particular preferred lower limit, but the substantial lower limit is 2.0. The "dielectric constant" is a value measured at 10 GHz using a dielectric constant measuring device and a network analyzer. The cured product for measuring the dielectric constant 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 dielectric constant measuring device may be CP521 (manufactured by Kanto Electronics Application Development Co., Ltd.), etc. The network analyzer may be N5224A PNA (manufactured by Keysight Technologies, Inc.), etc.

[0066] The curable resin composition of the present invention has a preferred upper limit of 50 ppm for the average linear expansion coefficient in the temperature range of 25° C. to 125° C. after curing. When the average linear expansion coefficient is 50 ppm or less, the obtained cured product has excellent dimensional stability and is capable of reducing warpage, etc. The more preferred upper limit of the average linear expansion coefficient is 45 ppm. The lower the average linear expansion coefficient, the more preferable it is. There is no particular preferred lower limit, but the substantial lower limit is 20 ppm. The average linear expansion coefficient can be measured for a 400 μm thick cured product using a thermomechanical analyzer. Specifically, a 1 cm long sample of the cured product is heated from 0° C. to 300° C. under a load of 5 g and a heating rate of 10° C. / min, then cooled and heated again from 0° C. to 300° C. under the same conditions. The average linear expansion coefficient in the temperature range from 25° C. to 125° C. can be calculated based on the data on temperature and dimensional change obtained in the second measurement. The cured product for measuring the average linear expansion coefficient is prepared by coating the curable resin composition on a substrate PET film, drying the composition, laminating the composition to a thickness of 400 μm, and heating the composition at 190° C. for 1 hour to cure the composition. The thermomechanical analyzer may be, for example, TMA / SS-6000 (manufactured by Hitachi High-Tech Science Corporation).

[0067] The curable resin composition of the present invention can be used in a wide range of applications. For example, it can be used as an adhesive for printed wiring boards, an adhesive for coverlays of flexible printed circuit boards, copper-clad laminates, adhesives for semiconductor bonding, interlayer insulating materials, prepregs, LED sealants, adhesives for structural materials, etc. A circuit board having the cured product of the present invention is also one of the present inventions. In particular, the curable resin composition of the present invention has a low dielectric constant, a low dielectric tangent, and excellent dielectric properties when cured, and therefore can be suitably used as an interlayer insulating material for multilayer printed wiring boards, etc. An interlayer insulating material obtained by using the curable resin composition of the present invention is also one aspect of the present invention. The present invention also provides a multilayer printed wiring board having a circuit board, a plurality of insulating layers arranged on the circuit board, and a metal layer arranged between the plurality of insulating layers, wherein the insulating layers contain a cured product of the interlayer insulating material of the present invention. Effect of the Invention

[0068] According to the present invention, it is possible to provide a compound that can be used in a curable resin composition that has excellent flexibility and processability before curing and excellent dielectric properties (particularly low dielectric constant) and low linear expansion after curing. In addition, according to the present invention, it is possible to provide a curable resin composition containing the compound, and an adhesive, an adhesive film, a cured product, a circuit board, an interlayer insulating material, and a multilayer printed wiring board that use the curable resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0069] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0070] (Synthesis Example 1 (Preparation of Compound A)) In a 500 mL flask equipped with a reflux tube, a pressure equalizing dropping funnel with a cock, and a Dimroth condenser, 190 mL of toluene and 10 mL of isobutanol were added as a mixed solvent at 25° C. in one go and mixed. Next, 34.7 g (0.1 mol) of 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene (Mitsui Fine Chemicals, Inc., "Bisphenol-M") and 17.0 g (0.1 mol) of isophoronediamine (Tokyo Chemical Industry Co., Ltd.) were added in one go and mixed in the flask at 25° C. Thereafter, the reaction solution was heated to 60° C., and 13.2 g (0.44 mol) of paraformaldehyde (Tokyo Chemical Industry Co., Ltd.) was added in the flask and mixed to obtain a mixed solution. The flask containing the resulting mixed solution was immersed in an oil bath set at 120°C and heated while refluxing to allow the reaction to proceed. One hour after the start of reflux, the water produced in the reaction system was distilled out of the system by azeotropy with toluene and methanol. After the reaction was allowed to proceed for 6 hours from the start of distillation, the flask was removed from the oil bath and the resulting reaction solution was cooled to 25°C. After cooling, the reaction solution was poured into 1 L of methanol to precipitate the reactant. The precipitated solid was dried under reduced pressure to obtain compound A. In addition, 1 By H-NMR, GPC, and FT-IR analyses, compound A was found to be a compound having a structure represented by the above formula (1) (A is a group derived from 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, B is a group represented by the above formula (4-4), R 1 ~R 4 It was confirmed that the compound A had a weight average molecular weight of 11,000.

