CN113767117B - Curable resin composition - Google Patents

Curable resin composition Download PDF

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Publication number
CN113767117B
CN113767117B CN202080030330.9A CN202080030330A CN113767117B CN 113767117 B CN113767117 B CN 113767117B CN 202080030330 A CN202080030330 A CN 202080030330A CN 113767117 B CN113767117 B CN 113767117B
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resin composition
maleimide
curable resin
compound
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CN113767117A (en
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下野智弘
冈本竜也
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DIC Corp
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DIC Corp
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    • 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
    • C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • 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
    • C08F22/00—Homopolymers and 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
    • C08F22/36—Amides or imides
    • C08F22/40—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
    • C08G59/62—Alcohols or phenols
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/298—Semiconductor material, e.g. amorphous silicon
    • 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
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides

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  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

Providing: curable resin composition having excellent heat resistance and dielectric characteristics as cured product thereof, prepreg, circuit board, laminated film, semiconductor sealing material, and semiconductor device having the above properties. The curable resin composition of the present invention is characterized by comprising: maleimide (A) having an indane skeleton, polyphenylene ether compound (B) and epoxy resin (C).

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 laminated film, a semiconductor sealing material, and a semiconductor device.
Background
As a material of a circuit board for electronic devices, there is widely used: a prepreg obtained by impregnating glass cloth with a thermosetting resin such as an epoxy resin system or a BT (bismaleimide-triazine) resin system and heat-drying the glass cloth, 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 the thinning of the semiconductor package substrate is advanced and warpage of the package substrate at the time of mounting becomes a problem, a material exhibiting high heat resistance is demanded in order to suppress such a situation.
In recent years, the speed and frequency of signals have been increased, and it has been desired to provide: a thermosetting resin composition which maintains a sufficiently low dielectric constant in these environments and which exhibits a sufficiently low dielectric loss tangent is provided.
In particular, in various electric material applications, particularly advanced material applications, further improvements in properties represented by heat resistance and dielectric properties, and materials and compositions having the properties have been demanded recently.
In response to such demands, maleimide resins are attracting attention as materials having both heat resistance and low dielectric constant/low dielectric loss tangent. However, in the past, although the maleimide resin has high heat resistance, the dielectric constant/dielectric loss tangent thereof has not reached a level required for advanced material applications, and the processability is poor due to the solubility of a poorly soluble agent, and therefore, development of a resin which maintains heat resistance, exhibits further low dielectric constant/low dielectric loss tangent, and is excellent in solvent solubility has been strongly desired.
In such a case, as a cyanate ester material having both high dielectric characteristics and heat resistance, a resin composition obtained by mixing a phenol novolac type cyanate ester resin, a bisphenol a cyanate ester resin, and a non-halogen epoxy resin is known (see patent document 1).
However, although the heat resistance and dielectric characteristics of the cured product of the resin composition described in patent document 1 are improved to some extent, the heat resistance has not reached the level required in recent years.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2004-182850
Disclosure of Invention
Problems to be solved by the invention
Accordingly, the present invention has been made to solve the problems, and an object of the present invention is to provide a curable resin composition having excellent heat resistance and dielectric characteristics as a cured product thereof, and a cured product thereof, a prepreg, a circuit board, a laminate film, a semiconductor sealing material, and a semiconductor device having the above-mentioned properties.
Solution for solving the problem
Accordingly, the present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a cured product of a curable resin composition containing a maleimide (a) having an indane skeleton, a polyphenylene ether compound (B) and an epoxy resin (C) can have a low dielectric constant and a low dielectric loss tangent, and also have excellent heat resistance, and have completed the present invention.
Specifically, the present invention relates to a curable resin composition comprising: maleimide (A) having an indane skeleton, polyphenylene ether compound (B) and epoxy resin (C).
In the curable resin composition of the present invention, the maleimide (a) is preferably represented by the following general formula (1).
( In the 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, 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 having 1 to 10 carbon atoms, an alkoxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, 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 an average number of repeating units and represents a number of 0.5 to 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 prepreg of the curable resin composition impregnated into the reinforcing base material.
The circuit board of the present invention is preferably obtained by laminating the prepreg and the copper foil and performing thermocompression bonding molding.
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
The curable resin composition of the present invention is useful for providing a curable resin composition which gives a cured product from the curable resin composition excellent in both heat resistance and dielectric characteristics and has the above properties, and a cured product, prepreg, circuit board, laminated film, semiconductor sealing material and semiconductor device which are obtained from the curable resin composition.
Detailed Description
The present invention will be described in detail below.
The present invention relates to a curable resin composition comprising: maleimide (a) having an indane skeleton (hereinafter, sometimes referred to as "(a) component"), polyphenylene ether compound (B) (hereinafter, sometimes referred to as "(B) component"), and epoxy resin (C) (hereinafter, sometimes referred to as "(C) component"). Among them, the maleimide (A) is preferably represented by the following general formula (1). The maleimide (a) has an indane skeleton, and therefore has a smaller proportion of polar functional groups in the structure than conventional maleimides, and is therefore preferable because of its excellent dielectric properties. Further, the cured product of the conventional maleimide resin tends to be brittle and is likely to be poor in brittleness resistance, but the maleimide (a) has an indane skeleton, and is excellent in flexibility, and improvement in brittleness resistance is expected to be preferable.
In the above general formula (1), ra independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, a cycloalkyl group having 3 to 10 carbon atoms (preferably 5 to 10), 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 having 1 to 10 carbon atoms, an alkoxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, 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 an average number of repeating units and represents a number of 0.5 to 20. In the case where r and q are 0, ra and Rb each represent a hydrogen atom.
Ra of 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 the use of an alkyl group having 1 to 4 carbon atoms is a preferred mode in which solvent solubility is improved due to a decrease in planarity in the vicinity of a maleimide group and a decrease in crystallinity, and a cured product can be obtained without impairing the reactivity of a maleimide group.
Q in the above general formula (1) is preferably 2 to 3, more preferably 2. When q is 2, the effect 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 a hydrogen atom, r is preferably 1 to 3, rb is preferably 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 in particular, when r is 0 and Rb is a hydrogen atom, steric hindrance is reduced at the time of formation of an indane skeleton in maleimide, and this is advantageous for production (synthesis) of maleimide, and a preferred embodiment is obtained.
< method for producing maleimide (A) having indane skeleton >
The method for producing maleimide (A) will be described below.
The following general formula (2) is the following compound: rc each independently represents a monovalent functional group selected from the group consisting of the following general formulae (3) and (4), the ortho-position of at least one Rc of 2 Rc is a hydrogen atom, and Rb and r represent the same as described above.
The following general formula (5) is: at least 1 of the ortho-position and para-position of the amino group is a hydrogen atom, ra and q each represent aniline or a derivative thereof similar to those described above, and an intermediate amine compound represented by the following general formula (6) can be obtained by reacting a compound of the above general formula (2) with a compound of the following general formula (5) in the presence of an acid catalyst. Ra, rb, q, and r in the following general formula (6) are the same as those described above.
The intermediate amine compound represented by the general formula (6) has the following general formula (7) having an indane skeleton, but has the following general formula (8) when q is 3 or less and at least 2 of the ortho-position and para-position of the amino group are hydrogen atoms in the aniline represented by the general formula (5) or a derivative thereof. Wherein Ra, rb, q and r in the following formula (8) are the same as those described above, and m is the number of repeating units and represents an integer value of 1 to 20. The structure represented by the following general formula (8) may be included in the structure of the above general formula (6).
