CN113728030A - Curable resin composition - Google Patents

Curable resin composition Download PDF

Info

Publication number
CN113728030A
CN113728030A CN202080031240.1A CN202080031240A CN113728030A CN 113728030 A CN113728030 A CN 113728030A CN 202080031240 A CN202080031240 A CN 202080031240A CN 113728030 A CN113728030 A CN 113728030A
Authority
CN
China
Prior art keywords
resin composition
maleimide
group
compound
curable resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202080031240.1A
Other languages
Chinese (zh)
Other versions
CN113728030B (en
Inventor
下野智弘
冈本竜也
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp filed Critical DIC Corp
Publication of CN113728030A publication Critical patent/CN113728030A/en
Application granted granted Critical
Publication of CN113728030B publication Critical patent/CN113728030B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—Prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Providing: a curable resin composition having a cured product thereof exhibiting both excellent heat resistance and dielectric properties, and a prepreg, a circuit board, a build-up film, a semiconductor sealing material and a semiconductor device having a cured product thereof exhibiting both of these properties. The curable resin composition of the present invention is characterized by containing: a maleimide having an indane skeleton, (B) a compound having a substituent having an unsaturated bond, and (C) an epoxy resin.

Description

Curable resin composition
Technical Field
The present invention relates to a curable resin composition, a cured product obtained from the curable resin composition, a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device.
Background
As materials for circuit boards for electronic devices, there are widely used: a prepreg obtained by impregnating a glass cloth with a heat-curable resin such as an epoxy resin-based resin or a BT (bismaleimide-triazine) resin-based resin and drying the resin by heating, a laminate obtained by heat-curing the prepreg, and a multilayer board obtained by heat-curing the laminate and the prepreg in combination. Among them, since semiconductor package substrates are becoming thinner and warpage of package substrates during mounting becomes a problem, materials exhibiting high heat resistance are required to suppress this.
In addition, in recent years, signal speeds and high frequencies have been advancing, and it is desired to provide a thermosetting resin composition that can obtain a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant under these circumstances.
In particular, recently, further improvement in performance represented by heat resistance and dielectric characteristics, and materials and compositions having the above performance have been demanded for various electronic material applications, particularly advanced material applications.
In response to such a demand, maleimide resins are attracting attention as materials having both heat resistance and low dielectric constant/low dielectric loss tangent. However, although the conventional maleimide resins exhibit high heat resistance, their dielectric constant/dielectric loss tangent values are not at a level required for the applications of the advanced materials, and their handling properties are poor due to the solubility of the poorly soluble agent, and therefore, there is a strong demand for the development of resins which exhibit further low dielectric constant/low dielectric loss tangent and also have excellent solvent solubility while maintaining heat resistance.
In such a case, as a cyanate ester material having both high dielectric characteristics and high heat resistance, a resin composition in which a phenol novolac type cyanate ester resin, a bisphenol a cyanate ester resin, and a non-halogen epoxy resin are blended is known (see patent document 1).
However, although the resin composition described in patent document 1 has improved heat resistance and dielectric properties of a cured product to some extent, the heat resistance has not yet reached the level required in recent years.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2004-182850
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide a curable resin composition having a cured product thereof having both excellent heat resistance and dielectric properties, a cured product thereof, and a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device having the above properties.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems, and as a result, have found that a curable resin composition containing a maleimide having an indane skeleton (a), a compound having an unsaturated bond-containing substituent (B), and an epoxy resin (C) can provide a cured product having both a low dielectric constant and a low dielectric loss tangent and excellent heat resistance, thereby completing the present invention.
That is, the present invention relates to a curable resin composition comprising: a maleimide having an indane skeleton, (B) a compound having a substituent having an unsaturated bond, and (C) an epoxy resin.
In the curable resin composition of the present invention, the maleimide (a) is preferably represented by the following general formula (1).
Figure BDA0003319414500000031
(in the formula (1), Ra independently represents alkyl, alkoxy or alkylthio with 1-10 carbon atoms, aryl, aryloxy or arylthio with 6-10 carbon atoms, cycloalkyl with 3-10 carbon atoms, halogen atom, nitro, hydroxyl or sulfydryl, q represents an integer value of 0-4, when q is 2-4, Ra is optionally the same or different in the same ring, Rb independently represents alkyl, alkoxy or alkylthio with 1-10 carbon atoms, aryl, aryloxy or arylthio with 6-10 carbon atoms, cycloalkyl with 3-10 carbon atoms, halogen atom, hydroxyl or sulfydryl, r represents an integer value of 0-3, when r is 2-3, Rb is optionally the same or different in the same ring, n is an average repeating unit number and represents a number of 0.5-20.)
The cured product of the present invention is preferably obtained by curing the curable resin composition.
The prepreg of the present invention preferably has a reinforcing base material and a semi-cured product of the curable resin composition impregnated in the reinforcing base material.
The circuit board of the present invention is preferably obtained by laminating the prepreg and the copper foil and then heating, pressure-bonding, and molding the laminate.
The laminate film of the present invention preferably contains the curable resin composition.
The semiconductor sealing material of the present invention preferably contains the curable resin composition.
The semiconductor device of the present invention preferably includes a cured product obtained by heat-curing the semiconductor sealing material.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the curable resin composition of the present invention, a cured product obtained from the curable resin composition can be provided which has both excellent heat resistance and dielectric properties and also the above properties, and a cured product obtained from the curable resin composition, a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device can be provided, and the curable resin composition is useful.
Detailed Description
The present invention will be described in detail below.
The present invention relates to a curable resin composition, characterized by containing: a maleimide having an indane skeleton (a) (hereinafter, sometimes referred to as "component (a)"), a compound (B) having an unsaturated bond-containing substituent (hereinafter, sometimes referred to as "component (B)"), and an epoxy resin (C) (hereinafter, sometimes referred to as "component (C)"). Among them, the maleimide (a) is preferably represented by the following general formula (1). The maleimide (a) has an indane skeleton, and is preferable because the proportion of polar functional groups in the structure of the maleimide (a) is smaller than that of conventional maleimides, and thus the dielectric properties are excellent. In addition, a cured product using a conventional maleimide resin tends to be brittle, and there is a fear that the brittleness resistance is poor, but the maleimide (a) has an indane skeleton and is excellent in flexibility, and improvement of the brittleness resistance is also expected, and is preferable.
Figure BDA0003319414500000041
In the general formula (1), Ra independently represents an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms, an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms (preferably 5 to 10 carbon atoms), a halogen atom, a nitro group, a hydroxyl group or a mercapto group, and q represents an integer of 0 to 4. When q is 2 to 4, Ra is optionally the same or different in the same ring. Rb each independently represents an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms, an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group, and r represents an integer of 0 to 3. When r is 2-3, Rb is optionally the same or different in the same ring. n is the average number of repeating units and represents a number of 0.5 to 20. When r and q are 0, Ra and Rb each represent a hydrogen atom.
Ra in the general formula (1) is preferably any of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and is a preferable embodiment in which the alkyl group having 1 to 4 carbon atoms or the like improves the solvent solubility due to a decrease in planarity and a decrease in crystallinity in the vicinity of the maleimide group, and a cured product can be obtained without impairing the reactivity of the maleimide group.
Q in the general formula (1) is preferably 2 to 3, and more preferably 2. When q is 2, the influence of steric hindrance is small, and the electron density on the aromatic ring is increased, which is a preferable mode in the production (synthesis) of maleimide.
In the general formula (1), r is preferably 0 and Rb is a hydrogen atom, and r is preferably 1 to 3, and Rb is at least 1 selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and particularly, when r is 0 and Rb is a hydrogen atom, steric hindrance is reduced when an indane skeleton in maleimide is formed, and this is a preferable mode in terms of an advantage in the production (synthesis) of maleimide.
< method for producing maleimide (A) having indane skeleton >
The following describes a method for producing the maleimide (A).
The following general formula (2) is a compound: rc each independently represents a monovalent functional group selected from the group consisting of the following general formulae (3) and (4), at least one of 2 Rc has a hydrogen atom in the ortho-position, and Rb and r have the same meanings as described above.
Figure BDA0003319414500000051
Figure BDA0003319414500000061
The following general formula (5) is: aniline or a derivative thereof in which at least 1 of the ortho-position and the para-position of the amino group is a hydrogen atom, and Ra and q each represent the same meaning as described above, can be reacted with a compound of the general formula (2) in the presence of an acid catalyst to obtain an intermediate amine compound represented by the general formula (6). In the following general formula (6), Ra, Rb, q, and r have the same meanings as described above.
Figure BDA0003319414500000062
The intermediate amine compound represented by the above general formula (6) has a structure represented by the following general formula (7) having an indane skeleton, but when q is 3 or less and at least 2 of ortho-position and para-position of the amino group are hydrogen atoms in the aniline or derivative thereof represented by the above general formula (5), it has a structure represented by the following general formula (8). Wherein Ra, Rb, q and r in the following general formula (8) are the same as above, and m is the number of repeating units and represents an integer of 1 to 20. Further, the structure represented by the following general formula (8) may be included in the structure of the above general formula (6).
Figure BDA0003319414500000071
The indane skeleton (see the general formula (7)) which is a characteristic of the maleimide (a) used in the present invention is 0.5 to 20, preferably 0.7 to 10.0, more preferably 0.95 to 10.0, further preferably 0.98 to 9.0, further preferably 0.99 to 8.0, further preferably 1.0 to 7.0, and further preferably 1.0 to 6.0 in terms of the average number of repeating units n (average value) in order to have a low melting point (low softening point) and a low melt viscosity and excellent handling properties. The maleimide (a) having an indane skeleton is preferable because it has excellent solvent solubility compared with conventionally used maleimides. When n is less than 0.5, the proportion of the high-melting-point substance in the structure of the maleimide (a) increases, the solubility in a solvent is poor, and the proportion of the high-molecular-weight component contributing to flexibility decreases, so that the brittleness resistance of the resulting cured product decreases, and the flexibility and flexibility decrease, which is not preferable. When n exceeds 20, the heat resistance may be poor, and the high molecular weight component may be excessive, which may result in poor flowability and poor handling properties when a cured product is formed. The value of n is preferably 0.5 to 10.0, more preferably 0.95 to 10.0, from the viewpoints of high heat distortion temperature, high glass transition temperature, and the like.
The compound represented by the above general formula (2) (hereinafter, "compound (a)") used in the present invention is not particularly limited, and typically, p-diisopropenylbenzene and m-diisopropenylbenzene, p-bis (. alpha. -hydroxyisopropyl) benzene and m-bis (. alpha. -hydroxyisopropyl) benzene, 1- (. alpha. -hydroxyisopropyl) -3-isopropenylbenzene, 1- (. alpha. -hydroxyisopropyl) -4-isopropenylbenzene, or a mixture thereof is used. In addition, nuclear alkyl substituted compounds of these compounds, such as diisopropenyltoluene and bis (. alpha. -hydroxyisopropyl) toluene, and further nuclear halogen substituted compounds, such as chlorodiisopropenylbenzene and chlorobis (. alpha. -hydroxyisopropyl) benzene, may be used.
Further, as the aforementioned compound (a), for example, 2-chloro-1, 4-diisopropenylbenzene, 2-chloro-1, 4-bis (. alpha. -hydroxyisopropyl) benzene, 2-bromo-1, 4-diisopropenylbenzene, 2-bromo-1, 4-bis (. alpha. -hydroxyisopropyl) benzene, 2-bromo-1, 3-diisopropenylbenzene, 2-bromo-1, 3-bis (. alpha. -hydroxyisopropyl) benzene, 4-bromo-1, 3-diisopropylbenzene, 4-bromo-1, 3-bis (. alpha. -hydroxyisopropyl) benzene, 5-bromo-1, 3-diisopropenylbenzene, 5-bromo-1, 3-bis (. alpha. -hydroxyisopropyl) benzene, 2-bromo-1, 4-diisopropenylbenzene, 2-bromo-bis (alpha. -hydroxyisopropyl) benzene, 2-bromo-1, 3-bis (alpha. -hydroxyisopropyl) benzene, 2-bromo-1, 4-diisopropenylbenzene, 2-hydroxy-1, 3-bis (alpha. -hydroxyisopropyl) benzene, 4-diisopropenylbenzene, 2-methoxy-1, 4-diisopropenylbenzene, 2-methoxy-1, 4-bis (. alpha. -hydroxyisopropyl) benzene, 5-ethoxy-1, 3-diisopropenylbenzene, 5-ethoxy-1, 3-bis (. alpha. -hydroxyisopropyl) benzene, 2-phenoxy-1, 4-diisopropenylbenzene, 2-phenoxy-1, 4-bis (. alpha. -hydroxyisopropyl) benzene, 2, 4-diisopropenylthiol, 2, 4-bis (. alpha. -hydroxyisopropyl) benzenethiol, 2, 5-diisopropenylthiol, 2, 5-bis (. alpha. -hydroxyisopropyl) benzenethiol, 2-methylthio-1, 4-diisopropenylbenzene, 2-methylthio-1, 4-bis (. alpha. -hydroxyisopropyl) benzene, 2-phenylthio-1, 3-diisopropenylbenzene, 2-phenylthio-1, 3-bis (. alpha. -hydroxyisopropyl) benzene, 2-phenyl-1, 4-diisopropenylbenzene, 2-phenyl-1, 4-bis (. alpha. -hydroxyisopropyl) benzene, 2-cyclopentyl-1, 4-diisopropenylbenzene, 2-cyclopentyl-1, 4-bis (. alpha. -hydroxyisopropyl) benzene, 5-naphthyl-1, 3-diisopropenylbenzene, 5-naphthyl-1, 3-bis (. alpha. -hydroxyisopropyl) benzene, 2-methyl-1, 4-diisopropenylbenzene, 2-methyl-1, 4-bis (. alpha. -hydroxyisopropyl) benzene, 5-butyl-1, 3-diisopropenylbenzene, 5-butyl-1, 3-bis (. alpha. -hydroxyisopropyl) benzene, 5-cyclohexyl-1, 3-diisopropenylbenzene, 5-cyclohexyl-1, 3-bis (. alpha. -hydroxyisopropyl) benzene, etc.