[0071] (Synthesis Example 2 (Preparation of Compound B)) Compound B was obtained in the same manner as in Synthesis Example 1, except that 26.8 g (0.1 mol) of cyclohexylidenebisphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene. In addition,1 H-NMR, GPC, and FT-IR analyses revealed that compound B is a compound having a structure represented by the above formula (1) (wherein A is a group derived from cyclohexylidene bisphenol, B is a group represented by the above formula (4-4), R 1 ~R 4 It was confirmed that the compound B had a weight average molecular weight of 14,000.

[0072] (Synthesis Example 3 (Preparation of Compound C)) Compound C was obtained in the same manner as in Synthesis Example 1, except that 31.0 g (0.1 mol) of 4,4'-(3,3,5-trimethylcyclohexylidene)bis(phenol) (manufactured by Honshu Chemical Industry Co., Ltd., "BisP-HTG") was used instead of 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene. In addition, 1 H-NMR, GPC, and FT-IR analyses revealed that compound C is a compound having a structure represented by formula (1) (wherein A is a group represented by formula (3-7), B is a group represented by formula (4-4), R 1 ~R 4 It was confirmed that the compound C had a weight average molecular weight of 10,000.

[0073] (Synthesis Example 4 (Preparation of Compound D)) Compound D was obtained in the same manner as in Synthesis Example 1, except that 31.0 g (0.1 mol) of 4,4'-(3,3,5-trimethylcyclohexylidene)bis(phenol) (manufactured by Honshu Chemical Industry Co., Ltd., "BisP-HTG") was used instead of 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, and 34.5 g (0.1 mol) of 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene (manufactured by Mitsui Fine Chemicals Co., Ltd., "Bisaniline-M") was used instead of isophoronediamine. In addition, 1 By H-NMR, GPC, and FT-IR analyses, compound D was found to be a compound having a structure represented by formula (1) above (wherein A is a group represented by formula (3-7) above, B is a group derived from 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, R1 ~R 4 It was confirmed that the compound D had a weight average molecular weight of 12,000.

[0074] (Synthesis Example 5 (Preparation of Compound E)) Compound E was obtained in the same manner as in Synthesis Example 1, except that 34.5 g (0.1 mol) of 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene (Mitsui Fine Chemicals, Inc., "Bisaniline-M") was used instead of isophoronediamine. In addition, 1 H-NMR, GPC, and FT-IR analyses revealed that compound E is a compound represented by the above formula (1), in which the moiety corresponding to A is a group derived from 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, the moiety corresponding to B is a group derived from 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, and R 1 ~R 4 It was confirmed that the compound E was a compound in which the moiety corresponding to was a hydrogen atom. The weight average molecular weight of compound E was 9,800.

[0075] (Synthesis Example 6 (Preparation of Compound F)) Compound F was obtained in the same manner as in Synthesis Example 1, except that 56.8 g (0.1 mol) of dimer diamine (manufactured by Croda, "Priamine 1073") was used instead of isophoronediamine. In addition, 1 H-NMR, GPC, and FT-IR analyses revealed that compound F is a compound represented by the above formula (1), in which the moiety corresponding to A is a group derived from 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, the moiety corresponding to B is a group derived from dimer diamine, and R 1 ~R 4 It was confirmed that the compound F was a compound in which the moiety corresponding to was a hydrogen atom. The weight average molecular weight of the compound F was 13,000.