In the indane skeleton (see the above general formula (7)) which is characteristic of the maleimide (a) used in the present invention, the average repeating unit number n is 0.5 to 20, preferably 0.7 to 10.0, more preferably 0.95 to 10.0, still more preferably 0.98 to 9.0, still more preferably 0.99 to 8.0, still more preferably 1.0 to 7.0, still more preferably 1.0 to 6.0, in terms of the average repeating unit number n (average value) in order to achieve a low melting point (low softening point), a low melt viscosity and excellent handleability. By providing the structure of the maleimide (a) with an indane skeleton, the maleimide is preferable because it is superior in solvent solubility to conventionally used maleimides. When n is less than 0.5, the content of the high-melting substance in the structure of the maleimide (a) becomes high, the solvent solubility becomes poor, and the proportion of the high-molecular-weight component contributing to flexibility becomes low, so that there is a concern that the resulting cured product will be less resistant to brittleness, and further, flexibility and softness will be reduced, which is not preferable. When n exceeds 20, heat resistance may be poor, and further, high molecular weight components may be excessive, and fluidity may be lowered and handleability may be poor when a cured product is formed, which is not preferable. 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 p-diisopropenylbenzene and m-diisopropenylbenzene, p-bis (α -hydroxyisopropyl) benzene and m-bis (α -hydroxyisopropyl) benzene, 1- (α -hydroxyisopropyl) -3-isopropenylbenzene, 1- (α -hydroxyisopropyl) -4-isopropenylbenzene, or a mixture thereof is typically used. Further, nuclear alkyl substituents such as diisopropenyltoluene and bis (. Alpha. -hydroxyisopropyl) toluene, and further nuclear halogen substituents such as chlorodiisopropenylbenzene and chlorobis (. Alpha. -hydroxyisopropyl) benzene, may be used.
Further, as the aforementioned compound (a), for example, examples of the (a) -bis (a) -hydroxyisopropyl) benzene include 2-chloro-1, 4-diisopropenylbenzene, 2-chloro-1, 4-bis (a-hydroxyisopropyl) benzene, 2-bromo-1, 4-diisopropenylbenzene, 2-bromo-1, 3-bis (a-hydroxyisopropyl) benzene, 4-bromo-1, 3-diisopropylbenzene, 4-bromo-1, 3-bis (a-hydroxyisopropyl) benzene, 5-bromo-1, 3-diisopropenylbenzene, 5-bromo-1, 3-bis (a-hydroxyisopropyl) benzene, 2-methoxy-1, 4-diisopropenylbenzene, 2-methoxy-1, 4-bis (a-hydroxyisopropyl) benzene, 5-ethoxy-1, 3-bis (a-hydroxyisopropyl) benzene, 2-phenoxy-1, 4-diisopropenylbenzene, 2-hydroxy-1, 4-bis (a-hydroxyisopropyl) benzene, 5-diisopropenylmercaptan, 2-diisopropenylmercaptan and 2-diisopropenylmercaptan, 2-methylsulfanyl-1, 4-bis (. Alpha. -hydroxyisopropyl) benzene, 2-phenylsulfanyl-1, 3-diisopropenylbenzene, 2-phenylsulfanyl-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 and the like.
In the case where the substituent contained in the compound (a) is not particularly limited, and the above-mentioned compound is used as the substituent having a large steric hindrance, the obtained maleimide is less likely to be deposited on each other than the substituent having a small steric hindrance, and the maleimide is less likely to be crystallized on each other, that is, the solvent solubility of the maleimide is improved, which is a preferable mode.
In addition, as the compound represented by the above general formula (5) (hereinafter, "compound (b)"), typically, dimethylaniline, diethylaniline, diisopropylaniline, ethylmethylaniline, chloroaniline, dichloroaniline, toluidine, dimethylaniline, phenylaniline, nitroaniline, aminophenol, cyclohexylaniline and the like can be used in addition to aniline. In addition, methoxyaniline, ethoxyaniline, phenoxyaniline, naphthyloxyaniline, aminothiol, methylthioaniline, ethylthioaniline and phenylthioaniline can be exemplified.
In the case where the maleimide group is directly bonded to the benzene ring as in the case of conventional maleimide (for example, N-phenylmaleimide), the benzene ring and the 5-membered ring of maleimide are stably aligned on the same plane, and therefore are easily stacked, and thus exhibit high crystallinity. Therefore, the solvent solubility is poor. In contrast, in the case of the present invention, the compound (b) is not particularly limited, and the compounds exemplified above can be used, and, for example, in the case of having a methyl group as a substituent such as 2, 6-dimethylaniline, it is preferable that the benzene ring and the 5-membered ring of maleimide form a distorted conformation due to steric hindrance of the methyl group and are less likely to accumulate, and therefore crystallinity is reduced and solvent solubility is improved. Among them, if the steric hindrance is too large, there is a concern that reactivity is hindered during synthesis of 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, after the compound (a) and the compound (b) are added and reacted in such a manner that the molar ratio of the compound (b) to the compound (a) (compound (b)/compound (a)) is preferably 0.1 to 2.0, more preferably 0.2 to 1.0 (stage 1), the compound (b) is further added and reacted in such an amount that the molar ratio of the compound (b) to the compound (a) added previously is preferably 0.5 to 20.0, more preferably 0.7 to 5.0 (stage 2), thereby obtaining maleimide (a) having an indane skeleton. In addition, the 2-stage reaction brings about preferable results in order to finish the reaction or from the viewpoint of handleability and the like. In the reaction in the 1 st stage, the molar ratio of the compound (b) to the compound (a) added previously (compound (b)/compound (a)) is preferably 0.10 to 0.49, more preferably 0.15 to 0.40, and still more preferably 0.20 to 0.39, whereby 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, and therefore, an intermediate amine compound and maleimide which are excellent in solvent solubility and further contributing to flexibility and brittleness can be obtained, is preferable.
The acid catalyst used in the above reaction may be, for example, an inorganic acid such as phosphoric acid, hydrochloric acid, sulfuric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid and other organic acids, activated clay, acid clay, silica-alumina, zeolite, a solid acid such as a strongly acidic ion exchange resin, heteropolyacid salt and the like, and a solid acid which can be easily removed from the catalyst by filtration after the reaction is preferable from the viewpoint of the handling property, and when other acids are used, it is preferable to perform the neutralization by alkali and the washing by water after the reaction.
The amount of the acid catalyst to be blended is preferably 5 to 30 parts by mass in terms of handling property and economical efficiency, with respect to 100 parts by mass of the total amount of the compound (a) and the compound (b) of the raw materials to be initially charged. The reaction temperature is usually in the range of 100 to 300. DegreeC, preferably 150 to 230. DegreeC, in order to suppress the formation of the isomer structure and avoid side reactions such as thermal decomposition.
Since the reaction time is not completely short and side reactions such as thermal decomposition reaction of the product are caused over a long period of time, the reaction temperature is usually in the range of 2 to 48 hours, preferably in the range of 2 to 24 hours, more preferably in the range of 4 to 24 hours, still more preferably in the range of 4 to 12 hours, in total, in order to reduce the low molecular weight component and increase the high molecular weight component.
In the above-described process for producing an intermediate amine compound, aniline or a derivative thereof serves as a solvent, and therefore, it is not necessary to use any other solvent, but a solvent may be used. For example, in the case of a reaction system that combines dehydration, 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, a solvent which can be azeotropically dehydrated such as toluene, xylene or chlorobenzene is used, and 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 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, and after the reaction, unreacted maleic anhydride and other impurities are removed by washing with water or the like, 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 general formula (7) having a skeleton of the general formula (1) and having an indane skeleton, and when q is 3 or less and at least 2 of the ortho-position and para-position of the amino group are hydrogen atoms, a structure corresponding to the general formula (8), that is, a structure represented by the general formula (9) may be included as a structure represented by the general formula (1).
Ra, rb, q, r and m in the general formula (9) are the same as those described above.
Examples of the organic solvent used in the maleinization 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, dimethylsulfoxide, N-methyl-2-pyrrolidone, acetonitrile and sulfolane, cyclic ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, aromatic solvents such as benzene, toluene and xylene, and the like, and these solvents may be used alone or in combination.
In the maleinization reaction, the intermediate amine compound and maleic anhydride are preferably mixed in an equivalent ratio of 1 to 1.5, more preferably 1.1 to 1.2, and the reaction is preferably carried out in an organic solvent in a mass ratio of 0.5 to 50, preferably 1 to 5, to the total amount of the intermediate amine compound and maleic anhydride.
Examples of the catalyst used in the maleinization reaction include acetates, chlorides, bromides, sulfates, nitrates, and other inorganic salts of nickel, cobalt, sodium, calcium, iron, lithium, manganese, and the like, phosphoric acid, hydrochloric acid, sulfuric acid, other inorganic acids, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, other organic acids, activated clay, acid clay, silica-alumina, zeolite, solid acids such as strongly acidic ion exchange resins, heteropolyacid salts, and the like, and toluene sulfonic acid is particularly preferably used.