The substituent contained in the compound (a) is not particularly limited, and the compounds exemplified above can be used, and when a substituent having a large steric hindrance is used, the resulting maleimide is less likely to be stacked and the crystallization of the maleimide is less likely to occur, that is, the solvent solubility of the maleimide is improved, as compared with a substituent having a small steric hindrance.
As the compound represented by the above general formula (5) (hereinafter, "compound (b)"), typically, in addition to aniline, there can be used dimethylaniline, diethylaniline, diisopropylaniline, ethylmethylaniline, chloroaniline, dichloroaniline, toluidine, dimethylaniline, phenylaniline, nitroaniline, aminophenol, cyclohexylaniline, and the like. Furthermore, methoxyaniline, ethoxyaniline, phenoxyaniline, naphthyloxyaniline, aminothiol, methylthioaniline, ethylthioaniline and phenylthioaniline may also be exemplified.
In the case where a maleimide group is directly bonded to a benzene ring as in the case of a conventional maleimide (e.g., N-phenylmaleimide), the benzene ring and the 5-membered ring of the maleimide are stably aligned on the same plane, and therefore, they are easily stacked, and high crystallinity is exhibited. Therefore, the solvent solubility is poor. In contrast, in the case of the present invention, the compound (b) is not particularly limited, and the above exemplified compounds can be used, and for example, in the case of 2, 6-dimethylaniline having a methyl group as a substituent, the benzene ring and the 5-membered ring of maleimide are distorted due to steric hindrance of the methyl group, and the compound is not easily accumulated, and therefore, the crystallinity is reduced and the solvent solubility is improved, which is a preferable embodiment. Among them, if the steric hindrance is too large, reactivity may be inhibited at the time of synthesizing maleimide, and therefore, for example, the compound (b) having an alkyl group having 2 to 4 carbon atoms is preferably used.
In the method for producing an intermediate amine compound represented by the general formula (6) used in the present invention, the compound (a) and the compound (b) are fed and reacted at a molar ratio of the compound (b) to the compound (a) (compound (b)/compound (a)) of preferably 0.1 to 2.0, more preferably 0.2 to 1.0 (stage 1), and then the compound (b) is further fed and reacted at a molar ratio of preferably 0.5 to 20.0, more preferably 0.7 to 5.0 to the previously fed compound (a) (stage 2), whereby a maleimide (a) having an indane skeleton can be obtained. In addition, the 2-stage reaction has preferable results in view of the completion of the reaction, the handling property, and the like. In the reaction of the 1 st stage, the compound (b) is preferably set to 0.10 to 0.49, more preferably 0.15 to 0.40, and further preferably 0.20 to 0.39 in terms of a molar ratio (compound (b)/compound (a)) to the previously added compound (a), so that the molecular weight distribution is broad, the content ratio of the low-molecular-weight high-melting-point substance is low, and the ratio of the high-molecular-weight component is high, whereby an intermediate amine compound and maleimide which are excellent in solvent solubility and can contribute to flexibility and brittleness resistance can be obtained, and thus, it is preferable.
The acid catalyst used in the reaction may be, for example, an inorganic acid such as phosphoric acid, hydrochloric acid or sulfuric acid, an organic acid such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid or fluoromethanesulfonic acid, a solid acid such as activated clay, acid clay, silica-alumina, zeolite or strongly acidic ion exchange resin, a heteropolyacid salt or the like, and the solid acid which can be removed easily by filtration after the reaction is preferable from the viewpoint of handling properties.
The amount of the acid catalyst to be mixed is preferably 5 to 40 parts by mass based on 100 parts by mass of the total amount of the compound (a) and the compound (b) of the raw materials to be initially charged, and 5 to 30 parts by mass in view of handling efficiency and economy. The reaction temperature is usually in the range of 100 to 300 ℃ and is preferably 150 to 230 ℃ in order to suppress the formation of an isomer structure and avoid side reactions such as thermal decomposition.
The reaction time is usually in the range of 2 to 48 hours, preferably 2 to 24 hours, more preferably 4 to 24 hours, and further preferably 4 to 12 hours in total, and more preferably 8 to 12 hours in total for reducing low molecular weight components and increasing high molecular weight components, because the reaction does not proceed completely when the reaction time is short, and side reactions such as thermal decomposition reaction of the product are caused when the reaction time is long.
In the method for producing the intermediate amine compound, aniline or a derivative thereof also serves as a solvent, and therefore, it is not necessary to use another solvent, and a solvent may be used. For example, in the case of a reaction system having a dehydration reaction, specifically, in the case of reacting a compound having an α -hydroxypropyl group as a raw material, the following method can be employed: after completion of the dehydration reaction using a solvent capable of azeotropic dehydration such as toluene, xylene or chlorobenzene, the solvent is distilled off, and then the reaction is carried out at the above-mentioned reaction temperature range.
The maleimide (a) used in the present invention can be obtained as follows: the intermediate amine compound represented by the above general formula (6) obtained by the above method is charged into a reactor, dissolved in an appropriate solvent, reacted in the presence of maleic anhydride and a catalyst, unreacted maleic anhydride and other impurities are removed by washing with water or the like after the reaction, and the solvent is removed by reducing the pressure. In addition, a dehydrating agent may be used in the reaction.
The maleimide (a) used in the present invention includes a structure represented by the above general formula (7) having a skeleton of the above general formula (1) and an indane skeleton, and when q is 3 or less and at least 2 of ortho-positions and para-positions of amino groups are hydrogen atoms, a structure corresponding to the above general formula (8), that is, a structure represented by the below general formula (9) may be included as the structure represented by the above general formula (1).
Figure BDA0003319414500000111
Ra, Rb, q, r and m in the above general formula (9) have the same meanings as described above.
Examples of the organic solvent used in the maleimidoylation reaction for synthesizing the maleimide (a) include ketones such as acetone, Methyl Ethyl Ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone, aprotic solvents such as N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane, cyclic ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, and aromatic solvents such as benzene, toluene, and xylene, and these solvents may be used alone or in combination.
In the maleimide-based reaction, it is preferable that the intermediate amine compound and maleic anhydride are mixed in such a manner that the equivalent ratio of maleic anhydride to the amino equivalent of the intermediate amine compound is 1 to 1.5, more preferably 1.1 to 1.2, and the reaction is carried out in an organic solvent in a mass ratio of 0.5 to 50, preferably 1 to 5, relative to the total amount of the intermediate amine compound and maleic anhydride.
Examples of the catalyst used in the maleimide reaction include inorganic salts such as acetates, chlorides, bromides, sulfates and nitrates of nickel, cobalt, sodium, calcium, iron, lithium and manganese, inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and fluoromethanesulfonic acid, solid acids such as activated clay, acid clay, silica-alumina, zeolite and strongly acidic ion exchange resins, and heteropolyacid salts, and toluenesulfonic acid is particularly preferably used.
Examples of the dehydrating agent used in the maleimide reaction include lower aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, oxides such as phosphorus pentoxide, calcium oxide and barium oxide, inorganic acids such as sulfuric acid, porous ceramics such as a molecular sieve, and the like, and acetic anhydride is preferably used.
The amount of the catalyst and the dehydrating agent used in the maleimide reaction is not limited, and usually, the catalyst is used in an amount of 0.0001 to 1.0 mol, preferably 0.001 to 0.5mol, more preferably 0.01 to 0.3 mol, and the dehydrating agent is used in an amount of 1 to 3mol, preferably 1 to 1.5mol, based on 1 equivalent of the amino group of the intermediate amine compound.
The maleimide reaction is carried out by charging the intermediate amine compound and maleic anhydride, reacting at 10 to 100 ℃, preferably 30 to 50 ℃ for 0.5 to 12 hours, preferably 1 to 8 hours, adding the catalyst, reacting at 90 to 130 ℃, preferably 105 to 120 ℃ for 2 to 24 hours, preferably 4 to 10 hours, and reducing the low molecular weight component and increasing the high molecular weight component, more preferably 6 to 10 hours. After the reaction, unreacted maleic anhydride and other impurities are removed by washing with water or the like, and the reaction product is aged by heating, so that the low molecular weight component is reduced and the high molecular weight component is increased.
The maleimide (A) has a molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) calculated by Gel Permeation Chromatography (GPC) measurement in the range of preferably 1.0 to 10.0, more preferably 1.1 to 9.0, still more preferably 1.1 to 8.0, still more preferably 1.2 to 5.0, still more preferably 1.2 to 4.0, still more preferably 1.3 to 3.8, particularly preferably 1.3 to 3.6, and most preferably 1.3 to 3.4, from the viewpoint of excellent low dielectric constant and low dielectric loss tangent. In addition, according to the GPC diagram obtained by the GPC measurement, when the molecular weight distribution is wide and the high molecular weight component is large, the ratio of the high molecular weight component contributing to flexibility is large, and therefore, compared with a cured product using a conventional maleimide, brittleness can be suppressed, and a cured product excellent in flexibility and flexibility can be obtained, which is a preferable embodiment.
< measurement of GPC >
The molecular weight distribution (Mw/Mn) of the maleimide (A) was measured based on Gel Permeation Chromatography (GPC) using the following conditions.
A measuring device: HLC-8320GPC, manufactured by Tosoh corporation "
Column: "HXL-L" manufactured by Tosoh corporation, "TSK-GEL G2000 HXL" manufactured by Tosoh corporation, "TSK-GEL G3000 HXL" manufactured by Tosoh corporation "+ TSK-GEL G4000HXL manufactured by Tosoh corporation"
A detector: RI (differential refractometer)
Data processing: "EcoSEC-WorkStation" of Tosoh corporation "
The measurement conditions were as follows: column temperature 40 deg.C
Tetrahydrofuran as developing solvent
Flow rate 1.0 ml/min
The standard is as follows: the following monodisperse polystyrenes having known molecular weights were used according to the manual of the aforementioned "EcoSeC-WorkStation by GPC WorkStation".
(use of polystyrene)
"A-500" made by Tosoh corporation "
"A-1000" made by Tosoh corporation "
"A-2500" made by Tosoh corporation "
"A-5000" manufactured by Tosoh corporation "
"F-1" made by Tosoh corporation "
"F-2" made by Tosoh corporation "
"F-4" made by Tosoh corporation "
"F-10" made by Tosoh corporation "
"F-20" made by Tosoh corporation "
"F-40" made by Tosoh corporation "
"F-80" made by Tosoh corporation "
"F-128" made by Tosoh corporation "
Sample preparation: a tetrahydrofuran solution of 1.0 mass% of the maleimide obtained in the synthesis example, in terms of resin solid content, was filtered through a microfilter (50. mu.l).
< Compound (B) having substituent having unsaturated bond >
The curable resin composition of the present invention is characterized by containing a compound (B) having an unsaturated bond-containing substituent (hereinafter, sometimes referred to as "component (B)"). Since the compound (B) having a substituent having an unsaturated bond can exhibit a high crosslinking density by reacting the substituent having an unsaturated bond (e.g., allyl group) with a maleimide group and can give a cured product having a low polarity change, the use of the curable resin composition containing the compound (B) having a substituent having an unsaturated bond can be utilized as a molding material for electronic materials and is useful. In addition, the reaction with the maleimide having an indane skeleton (a) can function as a curing agent, and three-dimensionally crosslink the maleimide, whereby a cured product having excellent heat resistance can be obtained, which is a preferred embodiment. Further, the epoxy resin (C) functions as a curing agent to improve adhesion to copper, and is useful for manufacturing a circuit board using a copper foil, for example.
The compound (B) having an unsaturated bond-containing substituent is not particularly limited as long as it has 2 or more unsaturated bond-containing substituents in the molecule, and examples of the unsaturated bond-containing substituent include allyl, isopropenyl, 1-propenyl, acryloyl, methacryloyl, styryl, styrylmethyl, and the like. Among these, allyl, 1-propenyl, styryl, styrylmethyl and the like are preferable in that they exhibit good reactivity with maleimide groups, provide a cured product having a high crosslinking density, and are excellent in heat resistance.
The compound (B) having an unsaturated bond-containing substituent may further have a reactive functional group other than the unsaturated bond-containing substituent. The reactive functional group is not particularly limited, and examples thereof include an isocyanate group, a hydroxyl group, an epoxy group, an active ester group, an amine group, an isocyanate group, a glycidyl group, and a phosphoric group. Among them, at least 1 selected from the group consisting of cyanate ester groups, hydroxyl groups, epoxy groups, and active ester groups is preferable, and cyanate ester groups are more preferable. By having a hydroxyl group, a cyanate group, an epoxy group, and an active ester group, the material tends to have high flexural strength and flexural modulus, low dielectric constant, high glass transition temperature (Tg), low thermal expansion coefficient, and further improved thermal conductivity.