[0076] (Synthesis Example 7 (Preparation of Compound G)) Compound G was obtained in the same manner as in Synthesis Example 1, except that 11.4 g (0.1 mol) of cyclohexanediamine (manufactured by Kanto Chemical Co., Ltd.) was used instead of isophoronediamine. In addition, 1 H-NMR, GPC, and FT-IR analyses revealed that compound G is a compound represented by the above formula (1), in which the moiety corresponding to A is a group derived from 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, the moiety corresponding to B is a group derived from cyclohexanediamine, and R 1 ~R 4 It was confirmed that the compound G had a hydrogen atom in the portion corresponding to the formula: In addition, the weight average molecular weight of the compound G was 11,000.

[0077] (Synthesis Example 8 (Preparation of Compound H)) Compound H was obtained in the same manner as in Synthesis Example 1, except that the amount of 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene added was changed to 69.4 g (0.2 mol). In addition, 1 By H-NMR, GPC, and FT-IR analysis, compound H is a compound having a structure represented by the above formula (1) (A is a group derived from 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, B is a group represented by the above formula (4-4), R 1 ~R 4 It was confirmed that the compound H had a weight average molecular weight of 1,800.

[0078] (Examples 1 to 4, Comparative Examples 1 to 4) Cyclohexanone was added as a solvent to each of the compounds A to H synthesized above to dissolve them, and a solution with a solid content of 30% by mass was obtained. Next, each material in the blending ratio shown in Table 1 was stirred and mixed at room temperature until a uniform solution was obtained, and a curable resin composition was obtained. Note that the composition in Table 1 shows the solid content (parts by mass) excluding the solvent. The obtained curable resin composition was applied onto a release-treated surface of a PET film (manufactured by Toray Industries, Inc., "XG284", thickness 25 μm) using an applicator. Then, the film was dried for 5 minutes in a gear oven at 100° C. to volatilize the solvent, thereby obtaining an uncured laminate film having a PET film and a 40 μm-thick curable resin composition layer on the PET film.

[0079] <Evaluation> The uncured laminate films thus obtained were subjected to the following evaluations, and the results are shown in Table 1.

[0080] (Flexibility and workability) Each of the obtained uncured laminate films was cut into a rectangle having a length of 10 cm and a width of 5 cm. The cut uncured laminate film was folded 180 degrees so that the PET film layer was on the inside, and then returned to a flat state, and the state of the curable resin composition layer was visually confirmed. Flexibility and processability were evaluated by rating "O" if no cracks occurred when bent 180 degrees, and rating "X" if cracks occurred when bent 180 degrees.

[0081] (Dielectric properties) Each uncured laminate film obtained was cut into a rectangle of 80 mm in length and 2 mm in width. The PET film was peeled off from the curable resin composition layer of the cut uncured laminate film, and five curable resin composition layers were laminated using a laminator to obtain a laminate of about 200 μm in thickness. The obtained laminate was heated at 190° C. for 90 minutes to obtain a cured product. The dielectric constant of the obtained cured product was measured by the cavity resonance method at 23° C. and a frequency of 10 GHz using a cavity resonance perturbation method dielectric constant measuring device CP521 (manufactured by Kanto Electronics Application Development Co., Ltd.) and a network analyzer N5224A PNA (manufactured by Keysight Technologies, Inc.). The dielectric properties were evaluated as follows: when the dielectric constant was 2.9 or less, it was marked "A", when it was more than 2.9 and less than 3.1, it was marked "O", and when it was more than 3.1, it was marked "X".