Examples of the dehydrating agent used in the maleinization reaction include lower aliphatic carboxylic 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 molecular sieves, and the like, and acetic anhydride is preferably used.
The amount of the catalyst and the dehydrating agent used in the maleinization reaction is not limited, but in general, the catalyst is used in an amount of 0.0001 to 1.0 mol, preferably 0.001 to 0.5 mol, more preferably 0.01 to 0.3 mol, and the dehydrating agent is used in an amount of 1 to 3 mol, preferably 1 to 1.5 mol, based on 1 equivalent of the amino group of the intermediate amine compound.
As the reaction conditions for the maleinization, the above-mentioned intermediate amine compound and maleic anhydride may be charged, and after the reaction is performed at a temperature of 10 to 100℃and preferably 30 to 50℃for 0.5 to 12 hours, preferably 1 to 8 hours, the above-mentioned catalyst is added, and the reaction is performed at a temperature of 90 to 130℃and preferably 105 to 120℃for 2 to 24 hours, preferably 4 to 10 hours, more preferably 6 to 10 hours, in order to reduce the low molecular weight component and increase the high molecular weight component. After the reaction, unreacted maleic anhydride and other impurities are removed by washing with water or the like, and the mixture is heated and aged, so that the low molecular weight component is also reduced and the high molecular weight component is increased.
The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the maleimide (a) as measured by Gel Permeation Chromatography (GPC) is preferably in the range of 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 chart obtained by the GPC measurement, when the molecular weight distribution is wide and the high molecular weight component is large, the proportion of the high molecular weight component contributing to flexibility is large, so that brittleness can be suppressed as compared with a cured product using conventional maleimide, and a cured product excellent in flexibility and softness can be obtained, which is a preferable mode.
< GPC measurement >
The molecular weight distribution (Mw/Mn) of maleimide (A) was determined based on Gel Permeation Chromatography (GPC) using the following conditions.
Measurement device: HLC-8320GPC manufactured by Tosoh Co., ltd "
Column: the protective column "HXL-L" manufactured by Tosoh corporation+TSK-GELG 2000HXL manufactured by Tosoh corporation+TSK-GELG 3000HXL manufactured by Tosoh corporation+TSK-GELG 4000HXL manufactured by Tosoh corporation'
A detector: RI (differential refractometer)
And (3) data processing: "GPC WorkStation EcoSEC-workbench" manufactured by Tosoh Co., ltd "
Measurement conditions: column temperature 40 DEG C
Developing solvent tetrahydrofuran
Flow rate 1.0 ml/min
Standard: according to the measurement manual of "GPC station EcoSEC-workbench", the following monodisperse polystyrene having a known molecular weight was used.
(use of polystyrene)
"A-500" manufactured by Tosoh Co., ltd "
"A-1000" manufactured by Tosoh Co., ltd "
"A-2500" manufactured by Tosoh Co., ltd "
"A-5000" manufactured by Tosoh Co., ltd "
F-1 manufactured by Tosoh Co., ltd "
F-2 manufactured by Tosoh Co., ltd "
F-4 manufactured by Tosoh Co., ltd "
F-10 manufactured by Tosoh Co., ltd "
F-20 manufactured by Tosoh Co., ltd "
F-40 manufactured by Tosoh Co., ltd "
F-80 manufactured by Tosoh Co., ltd "
F-128 manufactured by Tosoh Co., ltd "
Sample: the maleimide solution obtained in the synthesis example was filtered with a microfilter to obtain a 1.0 mass% tetrahydrofuran solution in terms of resin solid content (50. Mu.l).
< polyphenylene ether Compound (B) >)
The curable resin composition of the present invention is characterized by containing a polyphenylene ether compound (B) (hereinafter, sometimes referred to as "(B) component"). Since the polyphenylene ether (PPE) contained in the structure of the polyphenylene ether compound (B) has excellent dielectric characteristics such as dielectric constant and dielectric loss tangent, a curable resin composition which can give a cured product exhibiting a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even in a high frequency band (high frequency region) such as MHz band to GHz band can be produced, and thus can be used as a molding material for high frequency applications, and is useful. In addition, the reaction with the maleimide (a) having an indane skeleton can function as a curing agent, and three-dimensional crosslinking can be performed, whereby a cured product excellent in heat resistance can be obtained, which is a preferred embodiment. In addition, in general, a cured product using a maleimide resin is poor in brittleness resistance, but the brittleness tends to be improved by the reaction with the polyphenylene ether compound (B) described above, and is preferable. Further, the epoxy resin (C) described in detail below also functions as a curing agent, and improves adhesion to copper, and is useful for manufacturing, for example, a circuit board using a copper foil.
The polyphenylene ether compound (B) is not particularly limited, and has a structure represented by the following general formula (10) or (11), for example.
Rd in the general formulae (10) and (11) each independently includes a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioether group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an alkylcarbonyloxy group having 2 to 5 carbon atoms, an alkylsulfonyl group having 1 to 5 carbon atoms, and the like. S is an integer value of 1 to 30, and t and u also represent integer values of 1 to 30.
The alkyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, propyl and the like.
The alkenyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, isopropenyl group and the like.
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 methoxy, ethoxy, propoxy, isopropoxy, butoxy, and pentoxy groups.
The thioether group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include methylthio, ethylthio, propylthio, isopropylthio, butylthio, pentylthio and the like.
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, a butylcarbonyl group and the like.
The alkoxycarbonyl group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group and the like.
The alkylcarbonyloxy group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group and the like.
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, pentylsulfonyl group and the like.
Among these, the 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, an alkyl group having 1 to 5 carbon atoms, still more preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom or a methyl group.
The Y in the above (11) may be a 2-valent aromatic group derived from an aromatic compound having 2 phenolic hydroxyl groups.
The aromatic compound having 2 phenolic hydroxyl groups is not particularly limited, and 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, tetramethyl bisphenol a, and the like are exemplified. Among these, hydroquinone, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, 4 '-biphenol, bisphenol A, bisphenol E, bisphenol F are preferable, and 4,4' -biphenol, bisphenol A, and tetramethyl bisphenol A are more preferable.
Since 2 phenolic hydroxyl groups of the aromatic compound having 2 phenolic hydroxyl groups form a phenylene ether bond (2 oxygen atoms bonded to Y), Y is a 2-valent aromatic group derived from the aromatic compound having 2 phenolic hydroxyl groups.
In the general formulae (10) and (11), the terminal structure of the structure is usually an aryloxy group having a phenolic hydroxyl group. The aforementioned phenolic hydroxyl groups may be modified to other structural sites.
Examples of the structural moiety obtained by modifying the phenolic hydroxyl group include a polymerizable unsaturated bond-containing group such as a (meth) acryloyloxy group, an allyloxy group, and a vinyloxy group, and a structural moiety obtained by reacting an epoxy compound with a phenolic hydroxyl group. Among them, a phenolic hydroxyl group or the above-mentioned polymerizable unsaturated bond-containing group is preferable from the viewpoint of a curable composition which is a cured product excellent in balance of dielectric characteristics and heat resistance.
The polyphenylene ether compound (B) used in the present invention may be used in the form of an alloy polymer with polystyrene or the like. Examples of the alloyed polymer include an alloyed polymer of poly (2, 6-dimethyl-1, 4-phenylene) ether and polystyrene, and an alloyed polymer of poly (2, 6-dimethyl-1, 4-phenylene) ether and a styrene-butadiene copolymer.
The polyphenylene ether compound (B) used in the present invention may be any of various modified polyphenylene ether compounds such as a polyphenylene ether compound obtained by subjecting a polyphenylene ether compound and a phenolic compound to a decomposition rearrangement reaction in the presence of a reaction initiator, a polyphenylene ether compound obtained by modifying with a polybutadiene polymer, and the like, in addition to the resins mentioned above, in a range not impairing the characteristics of the present invention, and these may be used alone or in combination.
The weight average molecular weight (Mw) of the polyphenylene ether compound (B) is preferably 1000 to 5000, more preferably 1200 to 4000, and still more preferably 1400 to 3000. When the weight average molecular weight of the compound (B) is within the above range, a cured product having excellent balance of dielectric characteristics and heat resistance can be obtained more reliably, which is a preferred embodiment. The weight average molecular weight (Mw) herein may be a value measured by a usual molecular weight measurement method, and specifically, a value measured by GPC described above may be mentioned.