The unsaturated bond-containing substituent-containing compound (B) having a reactive functional group other than the unsaturated bond-containing substituent may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When 2 or more compounds (B) having an unsaturated bond-containing substituent having a reactive functional group other than an unsaturated bond-containing substituent are used in combination, the reactive functional groups other than the unsaturated bond-containing substituent may be the same or different. Among them, the compound (B) having an unsaturated bond-containing substituent in which the reactive functional group is a cyanate group and the compound (B) having an unsaturated bond-containing substituent in which the reactive functional group is an epoxy group are preferably contained. By using such a compound (B) having a substituent having an unsaturated bond in combination, the flexural strength, flexural modulus, glass transition temperature (Tg), and thermal conductivity tend to be further improved.
Examples of the compound (B) having an unsaturated bond-containing substituent include bisphenols in which a hydrogen atom of an aromatic ring is substituted with an allyl group, modified phenolic compounds in which a hydrogen atom of an aromatic ring is substituted with an allyl group and a phenolic hydroxyl group is modified with a reactive functional group other than a hydroxyl group among the reactive functional groups other than the unsaturated bond-containing substituent, and specifically, a cyanate compound of diallylbisphenol a, a type epoxy compound of diallylbisphenol a, an allyl phenol-terminated reactive ester compound, and the like.
The bisphenol is not particularly limited, and examples thereof include bisphenol a, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z. Among them, bisphenol A is preferred.
< epoxy resin (C) >
The curable resin composition of the present invention is characterized by containing an epoxy resin (C) (hereinafter, sometimes referred to as a "(C) component"). The epoxy resin (C) is useful because it has good fluidity in the production of a curable resin composition and can produce a curable resin composition that can give a cured product having excellent adhesion. In addition, when the compound (B) having a substituent having an unsaturated bond and the epoxy resin (C) are used, adhesion to copper is improved, and the compound (B) is useful for manufacturing a circuit board using a copper foil, for example.
The epoxy resin (C) is not particularly limited, and examples thereof include novolac-type epoxy resins such as phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, α -naphthol novolac-type epoxy resin, β -naphthol novolac-type epoxy resin, bisphenol a novolac-type epoxy resin, and biphenol novolac-type epoxy resin; aralkyl type epoxy resins such as phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin and the like; bisphenol type epoxy resins such as bisphenol a type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol a type epoxy resin; biphenyl type epoxy resins such as biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyl oxybenzene skeleton; naphthalene type epoxy resins; binaphthol type epoxy resins; a binaphthyl-type epoxy resin; dicyclopentadiene type epoxy resins such as dicyclopentadiene phenol type epoxy resins; glycidyl amine type epoxy resins such as tetraglycidyl diaminodiphenylmethane type epoxy resin, triglycidyl p-aminophenol type epoxy resin, and glycidyl amine type epoxy resin of diaminodiphenyl sulfone; diglycidyl ester type epoxy resins such as 2, 6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resin and glycidyl ester type epoxy resin of hexahydrophthalic anhydride; and benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. These may be used alone or in combination of 2 or more.
Among these, particularly preferred are phenol aralkyl type epoxy resins, biphenyl novolac type epoxy resins, naphthol novolac type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol copolycondensation novolac type epoxy resins, naphthol-cresol copolycondensation novolac type epoxy resins, crystalline biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, xanthene type epoxy resins, alkoxy group-containing aromatic ring-modified novolac type epoxy resins (compounds in which glycidyl group-containing aromatic rings and alkoxy group-containing aromatic rings are connected by formaldehyde), and the like, from the viewpoint of obtaining cured products excellent in heat resistance.
The curable resin composition of the present invention may contain a curing agent other than the compound (B) having a substituent having an unsaturated bond, within a range not impairing the curing of the present invention. The unsaturated bond-containing substituent-containing compound (B) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more, based on 100% by mass of the total amount of the curing agent.
Examples of the curing agent other than the compound (B) having an unsaturated bond-containing substituent include amine compounds, amide compounds, anhydride compounds, phenol compounds, polyphenylene ether compounds, cyanate compounds, diene polymers, and the like. These curing agents may be used alone, or 2 or more kinds may be used in combination.
Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, and BF3Amine complexes, guanidine derivatives, etc.
Examples of the amide compound include dicyandiamide and polyamide resins synthesized from a dimer of linolenic acid and ethylenediamine.
Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
Examples of the phenol compound include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition-type resins, phenol aralkyl resins (Xylock resins), polyhydric phenol novolac resins synthesized from a polyhydric hydroxyl compound and formaldehyde, such as resorcinol novolac resins, naphthol aralkyl resins, trimethylolmethane resins, tetraphenylethane resins, naphthol novolac resins, naphthol-phenol co-condensed novolac resins, naphthol-cresol co-condensed novolac resins, biphenyl-modified phenol resins (polyhydric phenol compounds obtained by connecting phenol cores with dimethylene), biphenyl-modified naphthol resins (polyhydric naphthol compounds obtained by connecting phenol cores with dimethylene), aminotriazine-modified phenol resins (polyhydric naphthol compounds obtained by connecting phenol cores with dimethylene), and the like, Polyphenol compounds such as benzoguanamine, which are composed of phenol nuclei linked together), and alkoxy group-containing aromatic ring-modified novolak resins (polyphenol compounds composed of phenol nuclei and alkoxy group-containing aromatic rings linked together with formaldehyde).
The polyphenylene ether compound has, for example, a structure represented by the following general formula (10) or (11).
Figure BDA0003319414500000181
Rd in the general formulae (10) and (11) is independently hydrogen, alkyl group having 1 to 5 carbon atoms, alkenyl group having 1 to 5 carbon atoms, cycloalkyl group having 3 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, thioether group having 1 to 5 carbon atoms, alkylcarbonyl group having 2 to 5 carbon atoms, alkoxycarbonyl group having 2 to 5 carbon atoms, alkylcarbonyloxy group having 2 to 5 carbon atoms, alkylsulfonyl group having 1 to 5 carbon atoms, or the like. Examples of the terminal structure of the structures of the general formulae (10) and (11) include a structure having a hydroxyl group or a group containing a reactive double bond. In addition, s is an integer value of 1 to 30, and t and u are also integer values of 1 to 30.
The alkyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a propyl group.
The alkenyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-pentenyl group, and an isopropenyl group.
The cycloalkyl group having 3 to 5 carbon atoms is not particularly limited, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, methylcyclobutyl and the like.
The alkoxy group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a pentoxy group.
The thioether group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, and a pentylthio group.
The alkylcarbonyl group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, an isopropylcarbonyl group, and a butylcarbonyl group.
The alkoxycarbonyl group having 2 to 5 carbon atoms is not particularly limited, and includes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl and the like.
The alkylcarbonyloxy group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, and a butylcarbonyloxy group.
The alkylsulfonyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, and pentylsulfonyl group.
Among these, Rd is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 3 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, further preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom or a methyl group.
Examples of Y in the above-mentioned (11) include 2-valent aromatic groups derived from an aromatic compound having 2 phenolic hydroxyl groups.
The aromatic compound having 2 phenolic hydroxyl groups is not particularly limited, and examples thereof include catechol, resorcinol, hydroquinone, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, 4' -biphenol, bisphenol a, bisphenol B, bisphenol BP, bisphenol C, bisphenol F, tetramethylbisphenol a, and the like. Among these, hydroquinone, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, 4 '-biphenol, bisphenol a, bisphenol E, and bisphenol F are preferable, and 4, 4' -biphenol, bisphenol a, and tetramethylbisphenol a are more preferable.
Since 2 phenolic hydroxyl groups of the aforementioned aromatic compound having 2 phenolic hydroxyl groups form a phenylene ether bond (2 oxygen atoms bonded to Y), Y becomes an aromatic group having a valence of 2 derived from the aromatic compound having 2 phenolic hydroxyl groups.
Examples of the cyanate ester compound include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol thioether type cyanate ester resin, phenylene ether type cyanate ester resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, triphenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol copolycondensation type cyanate ester resin, naphthol-cresol copolycondensation type cyanate ester resin, naphthol-phenol copolycondensation type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol thioether sulfide type cyanate ester resin, phenylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol type cyanate ester resin, and the like, Aromatic hydrocarbon formaldehyde resin-modified phenolic resin type cyanate ester resin, biphenyl-modified novolak type cyanate ester resin, anthracene type cyanate ester resin, and the like.
Examples of the diene polymer include non-modified diene polymers which are not modified with a polar group. The polar group is a functional group that affects dielectric characteristics, and examples thereof include a phenol group, an amino group, and an epoxy group. The diene polymer is not particularly limited, and for example, 1, 2-polybutadiene, 1, 4-polybutadiene, and the like can be used.
As the diene polymer, a homopolymer of butadiene having 1, 2-bond or more in 50% or more of the butadiene units in the polymer chain and a derivative thereof may be used.
Since the epoxy resin (C) is used in the present invention, a curing accelerator may be suitably used in combination with the curable resin composition of the present invention as needed. As the curing accelerator, various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts and the like. In particular, when the phosphorus-containing compound is used as a semiconductor sealing material, triphenylphosphine and 1, 8-diazacyclo- [5.4.0] -undecene (DBU) are preferable as the phosphorus-containing compound, from the viewpoint of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, and the like. These curing accelerators may be used alone or in combination of 2 or more. The amount of the curing accelerator added is preferably in the range of, for example, 1 to 10 parts by mass per 100 parts by mass of the epoxy resin (C).
< preparation of curable resin composition >
The curable resin composition of the present invention is characterized by containing: a maleimide having an indane skeleton, (B) a compound having a substituent having an unsaturated bond, and (C) an epoxy resin. By providing the maleimide (a) with an indane skeleton, a cured product having excellent dielectric properties can be obtained because the curable resin composition has excellent solvent solubility, is easy to prepare, and has excellent handling properties, compared with conventional maleimides, and because the proportion of polar functional groups in the structure of the maleimide (a) is small. The compound (B) having a substituent having an unsaturated bond, which functions as a curing agent, can contribute to the formation of a cured product having a high crosslinking density by reacting the unsaturated bond with a maleimide group, and the epoxy resin (C) has good fluidity when used for the preparation of a curable resin composition, and can give a cured product having excellent adhesion. In addition, the compound (B) having an unsaturated bond-containing substituent, which functions as a curing agent, is reacted with the maleimide (a) and the epoxy resin (C), whereby three-dimensional crosslinking can be caused, and a cured product having excellent heat resistance can be obtained, which is a preferred embodiment. Further, the reaction between the compound (B) having a substituent having an unsaturated bond and the epoxy resin (C) improves the adhesion to copper, and is useful for, for example, the production of a circuit board using a copper foil.
The blending ratio (parts by mass) of the component (a) to the components (B) and (C) is: the ratio of ((B) component + (C) component) is preferably 90: 10-10: 90, more preferably 80: 20-20: 80, more preferably 65: 35-35: 65, particularly preferably 55: 45-45: 55. by adjusting the compounding ratio within the above range, heat resistance, a low dielectric constant and a low dielectric loss tangent can be achieved, which is preferable.
In the curable resin composition of the present invention, the compounding ratio (parts by mass) of the compound (B) having an unsaturated bond-containing substituent to the epoxy resin (C) is not particularly limited, and the component (B): (C) the component is preferably 90: 10-10: 90, more preferably 80: 20-20: 80, more preferably 65: 35-35: 65. by adjusting the compounding ratio within the above range, heat resistance, a low dielectric constant and a low dielectric loss tangent can be achieved, which is preferable.