[0082] (Low linear expansion) The PET film was peeled off from the curable resin composition layer of each of the obtained uncured laminated films, and 10 curable resin composition layers were laminated using a laminator to obtain a laminate with a thickness of about 400 μm. The obtained laminate was heated at 190 ° C. for 90 minutes to obtain a cured product. The obtained cured product was heated from 0 ° C. to 300 ° C. with a load of 5 g, a heating rate of 10 ° C. / min, and a sample length of 1 cm using a thermomechanical analyzer (Hitachi High-Tech Science Corporation, "TMA / SS-6000"), and then cooled and heated again from 0 ° C. to 300 ° C. under the same conditions. Based on the data on temperature and dimensional change obtained in the second measurement, the average linear expansion coefficient in the temperature range from 25 ° C. to 150 ° C. was obtained. The low linear expansion property was evaluated by rating "O" when the average linear expansion coefficient was 50 ppm or less, and "X" when it exceeded 50 ppm.

[0083] [Table 1] [Industrial Applicability]

[0084] According to the present invention, it is possible to provide a compound that can be used in a curable resin composition that has excellent flexibility and processability before curing and excellent dielectric properties (particularly low dielectric constant) and low linear expansion after curing. In addition, according to the present invention, it is possible to provide a curable resin composition containing the compound, and an adhesive, an adhesive film, a cured product, a circuit board, an interlayer insulating material, and a multilayer printed wiring board that use the curable resin composition.

Claims

1. A compound having a structure represented by the following formula (1) and having a weight average molecular weight of 2,000 or more and 100,000 or less. 【Chemistry 1】 In formula (1), A and B are each independently a divalent hydrocarbon group, and at least one of A and B is a group represented by the following formula (2-1), (2-2), or (2-3). １ ~R ４ are each independently a hydrogen atom, a methyl group, or an ethyl group, and n is an integer of 2 or greater. 【Chemistry 2】 In formula (2-1), R ５ ~R １０ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R １１ , R １２ are each independently a bond or a methylene group, and * is a bonding position. When B in the formula (1) is not a group represented by the formula (2-1), (2-2), or (2-3), and A in the formula (1) is a group represented by the formula (2-1), R ５ ~R １０ When all of are hydrogen atoms, R １ ~R ４ At least one of R is a methyl group or an ethyl group. １３ ~R １６ are each independently a hydrogen atom or a methyl group; R １７ , R １８ are each independently a bond or an alkylene group having 1 to 3 carbon atoms, and * indicates a bonding position. １９ ~R ２２ are each independently a hydrogen atom or a methyl group, and * indicates the bonding position.

2. The compound according to claim 1, which does not have a straight-chain aliphatic skeleton having 4 or more carbon atoms.

3. The compound according to claim 1, wherein A in the formula (1) is a group represented by the formula (2-1), (2-2), or (2-3).

4. The compound according to claim 1, wherein B in the formula (1) is a group represented by the formula (2-1), (2-2), or (2-3).

5. The compound according to claim 1, wherein both A and B in the formula (1) are each independently a group represented by the formula (2-1), (2-2), or (2-3).

6. A curable resin composition comprising a curable resin and the compound according to claim 1.

7. The curable resin composition according to claim 6 , wherein the curable resin comprises at least one selected from the group consisting of an epoxy resin, a cyanate resin, a phenolic resin, an imide resin, and a maleimide resin.

8. The curable resin composition according to claim 6 or 7, further comprising a curing agent.

9. The curable resin composition according to claim 6 or 7, further comprising an inorganic filler, the inorganic filler including silica.

10. A cured product obtained by curing the curable resin composition according to claim 6 or 7.

11. A circuit board comprising the cured product according to claim 10.

12. An interlayer insulating material comprising the curable resin composition according to claim 6 or 7.

13. 13. A multilayer printed wiring board comprising a circuit board, a plurality of insulating layers disposed on the circuit board, and a metal layer disposed between the plurality of insulating layers, the insulating layers including a cured product of the interlayer insulating material according to claim 12.

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