< epoxy resin (C) >)
The curable resin composition of the present invention is characterized by containing an epoxy resin (C) (hereinafter, sometimes referred to as "component (C)"). The epoxy resin (C) is useful in that it has good fluidity in the preparation of a curable resin composition and can be prepared to give a cured product excellent in adhesion. When the polyphenylene ether compound (B) and the epoxy resin (C) are used, the adhesion to copper is improved, and for example, the polyphenylene ether compound (B) is useful for producing a circuit board or the like using a copper foil.
The epoxy resin (C) is not particularly limited, and examples thereof include novolac-type epoxy resins such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, α -naphthol novolac-type epoxy resins, β -naphthol novolac-type epoxy resins, bisphenol a novolac-type epoxy resins, biphenyl novolac-type epoxy resins, and the like; 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, and the like; biphenyl type epoxy resins such as biphenyl type epoxy resins, tetramethyl biphenyl type epoxy resins, epoxy resins having a biphenyl skeleton and a diglycidyl ether oxybenzene skeleton; naphthalene type epoxy resin; binaphthol type epoxy resins; 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 para-aminophenol type epoxy resin, and glycidyl amine type epoxy resin of diaminodiphenyl sulfone; diglycidyl ester type epoxy resins such as 2, 6-naphthalene dicarboxylic acid diglycidyl ester type epoxy resin and hexahydrophthalic anhydride glycidyl ester type epoxy resin; 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, 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 copolynovolac type epoxy resins, naphthol-cresol copolynovolac type epoxy resins, crystalline biphenyl type epoxy resins, tetramethyl biphenyl type epoxy resins, xanthene type epoxy resins, alkoxy group-containing aromatic ring-modified novolac type epoxy resins (compounds obtained by joining glycidyl group-containing aromatic rings and alkoxy group-containing aromatic rings with formaldehyde) and the like are particularly preferable 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 polyphenylene ether compound (B) within a range that does not impair the curing of the present invention. The polyphenylene ether compound (B) is preferably 50 mass% or more, more preferably 60 mass% or more, still more preferably 70 mass% or more, particularly preferably 80 mass% or more, and most preferably 90 mass% or more, based on 100 mass% of the total amount of the curing agent.
Examples of the curing agent other than the polyphenylene ether compound (B) include amine-based compounds, amide-based compounds, acid anhydride-based compounds, phenol-based compounds, cyanate-based compounds, compounds having a substituent containing an unsaturated double bond, and diene-based polymers. These curing agents may be used alone or in combination of 2 or more.
Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, and BF 3 Amine complexes, guanidine derivatives, etc.
Examples of the amide compound include dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, and the like.
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 phenolic compounds include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin modified phenol resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins (Xylock resins), resorcinol novolac resins, polyhydric phenol novolac resins represented by polyhydric hydroxyl compounds and formaldehyde, naphthol aralkyl resins, trimethylol methane resins, tetraphenolethane resins, naphthol novolac resins, naphthol-phenol copoly novolac resins, naphthol-cresol copoly novolac resins, biphenyl modified phenol resins (polyhydric phenol compounds obtained by joining phenol cores with a bisphenol), biphenyl modified naphthol resins (polyhydric phenol compounds obtained by joining phenol cores with a bisphenol), aminotriazine modified phenol resins (polyhydric phenol compounds obtained by joining phenol cores with a melamine, benzoguanamine, and the like), and polyhydric phenol compounds including an alkoxy group-containing aromatic ring modified phenol novolac resins (polyhydric phenol compounds obtained by joining phenol cores with a formaldehyde and an alkoxy group-containing aromatic ring).
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, polyhydroxy naphthalene 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 copoly type novolak type cyanate ester resin, naphthol-cresol copoly type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type cyanate ester resin, biphenyl modified phenolic novolak type cyanate ester resin, anthracene type cyanate ester resin, and the like.
The unsaturated bond-containing substituent is not particularly limited as long as it is a compound having 2 or more unsaturated bond-containing substituents in the molecule, and examples thereof include compounds having allyl, isopropenyl, 1-propenyl, acryl, methacryl, styryl, styrylmethyl, and the like.
Examples of the diene polymer include unmodified diene polymers which are not modified with polar groups. Here, the polar group is a functional group that affects dielectric properties, 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 50% or more of butadiene units in the polymer chain as a 1, 2-bond or a derivative thereof may be used.
Since the epoxy resin (C) is used in the present invention, a curing accelerator may be used in the curable resin composition of the present invention in an appropriate combination as required. As the curing accelerator, various substances 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 used as a semiconductor sealing material, the phosphorus compound is preferably triphenylphosphine or tertiary amine, and 1, 8-diazabicyclo- [5.4.0] -undecene (DBU) is preferred from the viewpoint of excellent curability, heat resistance, electrical characteristics, moisture resistance and reliability. These curing accelerators may be used alone or in combination of 2 or more. The amount of the curing accelerator to be added is preferably in the range of 1 to 10 parts by mass based on 100 parts by mass of the epoxy resin (C), for example.
< preparation of curable resin composition >
The curable resin composition of the present invention is characterized by comprising: maleimide (A) having an indane skeleton, polyphenylene ether compound (B) and epoxy resin (C). Since the maleimide (a) has an indane skeleton, it is excellent in solvent solubility as compared with conventional maleimides, and the curable resin composition is easy to prepare and excellent in handleability, and since the proportion of polar functional groups in the structure of the maleimide (a) is small, a cured product excellent in dielectric characteristics can be obtained. The polyphenylene ether (PPE) in the structure of the polyphenylene ether compound (B) functioning as a curing agent contributes to dielectric characteristics such as dielectric constant and dielectric loss tangent, and the epoxy resin (C) exhibits good fluidity during the preparation of the curable resin composition, so that a cured product having excellent adhesion can be obtained. In addition, the polyphenylene ether compound (B) functioning as a curing agent is preferably reacted with the maleimide (a) and the epoxy resin (C), whereby three-dimensional crosslinking can be performed, and a cured product excellent in heat resistance can be obtained. In addition, in general, a cured product using a maleimide resin is inferior in brittleness resistance, but the reaction with the polyphenylene ether compound (B) improves brittleness, and further improves adhesion to copper, and is useful, for example, in the production of a circuit board or the like using a copper foil.
The blending ratio (parts by mass) of the component (A) to the component (B) and the component (C) is as follows: the number of components (B) + (C) is preferably 90: 10-10: 90, more preferably 80: 20-20: 80, further preferably 65: 35-35: 65, particularly preferably 55: 45-45: 55. by adjusting the blending ratio within the above range, heat resistance, low dielectric constant, and low dielectric loss tangent can be achieved, which is preferable.
The blending ratio (parts by mass) of the polyphenylene ether compound (B) and the epoxy resin (C) in the curable resin composition of the present invention is not particularly limited, and the component (B) is from the viewpoint of good properties of the obtained cured product: the component (C) is preferably 90: 10-10: 90, more preferably 80: 20-20: 80, further preferably 65: 35-35: 65. by adjusting the blending ratio within the above range, heat resistance, low dielectric constant, and low dielectric loss tangent can be achieved, which is preferable.
The curable resin composition of the present invention may contain an alkenyl group-containing compound, for example, bismaleimides other than the maleimide (a), allyl ether-based compounds, allylamine-based compounds, triallyl cyanurate, alkenylphenol-based compounds, vinyl-containing polyolefin compounds, and the like, within a range that does not impair the object. In addition, other thermosetting resins such as thermosetting polyimide resin, phenol resin, active ester resin, benzoxazine resin, cyanate resin and the like are also suitably blended according to the purpose.
In order to exhibit flame retardancy, the curable resin composition of the present invention may be blended with a non-halogen flame retardant containing substantially no halogen atoms 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 organometallic salt flame retardants, which may be used alone or in combination.
The curable resin composition of the present invention may be blended with an inorganic filler as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. In particular, when the compounding amount of the inorganic filler is increased, fused silica is preferably used. The fused silica may be in any of crushed and spherical shapes, and in order to increase the amount of fused silica blended and to suppress the increase in melt viscosity of the molding material, it is preferable to mainly use a spherical shape. Further, in order to increase the blending amount of the spherical silica, the particle size distribution of the spherical silica is preferably appropriately adjusted. The filling ratio is preferably high in view of flame retardancy, and particularly preferably 20 mass% or more relative to the total amount of the curable resin composition. In the case where the curable resin composition is used for the purpose of conductive paste and the like described in detail below, a conductive filler such as silver powder or copper powder may be used.