The curable resin composition of the present invention may further contain an alkenyl group-containing compound, for example, bismaleimides other than the maleimide (a), triallyl cyanurate, an alkenyl phenol compound, a vinyl group-containing polyolefin compound, and the like, in such an amount that the object is not impaired. Other thermosetting resins, for example, thermosetting polyimide resins, polyphenylene ethers, phenol resins, active ester resins, benzoxazine resins, cyanate ester resins, and the like can be appropriately blended according to the purpose.
In order to exhibit flame retardancy, the curable resin composition of the present invention may contain a non-halogen flame retardant that does not substantially contain a halogen atom within a range that does not impair the object. Examples of the non-halogen flame retardant include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants, which may be used alone or in combination.
The curable resin composition of the present invention may contain an inorganic filler, if necessary. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. In particular, when the amount of the inorganic filler is increased, fused silica is preferably used. The fused silica may be in any shape of crushed or spherical, and it is preferable to mainly use spherical fused silica in order to increase the amount of fused silica to be blended and to suppress an increase in melt viscosity of the molding material. Further, in order to increase the amount of the spherical silica to be blended, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling ratio is preferably high in view of flame retardancy, and is particularly preferably 20% by mass or more based on the total amount of the curable resin composition. When the curable resin composition is used for the purpose of conductive paste or the like described in detail below, a conductive filler such as silver powder or copper powder can be used.
The curable resin composition of the present invention may contain various blending agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier, as required.
< cured product >
The cured product of the present invention is preferably obtained by curing the curable resin composition. The curable resin composition can be obtained by uniformly mixing the above-mentioned components, and a cured product can be easily produced by the same method as a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast molded products, adhesive layers, coating films, and films.
The curing (thermosetting) reaction can be easily carried out without a catalyst, and when a rapid reaction is desired, the addition of a polymerization initiator such as an organic peroxide or an azo compound, and a basic catalyst such as a phosphine compound or a tertiary amine is effective. Examples of the amount of the organic solvent include benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, and imidazoles, and the amount of the organic solvent is preferably 0.05 to 5% by mass of the entire curable resin composition.
< prepreg >
The prepreg of the present invention preferably has a reinforcing base material and a semi-cured product of the curable resin composition impregnated in the reinforcing base material. As the method for producing the prepreg, a known method can be used, and a prepreg can be produced by impregnating a reinforcing base material with a resin varnish in which the curable resin composition is dissolved (diluted) in an organic solvent, and thermally treating the reinforcing base material impregnated with the resin varnish to semi-cure (or not cure) the curable resin composition.
As the organic solvent, for example, one kind alone or a mixed solvent of 2 or more kinds may be used from toluene, xylene, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, Methyl Ethyl Ketone (MEK), methyl isobutyl ketone, dioxane, tetrahydrofuran, and the like.
The reinforcing base material impregnated with the resin varnish may be a woven fabric or a nonwoven fabric made of inorganic fibers such as glass fibers, polyester fibers and polyamide fibers or organic fibers, or a mat or a paper, and these may be used alone or in combination.
The mass ratio of the curable resin composition to the reinforcing base material in the prepreg is not particularly limited, and it is generally preferable to prepare the prepreg so that the curable resin composition (resin in the prepreg) is 20 to 60 mass%.
The conditions for the heat treatment of the prepreg may be suitably selected depending on the kind and amount of the organic solvent, catalyst, and various additives to be used, and are usually carried out at a temperature of 80 to 220 ℃ for 3 to 30 minutes.
< Heat-resistant Material and electronic Material >
The cured product obtained from the curable resin composition of the present invention is excellent in heat resistance and dielectric properties, and therefore can be suitably used for heat-resistant members and electronic members. In particular, the resin composition can be suitably used for circuit boards, semiconductor sealing materials, semiconductor devices, laminated films, laminated boards, adhesives, resist materials, and the like. In addition, the resin composition can be used as a matrix resin for a fiber-reinforced resin, and is particularly suitable as a prepreg having high heat resistance. In addition, the maleimide (a) having an indane skeleton contained in the curable resin composition exhibits excellent solubility in various solvents, and thus can be made into a coating material. The heat-resistant member and the electronic member obtained in this way can be suitably used for various applications, and examples thereof include industrial machine parts, general machine parts, parts of automobiles, railways, vehicles and the like, space and aviation-related parts, electronic and electric parts, building materials, container and packaging members, living goods, sports and leisure goods, and housing members for wind power generation, but are not limited to these.
Hereinafter, a typical product produced by using the curable resin composition of the present invention will be described by way of example.
< Circuit Board >
In the present invention, the circuit board is preferably obtained by laminating the prepreg and the copper foil and performing thermocompression bonding molding. Specifically, examples of the method for obtaining a circuit board from the curable resin composition of the present invention include the following methods: the prepreg is laminated by a conventional method, and is suitably laminated with a copper foil, and is subjected to thermocompression bonding molding at 170 to 300 ℃ for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.
< semiconductor sealing Material >
In the present invention, the curable resin composition is preferably contained as a semiconductor sealing material. Specifically, examples of the method for obtaining a semiconductor sealing material from the curable resin composition of the present invention include the following methods: in the curable resin composition, a curing accelerator as an optional component and a compounding agent such as an inorganic filler are further sufficiently melt-mixed using an extruder, a kneader, a roll, or the like as necessary until uniform. In this case, fused silica is generally used as the inorganic filler, and when used as a high-thermal-conductivity semiconductor sealing material for power transistors and power ICs, crystalline silica, alumina, silicon nitride, or the like having a higher thermal conductivity than fused silica is preferably used, and further, it is preferable to highly fill the same. The filling rate is preferably 30 to 95 parts by mass of an inorganic filler per 100 parts by mass of the curable resin composition, and more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more, in order to improve flame retardancy, moisture resistance and solder crack resistance and reduce a linear expansion coefficient.
< semiconductor device >
In the present invention, the semiconductor device preferably includes a cured product obtained by heat-curing the semiconductor sealing material. Specifically, as a semiconductor package molding method for obtaining a semiconductor device from the curable resin composition of the present invention, the following methods can be mentioned: the semiconductor sealing material is cast or molded by a transfer molding machine, an injection molding machine or the like, and further cured by heating at 50 to 250 ℃ for 2 to 10 hours.
< laminated substrate >
The method for obtaining a laminated substrate from the curable resin composition of the present invention includes the method including steps 1 to 3. In step 1, the curable resin composition containing a rubber, a filler, and the like as appropriate is applied to a circuit board on which a circuit is formed by a spray coating method, a curtain coating method, or the like, and then cured. In step 2, the circuit board coated with the curable resin composition is subjected to drilling of a predetermined through hole or the like, treated with a roughening agent, and the surface thereof is cleaned with hot water to form irregularities on the board and plated with a metal such as copper, if necessary. In step 3, the operations of steps 1 to 2 are sequentially repeated as desired, and the resin insulation layers and the conductor layers of the predetermined circuit pattern are alternately laminated to form a laminated substrate. In the above step, it is preferable that the through hole is drilled after the outermost resin insulation layer is formed. In the laminate substrate of the present invention, a resin-coated copper foil obtained by semi-curing the resin composition on a copper foil may be heat-pressed at 170 to 300 ℃ onto a wiring substrate having a circuit formed thereon to form a roughened surface, and the step of plating treatment may be omitted to produce a laminate substrate.
< laminated film >
The laminate film of the present invention preferably contains the curable resin composition. Examples of the method for obtaining a laminated film from the curable resin composition of the present invention include the following methods: after the curable resin composition is applied to the support film, it is dried, thereby forming a resin composition layer on the support film. When the curable resin composition of the present invention is used for a build-up film, it is important that the film is softened under the temperature conditions for lamination in a vacuum lamination method (usually 70 to 140 ℃), and exhibits fluidity (resin flow) that allows filling of resin present in via holes or through holes of a circuit board while laminating the circuit board, and it is preferable to blend the above components in order to exhibit such characteristics. In the obtained multilayer film and circuit board (such as a copper-clad laminate), uniformity in appearance is required so that predetermined performance is exhibited at any position without causing a phenomenon that a characteristic value is locally different due to phase separation or the like.
Here, the diameter of the through hole of the circuit board is usually 0.1 to 0.5mm, and the depth is usually 0.1 to 1.2mm, and the resin filling can be usually performed within this range. When both surfaces of the circuit board are laminated, it is desirable that about 1/2 of the through hole is filled.
Specific examples of the method for producing the laminated film include the following methods: the organic solvent is blended to prepare a varnished resin composition, and the varnished resin composition is applied to the surface of the support film (Y), and the organic solvent is dried by heating, hot air blowing, or the like to form the resin composition layer (X).
As the organic solvent used here, for example, ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide and N-methylpyrrolidone are preferably used in a proportion of 30 to 60 mass% of nonvolatile components.
The thickness of the resin composition layer (X) to be formed is generally required to be equal to or greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, and therefore, the thickness of the resin composition layer (X) is preferably 10 to 100 μm. The resin composition layer (X) in the present invention may be protected by a protective film described later. The protective film protects the surface of the resin composition layer from dust and the like and prevents damage.
Examples of the support film and the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonates, polyimides, and further metal foils such as release paper, copper foil, and aluminum foil. The support film and the protective film may be subjected to a matting treatment, a corona treatment, and a mold release treatment. The thickness of the support film is not particularly limited, and is usually 10 to 150 μm, preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.
The support film (Y) is laminated on a circuit board or is thermally cured to form an insulating layer and then peeled off. When the support film (Y) is peeled off after the resin composition layer constituting the laminated film is heat-cured, adhesion of dust and the like in the curing step can be prevented. When the support film is peeled after curing, the support film is usually subjected to a mold release treatment in advance.
A multilayer printed wiring board can be manufactured from the laminate film obtained as described above. For example, when the resin composition layer (X) is protected by a protective film, the resin composition layer (X) is peeled off and then laminated on one surface or both surfaces of a circuit board by, for example, a vacuum lamination method so as to be in direct contact with the circuit board. The lamination method may be a batch method or a continuous method using a roll. Further, the laminate film and the circuit board may be heated (preheated) as necessary before lamination, if necessary. For lamination conditions, the pressure is warmedThe degree (laminating temperature) is preferably 70 to 140 ℃, and the pressure bonding pressure is preferably 1 to 11kgf/cm2(9.8×104～107.9×104N/m2) The lamination is preferably performed under reduced pressure of 20mmHg (26.7hPa) or less.
< conductive paste >
As a method for obtaining a conductive paste from the curable resin composition of the present invention, for example, a method of dispersing conductive particles in the composition can be cited. The conductive paste may be a paste resin composition for circuit connection or an anisotropic conductive adhesive, depending on the type of conductive particles used.
Examples
The present invention is described specifically by examples and comparative examples, and the following "parts" and "%" are based on mass unless otherwise specified. The softening point, amine equivalent, GPC, and FD-MS spectra were measured and evaluated under the following conditions.
1) Softening point
The determination method comprises the following steps: the softening point (. degree. C.) of the intermediate amine compound obtained in the synthesis examples shown below was measured in accordance with JIS K7234 (Ring and ball method).
2) Amine equivalent
The amine equivalent of the intermediate amine compound was measured by the following measurement method.