The curable resin composition of the present invention may contain various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.
< 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 components, or can be easily produced into a cured product by the same method as the 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 (heat curing) reaction can be easily performed without a catalyst, and if a rapid reaction is desired, the addition of a polymerization initiator such as an organic peroxide or an azo compound, a basic catalyst such as a phosphine compound or a tertiary amine is effective. For example, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, etc., are preferable as the compounding amount, and 0.05 to 5 mass% of the entire curable resin composition is preferable.
< prepreg >
The prepreg of the present invention preferably has a reinforcing base material and a prepreg of the curable resin composition impregnated into the reinforcing base material. As a method for producing the prepreg, a known method can be used, and the prepreg can be produced by impregnating a reinforcing substrate with a resin varnish obtained by dissolving (diluting) the curable resin composition in an organic solvent, and heat-treating the reinforcing substrate impregnated with the resin varnish to semi-cure (or uncured) the curable resin composition.
The organic solvent may be, for example, toluene, xylene, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl Ethyl Ketone (MEK), methyl isobutyl ketone, dioxane, tetrahydrofuran, or the like, alone or in a mixed solvent of 2 or more.
The reinforcing base material impregnated with the resin varnish is a woven fabric, a nonwoven fabric, a mat, or paper made of inorganic fibers such as glass fibers, polyester fibers, and polyamide fibers, or an organic fiber, 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, but is preferably generally prepared so that the mass ratio of the curable resin composition in the prepreg (resin in the prepreg) is 20 to 60 mass%.
The conditions for the heat treatment of the prepreg may be appropriately selected according to the types and amounts of the organic solvent, catalyst, and various additives used, and are usually conducted 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 composition can be suitably used for circuit boards, semiconductor sealing materials, semiconductor devices, laminated films, laminated substrates, adhesives, resist materials, and the like. In addition, the resin composition can be used as a matrix resin of 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 used as a coating material. The heat-resistant member and the electronic member thus obtained can be suitably used for various applications, and examples thereof include industrial machine parts, general machine parts, parts for automobiles, railways, vehicles, etc., space/aviation-related parts, electronic/electric parts, building materials, containers/packaging members, living goods, sports/leisure goods, housing members for wind power generation, etc., but are not limited thereto.
Representative articles produced using the curable resin composition of the present invention will be described below 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, as a method for obtaining a circuit board from the curable resin composition of the present invention, the following methods are exemplified: the prepregs are laminated by a conventional method, and copper foil is suitably laminated, and the laminate is subjected to thermocompression bonding 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 the semiconductor sealing material. Specifically, as a method for obtaining a semiconductor sealing material from the curable resin composition of the present invention, the following methods are exemplified: in the curable resin composition, a curing accelerator, an inorganic filler and other compounding agents are further mixed by sufficiently melting and mixing them as necessary using an extruder, kneader, roll and the like until they are uniform. In this case, as the inorganic filler, usually, fused silica is used, and when it is used as a high heat conductive semiconductor sealing material for a power transistor or a power IC, it is preferable to use a highly filled crystal such as crystalline silica, alumina, or silicon nitride having a higher thermal conductivity than that of the fused silica, or fused silica, crystalline silica, alumina, or silicon nitride. The inorganic filler is preferably used in an amount of 30 to 95 parts by mass based on 100 parts by mass of the curable resin composition, and in order to improve flame retardancy, moisture resistance and weld cracking resistance and reduce the linear expansion coefficient, the inorganic filler is more preferably 70 parts by mass or more, and still more preferably 80 parts by mass or more.
< semiconductor device >
In the present invention, the semiconductor device preferably includes a cured product obtained by heat curing the semiconductor sealing material. Specifically, the following method is exemplified as the molding of a semiconductor package to obtain a semiconductor device from the curable resin composition of the present invention: the semiconductor sealing material is cast-molded or molded by a transfer molding machine, an injection molding machine, or the like, and is further heat-cured 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 through steps 1 to 3. In step 1, the curable resin composition suitably blended with rubber, filler, and the like is first applied to a circuit board on which a circuit is formed by a spray coating method, curtain coating method, or the like, and then cured. In step 2, a circuit board coated with the curable resin composition is drilled with a predetermined through hole and the like, and then treated with a roughening agent, and the surface thereof is cleaned with hot water, whereby the substrate is roughened and plated with a metal such as copper, as necessary. In step 3, the operations of steps 1 to 2 are repeated in order as desired, and the resin insulating layers and the conductor layers of the predetermined circuit pattern are alternately laminated to form a laminated substrate. In the above-described step, the hole may be drilled after the formation of the outermost resin insulation layer. In the laminate substrate of the present invention, the resin-coated copper foil obtained by semi-curing the resin composition on the copper foil may be heat-pressed at 170 to 300 ℃ against the wiring substrate on which the circuit is formed, thereby forming a roughened surface, and the step of plating treatment may be omitted, thereby producing the 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: the curable resin composition is applied to the support film and then dried, whereby a resin composition layer is formed on the support film. When the curable resin composition of the present invention is used in a laminated film, the film is important to exhibit fluidity (resin flow) as follows: the resin may be filled in the via holes or the through holes of the circuit board while the circuit board is laminated by softening the circuit board under the lamination temperature condition (usually 70 to 140 ℃) in the vacuum lamination method, and the components are preferably blended in order to exhibit such characteristics. The obtained laminated film and circuit board (copper-clad laminate or the like) are required to have a uniform appearance at any position so as not to cause a phenomenon that they locally exhibit different characteristic values 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, the depth is usually 0.1 to 1.2mm, and resin filling can be performed in this range. In the case of laminating both sides of the circuit board, it is preferable to fill about 1/2 of the through hole.
Specific methods for producing the laminated film include the following methods: an organic solvent is compounded to prepare a varnished resin composition, and then the varnished resin composition is applied to the surface of the support film (Y), and then the organic solvent is dried by heating, blowing with hot air, or the like to form a resin composition layer (X).
As the organic solvent used herein, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetates such as carbitol acetate, cellosolve, aromatic hydrocarbons such as butyl carbitol, toluene, xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferably used, and the nonvolatile content is preferably 30 to 60 mass%.
The thickness of the resin composition layer (X) to be formed is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70. Mu.m, the thickness of the resin composition layer (X) is preferably 10 to 100. Mu.m. The resin composition layer (X) in the present invention may be protected by a protective film described later. The protective film prevents adhesion of dust and the like to the surface of the resin composition layer and prevents damage.
Examples of the support film and the protective film include polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate, polyimide, and metal foil 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. Mu.m, preferably 25 to 50. Mu.m. The thickness of the protective film is preferably 1 to 40. Mu.m.
The support film (Y) is peeled off after being laminated on a circuit board or after being heat-cured to form an insulating layer. When the support film (Y) is peeled off after the resin composition layer constituting the laminate film is heat-cured, adhesion of dust or the like in the curing step can be prevented. When peeling is performed after curing, the support film is usually subjected to a mold release treatment in advance.
The multilayer printed wiring board can be produced from the laminated 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 or both sides of the circuit board by, for example, vacuum lamination to directly contact the circuit board. The lamination may be carried out either batchwise or continuously with rolls. The laminated film and the circuit board may be heated (preheated) as needed before lamination, if necessary. For the lamination conditions, the pressure bonding temperature (lamination temperature) is preferably set to 70 to 140℃and the pressure bonding pressure is preferably set to 1 to 11kgf/cm 2 (9.8×10 4 ～107.9×10 4 N/m 2 ) The lamination is preferably performed under reduced pressure of 20mmHg (26.7 hPa) 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 is mentioned. 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 will be specifically described with reference to examples and comparative examples, and "parts" and "%" hereinafter are mass-based unless otherwise specified. The softening point, amine equivalent, GPC, and FD-MS spectra were measured and evaluated under the following conditions.
1) Softening point of
Assay: the softening point (. Degree. C.) of the intermediate amine compound obtained in the synthesis example shown below was measured in accordance with JIS K7234 (Ring and ball method).