About 2.5g of an intermediate amine compound, 7.5g of pyridine, 2.5g of acetic anhydride, and 7.5g of triphenylphosphine were precisely weighed in a 500mL Erlenmeyer flask with a stopper, and then a condenser tube was attached to the weighed intermediate amine compound, and the weighed intermediate amine compound was heated and refluxed for 150 minutes in an oil bath set to 120 ℃.
After cooling, 5.0mL of distilled water, 100mL of propylene glycol monomethyl ether, and 75mL of tetrahydrofuran were added, and titration was carried out by potentiometric titration using a 0.5mol/L potassium hydroxide-ethanol solution. Blank tests were carried out and corrected in the same manner.
Amine equivalent (g/eq.) - (S × 2000)/(Blank-a)
S: amount of sample (g)
A: consumption of 0.5mol/L Potassium hydroxide-ethanol solution (mL)
Blank: consumption of 0.5mol/L Potassium hydroxide-ethanol solution in blank test (mL)
3) GPC measurement
The following measurement apparatus and measurement conditions were used to perform measurement, and GPC diagrams (fig. 1 to 9) of the maleimide obtained in the following synthesis examples were obtained. From the results of the GPC chart, the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) and the average number of repeating units "n" contributing to the indane skeleton in the maleimide were measured/calculated based on the number average molecular weight (Mn). Specifically, for a compound in which n is 0 to 4, the theoretical molecular weight and the molecular weight of each measured value in GPC are plotted on a scatter diagram, an approximate straight line is drawn, the number average molecular weight (Mn) is obtained from the point indicated by the measured value Mn (1) on the straight line, and n is calculated.
A measuring device: HLC-8320GPC, manufactured by Tosoh corporation "
Column: "HXL-L" manufactured by Tosoh corporation, "TSK-GEL G2000 HXL" manufactured by Tosoh corporation, "TSK-GEL G3000 HXL" manufactured by Tosoh corporation "+ TSK-GEL G4000HXL manufactured by Tosoh corporation"
A detector: RI (differential refractometer)
Data processing: "EcoSEC-WorkStation" of Tosoh corporation "
The measurement conditions were as follows: column temperature 40 deg.C
Tetrahydrofuran as developing solvent
Flow rate 1.0 ml/min
The standard is as follows: the following monodisperse polystyrenes having known molecular weights were used according to the manual of the aforementioned "EcoSeC-WorkStation by GPC WorkStation".
(use of polystyrene)
"A-500" made by Tosoh corporation "
"A-1000" made by Tosoh corporation "
"A-2500" made by Tosoh corporation "
"A-5000" manufactured by Tosoh corporation "
"F-1" made by Tosoh corporation "
"F-2" made by Tosoh corporation "
"F-4" made by Tosoh corporation "
"F-10" made by Tosoh corporation "
"F-20" made by Tosoh corporation "
"F-40" made by Tosoh corporation "
"F-80" made by Tosoh corporation "
"F-128" made by Tosoh corporation "
Sample preparation: a tetrahydrofuran solution of 1.0 mass% of the maleimide obtained in the synthesis example, in terms of resin solid content, was filtered through a microfilter (50. mu.l).
4) FD-MS spectra
The FD-MS spectrum was measured using the following measurement apparatus and measurement conditions.
A measuring device: JMS-T100GC AccuTOF
Measurement conditions
Measurement range: m/z is 4.00-2000.00
Rate of change: 51.2 mA/min
Final current value: 45mA
Cathode voltage: -10kV
Recording interval: 0.07 second
Synthesis example 1 Synthesis of Maleimide Compound A-1
(1) Synthesis of intermediate amine compounds
In a 1L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, 48.5g (0.4mol) of 2, 6-dimethylaniline, 272.0g (1.4mol) of α, α' -dihydroxy-1, 3-diisopropylbenzene, 280g of xylene and 70g of activated clay were charged, and the mixture was heated to 120 ℃ with stirring. The reaction was further carried out for 3 hours while the temperature was raised to 210 ℃ with distilled water removed with a dean-Stark tube. Thereafter, the reaction mixture was cooled to 140 ℃ and 145.4g (1.2mol) of 2, 6-dimethylaniline was added, and then the temperature was raised to 220 ℃ to carry out the reaction for 3 hours. After the reaction, the reaction mixture was cooled to 100 ℃ with air, diluted with 300g of toluene, and filtered to remove the activated clay, and low molecular weight substances such as the solvent and unreacted substances were distilled off under reduced pressure, whereby 364.1g of an intermediate amine compound represented by the following general formula (A-1) was obtained. The amine equivalent weight is 298 and the softening point is 70 ℃.
Figure BDA0003319414500000311
(2) Maleinization of
131.8g (1.3mol) of maleic anhydride and 700g of toluene were put into a 2L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, and stirred at room temperature. Then, a mixed solution of 364.1g of the reactant (A-1) and 175g of DMF was added dropwise over 1 hour.
After completion of the dropwise addition, the reaction was further carried out at room temperature for 2 hours. 37.1g of p-toluenesulfonic acid monohydrate was added, the reaction solution was heated, water azeotropic under reflux and toluene were cooled/separated, and then only toluene was returned to the system to conduct dehydration reaction for 8 hours. After air-cooling to room temperature, concentration under reduced pressure was carried out, and the brown solution was dissolved in 600g of ethyl acetate, washed 3 times with 150g of ion-exchanged water and 3 times with 150g of a 2% aqueous solution of sodium hydrogencarbonate, dried by adding sodium sulfate, and then concentrated under reduced pressure, and the resulting reaction product was dried under vacuum at 80 ℃ for 4 hours to obtain 413.0g of a maleimide compound A-1-containing product. In the FD-MS spectrum of the maleimide compound a-1, peaks of M + ═ 560, 718, and 876 were observed, and each peak corresponds to a case where n is 0, 1, or 2. The number n of repeating units in the indane skeleton portion of the maleimide a-1 (based on the number average molecular weight) was determined by GPC, and the GPC chart thereof was shown in fig. 1, where n was 1.47 and the molecular weight distribution (Mw/Mn) was 1.81.
Figure BDA0003319414500000321
Synthesis example 2 Synthesis of Maleimide Compound A-2
(1) Synthesis of intermediate amine compounds
In a 1L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, 48.5g (0.4mol) of 2, 6-dimethylaniline, 233.2g (1.2mol) of α, α' -dihydroxy-1, 3-diisopropylbenzene, 230g of xylene and 66g of activated clay were charged, and the mixture was heated to 120 ℃ with stirring. The distilled water was further removed by using a dean-Stark tube and the temperature was raised to 210 ℃ to conduct the reaction for 3 hours. Thereafter, the reaction mixture was cooled to 140 ℃ and 145.4g (1.2mol) of 2, 6-dimethylaniline was added, and then the temperature was raised to 220 ℃ to carry out the reaction for 3 hours. After the reaction, the reaction mixture was cooled to 100 ℃ with air, diluted with 300g of toluene, and the activated clay was removed by filtration, and low molecular weight substances such as the solvent and unreacted substances were distilled off under reduced pressure, whereby 278.4g of an intermediate amine compound represented by the following general formula (a-2) was obtained. The amine equivalent weight is 294 and the softening point is 65 ℃.
Figure BDA0003319414500000322
(2) Maleinization of
107.9g (1.1mol) of maleic anhydride and 600g of toluene were put into a 2L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, and stirred at room temperature. A mixed solution of 278.4g of the reactant (A-2) and 150g of DMF was then added dropwise over 1 hour.
After completion of the dropwise addition, the reaction was further carried out at room temperature for 2 hours. 27.0g of p-toluenesulfonic acid monohydrate was added, the reaction solution was heated, water azeotropic under reflux and toluene were cooled/separated, and then only toluene was returned to the system to conduct dehydration reaction for 8 hours. After air-cooling to room temperature, concentration was carried out under reduced pressure, the brown solution was dissolved in 500g of ethyl acetate, washed 3 times with 120g of ion-exchanged water and 3 times with 120g of a 2% aqueous solution of sodium hydrogencarbonate, dried by adding sodium sulfate, and then concentrated under reduced pressure, and the resulting reaction product was vacuum-dried at 80 ℃ for 4 hours to obtain 336.8g of a maleimide compound A-2-containing product. In the FD-MS spectrum of the maleimide compound a-2, peaks at M + ═ 560, 718, and 876 were observed, corresponding to the cases where n was 0, 1, and 2, respectively. The number n of repeating units in the indane skeleton portion of the maleimide a-2 (based on the number average molecular weight) was determined by GPC, and the GPC chart thereof was shown in fig. 2, where n was 1.25 and the molecular weight distribution (Mw/Mn) was 3.29.
Figure BDA0003319414500000331
Synthesis example 3 Synthesis of Maleimide Compound A-3
(1) Synthesis of intermediate amine compounds
In a 2L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, 48.5g (0.4mol) of 2, 6-dimethylaniline, 388.6g (2.0mol) of. alpha.,. alpha.' -dihydroxy-1, 3-diisopropylbenzene, 350g of xylene and 123g of activated clay were charged and heated to 120 ℃ with stirring. The distilled water was further removed by using a dean-Stark tube and the temperature was raised to 210 ℃ to conduct the reaction for 3 hours. Thereafter, the reaction mixture was cooled to 140 ℃ and 145.4g (1.2mol) of 2, 6-dimethylaniline was added, and then the temperature was raised to 220 ℃ to carry out the reaction for 3 hours. After the reaction, the reaction mixture was cooled to 100 ℃ with air, diluted with 500g of toluene, and filtered to remove the activated clay, and low molecular weight substances such as the solvent and unreacted substances were distilled off under reduced pressure, whereby 402.1g of an intermediate amine compound represented by the following general formula (A-3) was obtained. The amine equivalent weight is 306 and the softening point is 65 ℃.
Figure BDA0003319414500000341
(2) Maleinization of
A2L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer was charged with 152.1g (1.5mol) of maleic anhydride and 700g of toluene and stirred at room temperature. Subsequently, a mixed solution of 402.1g of the reactant (A-3) and 200g of DMF was added dropwise over 1 hour.
After completion of the dropwise addition, the reaction was further carried out at room temperature for 2 hours. 37.5g of p-toluenesulfonic acid monohydrate was added, the reaction solution was heated, water azeotropic under reflux and toluene were cooled/separated, and then only toluene was returned to the system to conduct dehydration reaction for 8 hours. After air-cooling to room temperature, concentration was carried out under reduced pressure, the brown solution was dissolved in 800g of ethyl acetate, washed 3 times with 200g of ion-exchanged water and 3 times with 200g of 2% aqueous sodium bicarbonate solution, dried by adding sodium sulfate, and then concentrated under reduced pressure, and the resulting reaction product was dried under vacuum at 80 ℃ for 4 hours to obtain 486.9g of a maleimide compound a-3-containing product. In the FD-MS spectrum of the maleimide compound a-3, peaks at M + ═ 560, 718, and 876 were observed, corresponding to the cases where n was 0, 1, and 2, respectively. The value of the number n of repeating units in the indane skeleton portion of the maleimide a-3 (based on the number average molecular weight) was determined by GPC, and the GPC chart thereof was as shown in fig. 3, where n was 1.96 and the molecular weight distribution (Mw/Mn) was 1.52.
Figure BDA0003319414500000342
Synthesis example 4 Synthesis of Maleimide Compound A-4
(1) Synthesis of intermediate amine compounds
59.7g (0.4mol) of 2, 6-diethylaniline, 272.0g (1.4mol) of α, α' -dihydroxy-1, 3-diisopropylbenzene, 350g of xylene and 94g of activated clay were put into a 2L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, and heated to 120 ℃ with stirring. The distilled water was further removed by using a dean-Stark tube and the temperature was raised to 210 ℃ to conduct the reaction for 3 hours. Thereafter, the reaction mixture was cooled to 140 ℃ and 179.1g (1.2mol) of 2, 6-diethylaniline was added, followed by heating to 220 ℃ to carry out the reaction for 3 hours. After the reaction, the reaction mixture was cooled to 100 ℃ with air, diluted with 500g of toluene, and filtered to remove the activated clay, and low molecular weight substances such as the solvent and unreacted substances were distilled off under reduced pressure, whereby 342.1g of an intermediate amine compound represented by the following general formula (A-4) was obtained. The amine equivalent weight is 364 and the softening point is 47 ℃.
Figure BDA0003319414500000351
(2) Maleinization of
107.9g (1.1mol) of maleic anhydride and 600g of toluene were put into a 2L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, and stirred at room temperature. Then, a mixed solution of 342.1g of the reactant (A-4) and 180g of DMF was added dropwise over 1 hour.
After completion of the dropwise addition, the reaction was further carried out at room temperature for 2 hours. 26.8g of p-toluenesulfonic acid monohydrate was added, the reaction solution was heated, water azeotropic under reflux and toluene were cooled/separated, and then only toluene was returned to the system to conduct dehydration reaction for 8 hours. After air-cooling to room temperature, concentration was carried out under reduced pressure, the brown solution was dissolved in 500g of ethyl acetate, washed 3 times with 200g of ion-exchanged water and 3 times with 200g of 2% aqueous sodium bicarbonate solution, dried by adding sodium sulfate, and then concentrated under reduced pressure, and the resulting reaction product was dried under vacuum at 80 ℃ for 4 hours to obtain 388.1g of a maleimide compound a-4-containing product. In the FD-MS spectrum of the maleimide compound a-4, peaks at M + ═ 616, 774, and 932 were observed, corresponding to the cases where n was 0, 1, and 2, respectively. The number n of repeating units in the indane skeleton portion of the maleimide a-4 (based on the number average molecular weight) was determined by GPC, and the GPC chart thereof was shown in fig. 4, where n was 1.64 and the molecular weight distribution (Mw/Mn) was 1.40.
Figure BDA0003319414500000361
Synthesis example 5 Synthesis of Maleimide Compound A-5
(1) Synthesis of intermediate amine compounds
In a 1L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, 70.9g (0.4mol) of 2, 6-diisopropylaniline, 272.0g (1.4mol) of α, α' -dihydroxy-1, 3-diisopropylbenzene, 350g of xylene and 97g of activated clay were charged, and the mixture was heated to 120 ℃ with stirring. The distilled water was further removed by using a dean-Stark tube and the temperature was raised to 210 ℃ to conduct the reaction for 3 hours. Thereafter, the reaction mixture was cooled to 140 ℃ and 212.7g (1.2mol) of 2, 6-diisopropylaniline was added thereto, followed by heating to 220 ℃ for 3 hours. After the reaction, the reaction mixture was cooled to 100 ℃ with air, diluted with 500g of toluene, and the active clay was removed by filtration, and low molecular weight substances such as the solvent and unreacted substances were distilled off under reduced pressure, whereby 317.5g of an intermediate amine compound represented by the following general formula (A-5) was obtained. The amine equivalent weight is 366 and the softening point is 55 ℃.