2) Amine equivalent weight
The amine equivalent of the intermediate amine compound was measured by the following measurement method.
After accurately weighing about 2.5g of an intermediate amine compound, 7.5g of pyridine, 2.5g of acetic anhydride and 7.5g of triphenylphosphine as samples in a 500mL Erlenmeyer flask with a stopper, a condenser was installed and heated and refluxed in an oil bath set at 120℃for 150 minutes.
After cooling, 5.0mL of distilled water, 100mL of propylene glycol monomethyl ether, and 75mL of tetrahydrofuran were added, and titration was performed by a potentiometric titration method using a 0.5mol/L potassium hydroxide-ethanol solution. Blank tests were performed and corrections were made 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 (mL) in blank test
3) GPC measurement
The following measurement apparatus and measurement conditions were used to measure the maleimide obtained in the synthesis examples shown below, and GPC charts (FIGS. 1 to 9) were obtained. Based on the results of the GPC diagram, the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) is measured/calculated, and based on the number average molecular weight (Mn), the average number of repeating units "n" contributing to the indane skeleton in maleimide is measured/calculated. Specifically, for the compounds having n=0 to 4, points are plotted on the scatter plot using the theoretical molecular weight and the molecular weight of each measured value in GPC, an approximate straight line is drawn, and the number average molecular weight (Mn) is calculated from the points indicated by the measured value Mn (1) on the straight line, and n is calculated.
Measurement device: HLC-8320GPC manufactured by Tosoh Co., ltd "
Column: the protective column "HXL-L" manufactured by Tosoh corporation+TSK-GELG 2000HXL manufactured by Tosoh corporation+TSK-GELG 3000HXL manufactured by Tosoh corporation+TSK-GELG 4000HXL manufactured by Tosoh corporation'
A detector: RI (differential refractometer)
And (3) data processing: "GPC WorkStation EcoSEC-workbench" manufactured by Tosoh Co., ltd "
Measurement conditions: column temperature 40 DEG C
Developing solvent tetrahydrofuran
Flow rate 1.0 ml/min
Standard: according to the measurement manual of "GPC station EcoSEC-workbench", the following monodisperse polystyrene having a known molecular weight was used.
(use of polystyrene)
"A-500" manufactured by Tosoh Co., ltd "
"A-1000" manufactured by Tosoh Co., ltd "
"A-2500" manufactured by Tosoh Co., ltd "
"A-5000" manufactured by Tosoh Co., ltd "
F-1 manufactured by Tosoh Co., ltd "
F-2 manufactured by Tosoh Co., ltd "
F-4 manufactured by Tosoh Co., ltd "
F-10 manufactured by Tosoh Co., ltd "
F-20 manufactured by Tosoh Co., ltd "
F-40 manufactured by Tosoh Co., ltd "
F-80 manufactured by Tosoh Co., ltd "
F-128 manufactured by Tosoh Co., ltd "
Sample: the maleimide solution obtained in the synthesis example was filtered with a microfilter to obtain a 1.0 mass% tetrahydrofuran solution in terms of resin solid content (50. Mu.l).
4) FD-MS Spectroscopy
The FD-MS spectrum was measured using the following measuring apparatus and measuring conditions.
Measurement device: JMS-T100GCAccuTOF
Measurement conditions
Measurement range: m/z=4.00-2000.00
Rate of change: 51.2 mA/min
Final current value: 45mA
Cathode voltage: -10kV
Recording interval: 0.07 seconds
Synthesis example 1 Synthesis of maleimide Compound A-1
(1) Synthesis of intermediate amine compounds
48.5g (0.4 mol) of 2, 6-dimethylaniline, 272.0g (1.4 mol) of alpha, alpha' -dihydroxy-1, 3-diisopropylbenzene, 280g of xylene and 70g of activated clay were charged into a 1L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, and the mixture was heated to 120℃with stirring. The distilled wastewater was then removed using a dean-Stark tube and warmed to 210℃for 3 hours. Thereafter, the reaction mixture was cooled to 140℃and 145.4g (1.2 mol) of 2, 6-dimethylaniline was charged thereto, and then the temperature was raised to 220℃to effect a reaction for 3 hours. After the reaction, air was cooled to 100℃and diluted with 300g of toluene, activated clay was removed by filtration, and low molecular weight substances such as solvents 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 was 298 and the softening point was 70 ℃.
(2) Maleinization of
Into a 2L flask equipped with a thermometer, a condenser, a dean-Stark trap, and a stirrer, 131.8g (1.3 mol) of maleic anhydride and 700g of toluene were charged, and stirred at room temperature. A mixed solution of 364.1g of the reactant (A-1) and 175g of DMF was then added dropwise over 1 hour.
After the 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 mixture was heated, and azeotropic water and toluene under reflux were cooled/separated, and then toluene alone was returned to the system and dehydration reaction was carried out for 8 hours. After air cooling to room temperature, concentration under reduced pressure was performed, 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 2% aqueous sodium bicarbonate solution, dried by adding sodium sulfate, and then concentrated under reduced pressure, and the obtained reaction product was dried under vacuum at 80℃for 4 hours, to obtain 413.0g of a product containing maleimide compound A-1. In the FD-MS spectrum of the maleimide compound a-1, peaks m+=560, 718, 876 were confirmed, and each peak corresponds to the case where n is 0, 1, 2. The number n of repeating units in the indane skeleton portion in maleimide a-1 was obtained by GPC (based on number average molecular weight), and as a result, the GPC diagram was shown in fig. 1, n=1.47, and the molecular weight distribution (Mw/Mn) =1.81.
Synthesis example 2 Synthesis of maleimide Compound A-2
(1) Synthesis of intermediate amine compounds
48.5g (0.4 mol) of 2, 6-dimethylaniline, 233.2g (1.2 mol) of alpha, alpha' -dihydroxy-1, 3-diisopropylbenzene, 230g of xylene and 66g of activated clay were charged into a 1L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, and heated to 120℃with stirring. The distilled wastewater was then removed using a dean-Stark tube and warmed to 210℃for 3 hours. Thereafter, the reaction mixture was cooled to 140℃and 145.4g (1.2 mol) of 2, 6-dimethylaniline was charged thereto, and then the temperature was raised to 220℃to effect a reaction for 3 hours. After the reaction, air was cooled to 100℃and diluted with 300g of toluene, activated clay was removed by filtration, and low molecular weight substances such as solvents 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 was 294 and the softening point was 65 ℃.
(2) Maleinization of
Into a 2L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, 107.9g (1.1 mol) of maleic anhydride and 600g of toluene were charged 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 the 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 mixture was heated, and azeotropic water and toluene under reflux were cooled/separated, and then toluene alone was returned to the system and dehydration reaction was carried out for 8 hours. After air cooling to room temperature, concentration under reduced pressure was performed, 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 2% aqueous sodium hydrogencarbonate, dried by adding sodium sulfate, and then concentrated under reduced pressure, and the obtained reaction product was dried under vacuum 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 m+=560, 718, 876 were confirmed, which correspond to the cases where n was 0, 1, and 2, respectively. The number n of repeating units in the indane skeleton portion in maleimide a-2 was obtained by GPC (based on number average molecular weight), and as a result, the GPC diagram was shown in fig. 2, n=1.25, and the molecular weight distribution (Mw/Mn) =3.29.
Synthesis example 3 Synthesis of maleimide Compound A-3
(1) Synthesis of intermediate amine compounds
48.5g (0.4 mol) of 2, 6-dimethylaniline, 388.6g (2.0 mol) of alpha, alpha' -dihydroxy-1, 3-diisopropylbenzene, 350g of xylene and 123g of activated clay were charged 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 wastewater was then removed using a dean-Stark tube and warmed to 210℃for 3 hours. Thereafter, the reaction mixture was cooled to 140℃and 145.4g (1.2 mol) of 2, 6-dimethylaniline was charged thereto, and then the temperature was raised to 220℃to effect a reaction for 3 hours. After the reaction, air was cooled to 100℃and diluted with 500g of toluene, activated clay was removed by filtration, and low molecular weight substances such as solvents 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 was 306 and the softening point was 65 ℃.