Figure BDA0003319414500000371
(2) Maleinization of
107.9g (1.1mol) of maleic anhydride and 600g of toluene were put in a 2L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer and stirred at room temperature. Then, a mixed solution of 317.5g of the reactant (A-5) and 175g of DMF was added dropwise over 1 hour.
After completion of the dropwise addition, the reaction was further carried out at room temperature for 2 hours. 24.8g of p-toluenesulfonic acid monohydrate was added, the reaction solution was heated, water azeotropic under reflux and toluene were cooled/separated, and then only toluene was returned to the system to conduct dehydration reaction for 8 hours. After air-cooling to room temperature, concentration was carried out under reduced pressure, the brown solution was dissolved in 600g of ethyl acetate, washed 3 times with 200g of ion-exchanged water and 3 times with 200g of 2% aqueous sodium bicarbonate solution, dried by adding sodium sulfate, and then concentrated under reduced pressure, and the resulting reaction product was dried under vacuum at 80 ℃ for 4 hours to obtain 355.9g of a maleimide compound a-5-containing product. In the FD-MS spectrum of the maleimide compound a-5, peaks at M + ═ 672, 830, and 988 were observed, which corresponds to the cases where n was 0, 1, and 2, respectively. The number n of repeating units in the indane skeleton portion of the maleimide a-5 (based on the number average molecular weight) was determined by GPC, and the GPC chart thereof was shown in fig. 5, where n was 1.56 and the molecular weight distribution (Mw/Mn) was 1.24.
Figure BDA0003319414500000372
Synthesis example 6 Synthesis of Maleimide Compound A-9
(1) Synthesis of intermediate amine compounds
In the synthesis method of the intermediate amine compound A-1, 345.2g of an intermediate amine compound represented by the following general formula (A-9) was obtained by carrying out the same operation with the reaction time at 210 ℃ being changed to 6 hours and the reaction time at 220 ℃ being changed to 3 hours. The amine equivalent weight is 348 and the softening point is 71 ℃.
Figure BDA0003319414500000381
(2) Maleinization of
The same operation was carried out in the same manner as the above-described synthesis method for the maleimide compound A-1 except that the intermediate was replaced with A-9, whereby 407.6g of a maleimide compound A-9-containing product was obtained. In the FD-MS spectrum of the maleimide compound a-9, peaks of M + ═ 560, 718, and 876 were observed, and each peak corresponds to a case where n is 0, 1, or 2. The GPC chart of fig. 6 shows that the value of the number n of repeating units in the indane skeleton portion of the maleimide a-9 (based on the number average molecular weight) was obtained by GPC, where n is 2.59 and the molecular weight distribution (Mw/Mn) is 1.49.
Figure BDA0003319414500000382
Synthesis example 7 Synthesis of Maleimide Compound A-10
415.6g of a maleimide compound A-10-containing product was obtained under the same conditions as in the above-mentioned synthesis method for a maleimide compound A-1, except that the same operation was carried out except that the reaction time at 210 ℃ was changed to 6 hours and the reaction time at 220 ℃ was changed to 3 hours, and the dehydration reaction under reflux in the maleimide-based reaction was carried out for 10 hours with respect to the synthesized intermediate amine compound (amine equivalent: 347, softening point: 71 ℃). In the FD-MS spectrum of this maleimide compound a-10, peaks of M + ═ 560, 718, and 876 were observed, and each peak corresponds to the case where n is 0, 1, or 2. The GPC chart of fig. 7 shows that the value of the number n of repeating units in the indane skeleton portion of the maleimide a-10 (based on the number average molecular weight) was determined by GPC, and that n is 2.91 and the molecular weight distribution (Mw/Mn) is 1.64.
Figure BDA0003319414500000391
Synthesis example 8 Synthesis of Maleimide Compound A-11
The same conditions as in the above-mentioned synthesis method for maleimide compound A-1 were used except that the reaction time at 210 ℃ was changed to 9 hours and the reaction time at 220 ℃ was changed to 3 hours in the same manner in the synthesis method for intermediate amine compound A-1, and that dehydration reaction under reflux in the maleimide-based reaction was 10 hours for the synthesized intermediate amine compound (amine equivalent: 342 and softening point: 69 ℃), thereby obtaining 398.7g of a product containing maleimide compound A-11. In the FD-MS spectrum of the maleimide compound a-11, peaks of M + ═ 560, 718, and 876 were observed, and each peak corresponds to a case where n is 0, 1, or 2. The GPC chart of fig. 8 shows that the value of the number n of repeating units in the indane skeleton portion of the maleimide a-11 (based on the number average molecular weight) was obtained by GPC, where n is 3.68 and the molecular weight distribution (Mw/Mn) is 2.09.
Figure BDA0003319414500000392
Synthesis example 9 Synthesis of Maleimide Compound A-12
422.7g of a maleimide compound A-12-containing product was obtained under the same conditions as in the above-mentioned synthesis method for a maleimide compound A-1, except that the same operation was carried out with respect to the synthesized intermediate amine compound (amine equivalent: 347, softening point: 70 ℃) in which the reaction time at 210 ℃ was changed to 9 hours and the reaction time at 220 ℃ was changed to 3 hours, and the dehydration reaction under reflux in the maleimide reaction was 12 hours. In the FD-MS spectrum of the maleimide compound a-12, peaks of M + ═ 560, 718, and 876 were observed, and each peak corresponds to a case where n is 0, 1, or 2. The number n of repeating units in the indane skeleton portion of the maleimide a-12 (based on the number average molecular weight) was determined by GPC, and the GPC chart thereof was shown in fig. 9, where n was 4.29 and the molecular weight distribution (Mw/Mn) was 3.02.
Figure BDA0003319414500000401
[ examples 1 to 9 and comparative example 1]
< solvent solubility of maleimide >
The solubilities of the maleimides (A-1) to (A-5) and (A-9) to (A-12) obtained in Synthesis examples 1 to 9 and a comparative commercially available maleimide (A-6) (4, 4' -diphenylmethane bismaleimide, manufactured by Kogyo chemical Co., Ltd., "BMI-1000") were evaluated with respect to toluene and Methyl Ethyl Ketone (MEK), and the evaluation results are shown in Table 1.
As a method for evaluating the solubility in a solvent, a toluene solution and a Methyl Ethyl Ketone (MEK) solution were prepared so that nonvolatile components became 10, 20, 30, 40, 50, 60, and 70 mass%, using each of the maleimides obtained in the above synthesis examples and comparative examples.
Specifically, the vials containing each of the maleimides obtained in the synthesis examples and comparative examples were left at room temperature (25 ℃) for 60 days, and the nonvolatile components were uniformly dissolved in each solution (without insoluble matter) and evaluated as good, and the insoluble (with insoluble matter) was evaluated as x (visual). It is practically preferable if the nonvolatile matter is soluble in the solvent at 20 mass% or more.
[ examples 10 to 14 and comparative examples 2 to 4 ]
< preparation of curable resin composition >
The maleimide compounds (A-1), (A-9) and (A-12) obtained in Synthesis examples 1 and 6 to 9, comparative maleimide (A-6) (4,4 '-diphenylmethane bismaleimide, "BMI-1000", manufactured by Dazawa Kaisha Co., Ltd.), comparative maleimide (A-7) (bisphenol A diphenylether bismaleimide, "BMI-4000" Dazakha Kaisha Co., Ltd.), comparative maleimide (A-8) (3, 3' -dimethyl-5, 5 '-diethyl-4, 4' -diphenylmethane bismaleimide, "BMI-5100", manufactured by Dazakha Kaisha Co., Ltd.), and a compound (B-1) having an unsaturated bond-containing substituent ("DABPA"), Diallyl bisphenol A, allyl equivalent, manufactured by Dahe chemical industries, Ltd.: 154g/eq), epoxy resin (C-1) (BPA-type epoxy resin "850-S", equivalent: 188g/eq, available from DIC K.K.), a curing accelerator (D-1) (triphenylphosphine, available from Tokyo chemical industry Co., Ltd.), and Methyl Ethyl Ketone (MEK) were mixed in the proportions shown in Table 2 to prepare a curable resin composition.
< solubility of varnish and uniformity of film appearance >
Whether or not the curable resin compositions of examples 10 to 14 and comparative examples 2 to 4 were uniformly dissolved was visually checked (confirmation of varnish solubility). The case of uniform dissolution was evaluated as good, and the case of non-uniform dissolution or complete non-dissolution was evaluated as x (e.g., the case of presence of insoluble matter, etc.).
Further, 5g of each curable resin composition was applied to a release PET film (thickness after drying: 295 μm), dried (heated) at 80 ℃ for 1 hour, and further dried (heated) at 120 ℃ for 1 hour to prepare a film molded article, and the appearance of the obtained film molded article was visually confirmed. The film appearance was evaluated as good, and the film appearance was evaluated as not good (for example, turbidity, insoluble matter, etc. could be observed). The evaluation results are shown in table 3.
< preparation of cured product (molded article) >
The curable resin composition was subjected to the following conditions to prepare a cured product (molded product).
Curing conditions are as follows: after heating at 200 ℃ for 2 hours, further heating at 250 ℃ for 2 hours was carried out to cure.
Thickness of cured product (molded product) after molding: 2.4mm
The obtained cured product was evaluated for various physical properties and characteristics by the following methods. The evaluation results are shown in table 3.
< glass transition temperature (Tg) >
A cured product having a thickness of 2.4mm was cut into a size of 5mm in width and 54mm in length to prepare a test piece. The test piece was evaluated by using a viscoelasticity measuring apparatus (DMA: solid viscoelasticity measuring apparatus "DMS 6100" manufactured by Hitachi High-Tech Science Corporation, deformation mode: bending with both ends fixed, measurement mode: sine wave oscillation, frequency 1Hz, temperature rise rate 3 ℃/min) and setting the temperature at which the change in elastic modulus is the largest (tan. delta. change rate is the largest) as the glass transition temperature Tg (. degree.C.). From the viewpoint of heat resistance, the glass transition temperature Tg is preferably 220 ℃ or higher, and more preferably 230 ℃ or higher.
< dielectric characteristics >
The dielectric constant and dielectric loss tangent at 1GHz of the test piece after being stored in a room at 23 ℃ and a humidity of 50% for 24 hours after the test piece was completely dried were measured by the cavity resonator method using a network analyzer "E8362C" manufactured by Agilent Technologies, Ltd., according to JIS-C-6481. The dielectric constant and the dielectric loss tangent are preferably 2.90 or less, more preferably 2.80 or less, from the viewpoint of reducing the transmission loss as an electronic material. The dielectric loss tangent is preferably 0.019 or less, more preferably 0.015 or less.
[ Table 1]
Figure BDA0003319414500000431
[ Table 2]
Figure BDA0003319414500000441
[ Table 3]
Figure BDA0003319414500000451
From the evaluation results of table 1 above, it was confirmed that: in examples 1 to 9, since maleimide having an indane skeleton was used, the nonvolatile content was soluble even at 20 mass% in the preparation of the toluene solution, and the nonvolatile content was soluble even at 50 mass% in the preparation of the MEK solution, and the solvent solubility was excellent. On the other hand, it was confirmed that the commercially available maleimide used in comparative example 1 had no indane skeleton in the structure and was poor in solvent solubility.
According to the evaluation results of table 2 above, it was confirmed that: in examples 10 to 14, the curable resin composition solution (varnish) containing maleimide having an indane skeleton was uniformly dissolved, and the film obtained by coating and drying the curable resin composition solution (varnish) had a uniform appearance, and the film was used for applications such as a circuit board (e.g., a copper-clad laminate) as typified by a laminate film in which uniformity in appearance of the film obtained is particularly required. On the other hand, it was confirmed that: in comparative examples 2 to 4, since a commercially available maleimide having no indane skeleton was used, the film had an uneven appearance, and it was difficult to use the film for applications such as a build-up film and a circuit board (e.g., a copper-clad laminate).
From the evaluation results of table 3 above, it was confirmed that: in examples 10 to 14, in addition to the use of maleimide having an indane skeleton, the use of an epoxy resin and the use of a compound (B) having an unsaturated bond-containing substituent as a curing agent resulted in a high glass transition temperature and excellent heat resistance. In addition, it was also confirmed that: the dielectric constant and the dielectric loss tangent are also suppressed to be low, and the dielectric characteristics are excellent. On the other hand, it was confirmed that: in comparative examples 2 to 4, the glass transition temperature was low, the dielectric constant and the dielectric loss tangent were high, and the heat resistance and the dielectric characteristics were inferior to those of example 6. In particular, it was confirmed that: in comparative example 4, the glass transition temperature was greatly lowered, and the heat resistance was problematic.
Industrial applicability
The cured product of the curable resin composition of the present invention is excellent in heat resistance and dielectric properties, and therefore can be suitably used for heat-resistant members and electronic members, particularly for semiconductor sealing materials, circuit boards, build-up films, build-up boards, and the like, adhesives, and resist materials. Further, the resin composition can be suitably used as a matrix resin for a fiber-reinforced resin, and is suitably used as a prepreg having high heat resistance.
Drawings
FIG. 1 is a GPC chart of the maleimide compound (A-1) obtained in Synthesis example 1.
FIG. 2 is a GPC chart of the maleimide compound (A-2) obtained in Synthesis example 2.
FIG. 3 is a GPC chart of the maleimide compound (A-3) obtained in Synthesis example 3.
FIG. 4 is a GPC chart of the maleimide compound (A-4) obtained in Synthesis example 4.
FIG. 5 is a GPC chart of the maleimide compound (A-5) obtained in Synthesis example 5.
FIG. 6 is a GPC chart of the maleimide compound (A-9) obtained in Synthesis example 6.
FIG. 7 is a GPC chart of the maleimide compound (A-10) obtained in Synthesis example 7.
FIG. 8 is a GPC chart of the maleimide compound (A-11) obtained in Synthesis example 8.
FIG. 9 is a GPC chart of the maleimide compound (A-12) obtained in Synthesis example 9.