(2) Maleinization of
Into a 2L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, 152.1g (1.5 mol) of maleic anhydride and 700g of toluene were charged and stirred at room temperature. A mixed solution of 402.1g of the reactant (A-3) and 200g of DMF was then added dropwise over 1 hour.
After the 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 mixture was heated, and azeotropic water and toluene under reflux were cooled/separated, and then toluene alone was returned to the system and dehydration reaction was carried out for 8 hours. After air cooling to room temperature, concentration under reduced pressure was performed, and a 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 hydrogencarbonate, dried by adding sodium sulfate, and then concentrated under reduced pressure, and the obtained reaction product was dried under vacuum at 80℃for 4 hours, whereby 486.9g of a maleimide compound A-3-containing product was obtained. In the FD-MS spectrum of the maleimide compound a-3, peaks m+=560, 718, 876 were confirmed, which correspond 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 in maleimide a-3 (based on the number average molecular weight) was obtained by GPC, and as a result, the GPC diagram was shown in fig. 3, n=1.96, and the molecular weight distribution (Mw/Mn) =1.52.
Synthesis example 4 Synthesis of maleimide Compound A-4
(1) Synthesis of intermediate amine compounds
59.7g (0.4 mol) of 2, 6-diethylaniline, 272.0g (1.4 mol) of α, α' -dihydroxy-1, 3-diisopropylbenzene, 350g of xylene and 94g of activated clay were charged into a 2L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, and the mixture was heated to 120℃with stirring. The distilled wastewater was then removed using a dean-Stark tube and warmed to 210℃for 3 hours. Thereafter, the reaction mixture was cooled to 140℃and 179.1g (1.2 mol) of 2, 6-diethylaniline was introduced thereinto, followed by heating to 220℃to conduct the reaction for 3 hours. After the reaction, air was cooled to 100℃and diluted with 500g of toluene, activated clay was removed by filtration, and low molecular weight substances such as solvents 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 was 364 and the softening point was 47 ℃.
(2) Maleinization of
Into a 2L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, 107.9g (1.1 mol) of maleic anhydride and 600g of toluene were charged 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 the 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 mixture was heated, and azeotropic water and toluene under reflux were cooled/separated, and then toluene alone was returned to the system and dehydration reaction was carried out for 8 hours. After air cooling to room temperature, concentration was performed under reduced pressure, a brown solution was dissolved in 500g of ethyl acetate, washing was performed 3 times with 200g of ion-exchanged water and 3 times with 200g of 2% aqueous sodium bicarbonate solution, drying was performed by adding sodium sulfate, concentration was performed under reduced pressure, and the obtained 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 m+=616, 774, 932 were confirmed, which correspond to the cases where n is 0, 1, 2, respectively. The number n of repeating units in the indane skeleton portion in maleimide a-4 was obtained by GPC (based on number average molecular weight), and as a result, the GPC diagram was shown in fig. 4, n=1.64, and the molecular weight distribution (Mw/Mn) =1.40.
Synthesis example 5 Synthesis of maleimide Compound A-5
(1) Synthesis of intermediate amine compounds
70.9g (0.4 mol) of 2, 6-diisopropylaniline, 272.0g (1.4 mol) of α, α' -dihydroxy-1, 3-diisopropylbenzene, 350g of xylene and 97g of activated clay were charged into a 1L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, and heated to 120℃with stirring. The distilled wastewater was then removed using a dean-Stark tube and warmed to 210℃for 3 hours. Thereafter, the reaction mixture was cooled to 140℃and 212.7g (1.2 mol) of 2, 6-diisopropylaniline was charged, followed by heating to 220℃to conduct a reaction for 3 hours. After the reaction, air was cooled to 100℃and diluted with 500g of toluene, activated clay was removed by filtration, and low molecular weight substances such as solvents 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 was 366 and the softening point was 55 ℃.
(2) Maleinization of
Into a 2L flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, 107.9g (1.1 mol) of maleic anhydride and 600g of toluene were charged 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 the 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 mixture was heated, and azeotropic water and toluene under reflux were cooled/separated, and then toluene alone was returned to the system and dehydration reaction was carried out for 8 hours. After air cooling to room temperature, concentration was performed under reduced pressure, a brown solution was dissolved in 600g of ethyl acetate, washing was performed 3 times with 200g of ion-exchanged water and 3 times with 200g of 2% aqueous sodium bicarbonate solution, drying was performed by adding sodium sulfate, concentration was performed under reduced pressure, and the obtained 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 m+=672, 830, 988 were confirmed, which correspond to the cases where n is 0, 1, 2, respectively. The number n of repeating units in the indane skeleton portion in maleimide a-5 was obtained by GPC (based on number average molecular weight), and as a result, the GPC diagram was shown in fig. 5, n=1.56, and the molecular weight distribution (Mw/Mn) =1.24.
Synthesis example 6 Synthesis of maleimide Compound A-9
(1) Synthesis of intermediate amine compounds
In the synthesis of the intermediate amine compound A-1, 345.2g of the intermediate amine compound represented by the following general formula (A-9) was obtained by the same procedure as described above except that the reaction time at 210℃was changed to 6 hours and the reaction time at 220℃was changed to 3 hours. The amine equivalent was 348 and the softening point was 71 ℃.
(2) Maleinization of
According to the aforementioned synthesis method of maleimide compound A-1, the same operation was performed except that the intermediate was replaced with A-9, to obtain 407.6g of a product containing maleimide compound A-9. In the FD-MS spectrum of the maleimide compound a-9, peaks m+=560, 718, 876 were confirmed, and each peak corresponds to the case where n is 0, 1, 2. The number n of repeating units in the indane skeleton portion in maleimide a-9 was obtained by GPC (based on number average molecular weight), and as a result, the GPC diagram was shown in fig. 6, n=2.59, and the molecular weight distribution (Mw/Mn) =1.49.
Synthesis example 7 Synthesis of maleimide Compound A-10
In the synthesis of the intermediate amine compound A-1, 415.6g of a product containing the maleimide compound A-10 was obtained by the same conditions as in the synthesis of the maleimide compound A-1 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 maleinization reaction was changed to 10 hours for the synthesized intermediate amine compound (amine equivalent: 347 and softening point: 71 ℃). In the FD-MS spectrum of the maleimide compound a-10, peaks m+=560, 718, 876 were confirmed, and each peak corresponds to the case where n is 0, 1, 2. The number n of repeating units in the indane skeleton portion in maleimide a-10 was obtained by GPC (based on number average molecular weight), and as a result, the GPC diagram was shown in fig. 7, n=2.91, and the molecular weight distribution (Mw/Mn) =1.64.
Synthesis example 8 Synthesis of maleimide Compound A-11
In the synthesis of the intermediate amine compound A-1, 398.7g of a product containing the maleimide compound A-11 was obtained by the same conditions as in the synthesis of the maleimide compound A-1 except that 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 maleinization reaction was changed to 10 hours for the synthesized intermediate amine compound (amine equivalent: 342 and softening point: 69 ℃). In the FD-MS spectrum of the maleimide compound a-11, peaks m+=560, 718, 876 were confirmed, and each peak corresponds to the case where n is 0, 1, 2. The number n of repeating units in the indane skeleton portion in maleimide a-11 was obtained by GPC (based on number average molecular weight), and as a result, the GPC diagram was shown in fig. 8, n=3.68, and the molecular weight distribution (Mw/Mn) =2.09.
Synthesis example 9 Synthesis of maleimide Compound A-12
In the synthesis of the intermediate amine compound A-1, 422.7g of a maleimide compound A-12-containing product was obtained under the same conditions as in the synthesis of the maleimide compound A-1 except that 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 maleinization reaction was carried out for the synthesized intermediate amine compound (amine equivalent: 347 and softening point: 70 ℃ C.). In the FD-MS spectrum of the maleimide compound a-12, peaks m+=560, 718, 876 were confirmed, and each peak corresponds to the case where n is 0, 1, 2. The number n of repeating units in the indane skeleton portion in maleimide a-12 was obtained by GPC (based on number average molecular weight), and as a result, the GPC diagram was shown in fig. 9, n=4.29, and the molecular weight distribution (Mw/Mn) =3.02.
[ examples 1 to 9 and comparative example 1 ]
< solvent solubility of maleimide >
The maleimides (A-1) to (A-5), (A-9) to (A-12) obtained in Synthesis examples 1 to 9 were evaluated for solubility in toluene and Methyl Ethyl Ketone (MEK) by comparison of commercially available maleimides (A-6) (4, 4' -diphenylmethane bismaleimide, "BMI-1000" manufactured by Kagaku Kogyo Co., ltd.) and the evaluation results are shown in Table 1.
As a method for evaluating the solvent solubility, toluene solution and Methyl Ethyl Ketone (MEK) solution were prepared so that the nonvolatile components became 10, 20, 30, 40, 50, 60, and 70 mass% using the respective maleimides obtained in the above synthesis examples and comparative examples.
Specifically, vials containing the maleimides obtained in the above synthesis examples and comparative examples were left at room temperature (25 ℃) for 60 days, and the nonvolatile components were evaluated as good when they were uniformly dissolved in the solutions (no insoluble matter), and as X (visual) when they were not dissolved. When the nonvolatile component is 20 mass% or more, it is practically preferable that the composition is soluble in a solvent.
[ examples 10 to 18, comparative examples 2 to 4 ]
< preparation of curable resin composition >
The compositions were prepared by mixing the maleimide (A-1) to (A-5) and (A-9) to (A-12) obtained in Synthesis examples 1 to 9, comparative maleimide (A-6) (4, 4 '-diphenylmethane bismaleimide, "BMI-1000", manufactured by Kagaku Kogyo Co., ltd.), comparative maleimide (A-7) (bisphenol A diphenylether bismaleimide, "BMI-4000" manufactured by Kagaku Kogyo Co., ltd.), comparative maleimide (A-8) (1, 6' -bismaleimide- (2, 4-trimethyl) hexane, "BMI-TMH" manufactured by Kagaku Kogyo Co., ltd.), polyphenylene ether compound (B-1) ("SA-90", manufactured by SABIC Co., mw: BPA), epoxy resin (C-1) (epoxy resin "850-S", equivalent weight: 188g/eq, manufactured by DIC Co., ltd.) and curing accelerator (D-1) (triphenylphosphine, manufactured by Kagaku Kogyo Co., ltd.) in the proportions shown in Table of Kagaku Kogyo Co., ltd.2.
[ examples 10, 15 to 18, and comparative examples 2 to 4 ]
< uniformity of appearance of film >
In examples 10, 15 to 18 and comparative examples 2 to 4, the curable resin compositions were obtained by mixing and dissolving Methyl Ethyl Ketone (MEK) 14.81g in the proportions shown in table 2. 5g of each curable resin composition was applied in the form of a release PET film (thickness after drying: 295 μm), dried (heated) at 80℃for 1 hour, and dried (heated) at 120℃for 1 hour, whereby a film-shaped article was produced, and the appearance of the obtained film-shaped article was visually confirmed. The film appearance was evaluated as uniform, and the film appearance was evaluated as non-uniform (for example, turbidity, insoluble matter, etc. could be confirmed). 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: after heating at 200℃for 2 hours, further heating and curing at 250℃for 2 hours.
Thickness of the 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 4.
< glass transition temperature (Tg) >)
The cured product having a thickness of 2.4mm was cut into a size of 5mm in width and 54mm in length, and used as a test piece. The test piece was evaluated using a viscoelasticity measuring apparatus (DMA: hitachi High-Tech Science Corporation solid viscoelasticity measuring apparatus "DMS6100", deformation mode: double-sided bending, measuring mode: sine wave oscillation, frequency 1Hz, heating rate 3 ℃/min), and the temperature at which the elastic modulus was the largest (the maximum rate of change in tan. Delta.) was set to the glass transition temperature Tg (. Degree.C.). From the viewpoint of heat resistance, the glass transition temperature Tg is preferably 135 ℃ or higher, more preferably 140 ℃ or higher.
< thermal decomposition resistance >
The cured product having a thickness of 2.4mm was cut into small pieces, and the pieces were evaluated by using a thermogravimetric analysis device (a thermal gravimetric measurement device "TGA/DSC1" manufactured by METTER TOREDO Co.) at a temperature rise rate of 5℃per minute under a nitrogen atmosphere, and at a temperature at which the weight of 5% was reduced, at a thermal decomposition temperature (Td 5) (DEG C).
< dielectric Property >
According to JIS-C-6481, the dielectric constant and dielectric loss tangent at 1GHz of a test piece after being stored in a room at 23℃and 50% humidity for 24 hours after being oven-dried were measured by a cavity method using a network analyzer "E8362C" manufactured by Agilent Technologies Co., ltd. The dielectric constant and the dielectric loss tangent are preferably 2.75 or less, more preferably 2.70 or less, from the viewpoint of reducing the transmission loss as an electronic material. The dielectric loss tangent is preferably 0.020 or less, more preferably 0.018 or less.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
From the evaluation results of table 1, it was confirmed that: in examples 1 to 9, since maleimide having an indane skeleton was used, the nonvolatile components were dissolved even at 20 mass% in the preparation of a toluene solution, and were dissolved even at 50 mass% in the preparation of a 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 in structure and had poor solubility in the skeletal solvent.
From the evaluation results of table 3, it was confirmed that: in examples 10 and 15 to 18, films obtained by coating and drying a curable resin composition solution (varnish) containing a maleimide having an indane skeleton have a uniform appearance, and in particular, laminated films, which require uniformity in appearance of the obtained films, are used for applications such as circuit boards (copper-clad laminates, etc.). On the other hand, confirm: in comparative examples 2 to 4, since maleimide which is commercially available and does not have an indane skeleton is used, the appearance of the film is uneven, and it is difficult to use the film for applications such as laminated films and circuit boards (copper-clad laminate, etc.).
From the evaluation results of table 4, it was confirmed that: in examples 10 to 18, an epoxy resin was added as a curing agent in addition to maleimide having an indane skeleton, and a polyphenylene ether compound contributing to dielectric properties was used, whereby the glass transition temperature, the thermal decomposition temperature, the heat resistance and the thermal decomposition resistance were excellent. It can be confirmed that: the dielectric constant and dielectric loss tangent are also suppressed to be low, and the dielectric characteristics are excellent. On the other hand, it can be confirmed that: in comparative example 2, the glass transition temperature and the thermal decomposition resistance were lower than those of examples, and the dielectric constant and the dielectric loss tangent were inferior to those of examples, so that evaluation samples could not be produced at all due to the influence of brittleness of the cured product.
Industrial applicability
The curable resin composition of the present invention is excellent in heat resistance and dielectric properties of a cured product thereof, and therefore, can be suitably used for heat-resistant members and electronic members, and particularly, can be suitably used for semiconductor sealing materials, circuit boards, laminated films, laminated substrates, etc., adhesives, and corrosion-resistant materials. In addition, the resin composition may 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 a 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 a maleimide compound (A-10) obtained in Synthesis example 7.
FIG. 8 is a GPC chart of a maleimide compound (A-11) obtained in Synthesis example 8.
FIG. 9 is a GPC chart of a maleimide compound (A-12) obtained in Synthesis example 9.

Claims (7)

1. A curable resin composition characterized by comprising: a maleimide (A) having an indane skeleton, a polyphenylene ether compound (B) and an epoxy resin (C), wherein the maleimide (A) is represented by the following general formula (1),
in the 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, a halogen atom, a nitro group, a hydroxyl group or a mercapto group, ra is optionally the same or different in the same ring, rb 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, r represents an integer of 0 to 3, rb is optionally the same or different in the same ring when r is 2 to 3, and n represents an average repeating unit number of 0.95 to 10.0.
2. A cured product obtained by curing the curable resin composition according to claim 1.
3. A prepreg comprising a reinforcing substrate and a prepreg impregnated with the curable resin composition according to claim 1.
4. A circuit board obtained by laminating the prepreg according to claim 3 and a copper foil and performing thermocompression bonding molding.
5. A laminated film comprising the curable resin composition according to claim 1.
6. A semiconductor sealing material comprising the curable resin composition according to claim 1.
7. A semiconductor device comprising a cured product obtained by heat curing the semiconductor sealing material according to claim 6.
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KR20230107249A (en) * 2020-11-16 2023-07-14 가부시끼가이샤 레조낙 Maleimide resin composition, prepreg, laminated board, resin film, printed wiring board and semiconductor package
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