Claims (8)

1. A curable resin composition characterized by containing: a maleimide having an indane skeleton, (B) a compound having a substituent having an unsaturated bond, and (C) an epoxy resin.
2. The curable resin composition according to claim 1, wherein the maleimide (A) is represented by the following general formula (1),
Figure FDA0003319414490000011
in the formula (1), Ra independently represents alkyl, alkoxy or alkylthio with 1-10 carbon atoms, aryl, aryloxy or arylthio with 6-10 carbon atoms, cycloalkyl with 3-10 carbon atoms, halogen atoms, nitro, hydroxyl or sulfydryl, q represents an integer value of 0-4, when q is 2-4, Ra is optionally the same or different in the same ring, Rb independently represents alkyl, alkoxy or alkylthio with 1-10 carbon atoms, aryl, aryloxy or arylthio with 6-10 carbon atoms, cycloalkyl with 3-10 carbon atoms, halogen atoms, hydroxyl or sulfydryl, r represents an integer value of 0-3, when r is 2-3, Rb is optionally the same or different in the same ring, and n is an average repeating unit number and represents a numerical value of 0.5-20.
3. A cured product obtained by curing the curable resin composition according to claim 1 or 2.
4. A prepreg comprising a reinforcing base material and a prepreg of the curable resin composition according to claim 1 or 2 impregnated in the reinforcing base material.
5. A circuit board obtained by laminating the prepreg according to claim 4 and a copper foil and performing thermocompression bonding molding.
6. A multilayer film comprising the curable resin composition according to any one of claims 1 to 3.
7. A semiconductor sealing material comprising the curable resin composition according to any one of claims 1 to 3.
8. A semiconductor device comprising a cured product obtained by heat-curing the semiconductor sealing material according to claim 7.
CN202080031240.1A 2019-04-26 2020-02-20 Curable resin composition Active CN113728030B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2019-086445 2019-04-26
JP2019086445 2019-04-26
PCT/JP2020/006795 WO2020217677A1 (en) 2019-04-26 2020-02-20 Curable resin composition

Publications (2)

Publication Number Publication Date
CN113728030A true CN113728030A (en) 2021-11-30
CN113728030B CN113728030B (en) 2023-08-15

Family

ID=72942318

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080031240.1A Active CN113728030B (en) 2019-04-26 2020-02-20 Curable resin composition

Country Status (4)

Country Link
JP (1) JP7198420B2 (en)
KR (1) KR20210141564A (en)
CN (1) CN113728030B (en)
WO (1) WO2020217677A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022054867A1 (en) * 2020-09-11 2022-03-17 パナソニックＩｐマネジメント株式会社 Resin composition, prepreg, resin-coated film, resin-coated metal foil, metal-cladded laminate board, and wiring board
WO2023281692A1 (en) * 2021-07-08 2023-01-12 昭和電工マテリアルズ株式会社 Resin composition, resin film, multilayered printed wiring board, and semiconductor package
KR20240019380A (en) * 2021-08-25 2024-02-14 미츠비시 가스 가가쿠 가부시키가이샤 Resin composition, cured object, prepreg, metal-foil-clad laminate, resin sheet, and printed wiring board
JP7353412B1 (en) 2022-03-28 2023-09-29 日本化薬株式会社 Maleimide compounds, curable resin compositions and cured products thereof, and amine compounds

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5218069A (en) * 1989-04-20 1993-06-08 Kawasaki Steel Corporation Imidated copolymers and uses thereof
US5399715A (en) * 1991-12-27 1995-03-21 Sumitomo Chemical Company, Limited Polyamino oligomers and polymaleimide compounds
JP2009084391A (en) * 2007-09-28 2009-04-23 Sekisui Chem Co Ltd Method for producing thermosetting resin having dihydrobenzoxazine ring structure
CN104341581A (en) * 2013-08-09 2015-02-11 新日铁住金化学株式会社 An epoxy resin composition and a curing compound thereof
JP2015174986A (en) * 2014-03-18 2015-10-05 Dic株式会社 Active ester resin, epoxy resin composition, hardened product of the composition, prepreg, circuit board and build-up film

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2014877C (en) * 1989-04-20 1995-09-12 Norihide Enomoto Imidated copolymers and uses thereof
JP2004182850A (en) 2002-12-03 2004-07-02 Mitsubishi Gas Chem Co Inc Prepreg having excellent balance of characteristics and laminated sheet

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5218069A (en) * 1989-04-20 1993-06-08 Kawasaki Steel Corporation Imidated copolymers and uses thereof
US5399715A (en) * 1991-12-27 1995-03-21 Sumitomo Chemical Company, Limited Polyamino oligomers and polymaleimide compounds
JP2009084391A (en) * 2007-09-28 2009-04-23 Sekisui Chem Co Ltd Method for producing thermosetting resin having dihydrobenzoxazine ring structure
CN104341581A (en) * 2013-08-09 2015-02-11 新日铁住金化学株式会社 An epoxy resin composition and a curing compound thereof
JP2015174986A (en) * 2014-03-18 2015-10-05 Dic株式会社 Active ester resin, epoxy resin composition, hardened product of the composition, prepreg, circuit board and build-up film

Also Published As

Publication number Publication date
JPWO2020217677A1 (en) 2021-12-02
TW202041595A (en) 2020-11-16
JP7198420B2 (en) 2023-01-04
KR20210141564A (en) 2021-11-23
WO2020217677A1 (en) 2020-10-29
CN113728030B (en) 2023-08-15

Similar Documents

Publication Publication Date Title
JP7212323B2 (en) Curable resin composition
CN113767117B (en) Curable resin composition
JP7176623B2 (en) Curable resin composition
CN113728030B (en) Curable resin composition
CN113748152B (en) Curable resin composition
CN113728019B (en) Curable resin composition
TWI833907B (en) Hardening resin composition
TWI833906B (en) Hardening resin composition
KR20230141567A (en) Curable composition, cured product, prepreg, circuit board, build-up film, semiconductor sealing material and semiconductor device
CN116891632A (en) Curable composition, cured product, prepreg, circuit board, laminate film, semiconductor sealing material, and semiconductor device
CN116891634A (en) Curable composition, cured product, prepreg, circuit board, laminated film, semiconductor sealing material, and semiconductor device
CN116891635A (en) Curable composition, cured product, prepreg, circuit board, laminated film, semiconductor sealing material, and semiconductor device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant