WO2020217676A1 - 硬化性樹脂組成物 - Google Patents

硬化性樹脂組成物 Download PDF

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WO2020217676A1
WO2020217676A1 PCT/JP2020/006786 JP2020006786W WO2020217676A1 WO 2020217676 A1 WO2020217676 A1 WO 2020217676A1 JP 2020006786 W JP2020006786 W JP 2020006786W WO 2020217676 A1 WO2020217676 A1 WO 2020217676A1
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group
resin composition
maleimide
curable resin
compound
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PCT/JP2020/006786
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English (en)
French (fr)
Japanese (ja)
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智弘 下野
竜也 岡本
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Dic株式会社
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Priority to KR1020217032266A priority Critical patent/KR102577053B1/ko
Priority to CN202080030330.9A priority patent/CN113767117B/zh
Priority to JP2020537672A priority patent/JP6799803B1/ja
Publication of WO2020217676A1 publication Critical patent/WO2020217676A1/ja

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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

Definitions

  • the present invention relates to a curable resin composition, a cured product obtained from the curable resin composition, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device.
  • thermosetting resin such as an epoxy resin or BT (bismaleimide-triazine) resin and heat-dried to obtain a prepreg, which is heat-cured.
  • a laminated board, a multilayer board obtained by combining the laminated board and the prepreg and being heat-cured is widely used.
  • semiconductor package substrates are becoming thinner, and warpage of the package substrate during mounting becomes a problem.
  • a material exhibiting high heat resistance is required.
  • thermosetting resin composition that provides a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant under these environments has been provided. It is desired.
  • maleimide resin is attracting attention as a material that has both heat resistance, low dielectric constant, and low dielectric loss tangent.
  • the conventional maleimide resin exhibits high heat resistance, its dielectric constant and dielectric loss tangent value do not reach the level required for advanced material applications, and in addition, it is difficult to dissolve in a solvent and is inferior in handleability.
  • a cyanate ester-based material having high dielectric properties and heat resistance a phenol novolac type cyanate ester resin, a bisphenol A cyanate ester resin, and a non-halogen epoxy resin are blended.
  • a resin composition is known (see Patent Document 1).
  • the problem to be solved by the present invention is a curable resin composition having excellent heat resistance and dielectric properties in the cured product and the cured product thereof, and a prepreg, a circuit board, and a build having these performances. It is an object of the present invention to provide an up film, a semiconductor encapsulant, and a semiconductor device.
  • the present inventors have made a curable resin composition containing maleimide (A) having an indan skeleton, a polyphenylene ether compound (B), and an epoxy resin (C). It has been found that the cured product can have a low dielectric constant and a low dielectric loss tangent and also have excellent heat resistance, and has completed the present invention.
  • the present invention relates to a curable resin composition containing maleimide (A) having an indane skeleton, a polyphenylene ether compound (B), and an epoxy resin (C).
  • the maleimide (A) is preferably represented by the following general formula (1).
  • Ra independently has an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, and 3 to 3 carbon atoms. It represents a cycloalkyl group of 10, a halogen atom, a nitro group, a hydroxyl group or a mercapto group, where q represents an integer value of 0 to 4. When q is 2 to 4, Ra may be the same in the same ring. Rb may be different, respectively.
  • Rb is an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, and 3 to 10 carbon atoms.
  • Rb may be the same or different in the same ring. It may be.
  • N is the average number of repeating units and indicates a numerical value of 0.5 to 20.
  • the cured product of the present invention is preferably formed by subjecting the curable resin composition to a curing reaction.
  • the prepreg of the present invention preferably has a reinforcing base material and a semi-cured product of the curable resin composition impregnated in the reinforcing base material.
  • the circuit board of the present invention is preferably obtained by laminating the prepreg and copper foil and heat-pressing molding.
  • the build-up film of the present invention preferably contains the curable resin composition.
  • the semiconductor encapsulant of the present invention preferably contains the curable resin composition.
  • the semiconductor device of the present invention preferably contains a cured product obtained by heat-curing the semiconductor encapsulant.
  • the curable resin composition obtained from the curable resin composition has excellent heat resistance and dielectric properties, and has these performances. It is possible to provide a cured product, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device obtained from the curable resin composition, which is useful.
  • maleimide (A) having an indane skeleton hereinafter, may be referred to as “component (A)”
  • polyphenylene ether compound (B) hereinafter, may be referred to as “component (B)”
  • component (C) polyphenylene ether compound
  • the present invention relates to a curable resin composition, which comprises an epoxy resin (C) (hereinafter, may be referred to as “component (C)”).
  • component (C) epoxy resin
  • the maleimide (A) is represented by the following general formula (1). Since the maleimide (A) has an indane skeleton, the proportion of polar functional groups in the structure of the maleimide (A) is smaller than that of the conventional maleimide, and thus the dielectric property is excellent, which is preferable.
  • a cured product using a conventional maleimide resin tends to be brittle and may be inferior in brittleness.
  • the maleimide (A) has an indane skeleton, it has excellent flexibility and brittleness. Improvement is also expected and is preferable.
  • Ra independently has an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, and 3 carbon atoms. It represents a cycloalkyl group of ⁇ 10 (preferably 5-10), a halogen atom, a nitro group, a hydroxyl group or a mercapto group, and q represents an integer value of 0 to 4. When q is 2 to 4, Ra may be the same or different in the same ring.
  • Rb is independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy 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, and a halogen atom.
  • a hydroxyl group or a mercapto group, and r represents an integer value of 0 to 3. When r is 2 to 3, Rb may be the same or different in the same ring.
  • n is the average number of repeating units, and represents a numerical value of 0.5 to 20. When r and q are 0, Ra and Rb each refer to a hydrogen atom.
  • the Ra of the general formula (1) is preferably any one 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 carbon number 1 is 1.
  • an alkyl group of to 4 or the like the solvent solubility is improved due to the decrease in flatness and the decrease in crystallinity in the vicinity of the maleimide group, and a cured product can be obtained without impairing the reactivity of the maleimide group. This is a possible preferred embodiment.
  • the q in the general formula (1) is preferably 2 to 3, and more preferably 2.
  • q 2 to 3
  • the influence of steric hindrance is small, the electron density on the aromatic ring is improved, and this is a preferable embodiment in the production (synthesis) of maleimide.
  • r is 0 and Rb is preferably a hydrogen atom, r is 1 to 3, and Rb is an alkyl group having 1 to 4 carbon atoms and 3 carbon atoms. It is preferably at least one selected from the group consisting of a cycloalkyl group of to 6 and an aryl group having 6 to 10 carbon atoms, and in particular, r is 0 and Rb is a hydrogen atom. Therefore, steric hindrance is reduced during the formation of the indan skeleton in maleimide, which is advantageous for the production (synthesis) of maleimide, which is a preferable embodiment.
  • the following general formula (2) represents a monovalent functional group in which Rc is independently selected from the group consisting of the following general formulas (3) and (4), and the ortho of at least one of the two Rc is Rc.
  • the position is a hydrogen atom, and Rb and r are compounds showing the same as above.
  • At least one of the ortho-position and para-position of the amino group is a hydrogen atom
  • Ra and q are aniline or a derivative thereof having the same characteristics as described above.
  • the following general formula (7) having an indan skeleton is included in the structure, and among the aniline or its derivative represented by the general formula (5), q Is 3 or less, and when at least two of the ortho and para positions of the amino group are hydrogen atoms, the structure is represented by the following general formula (8).
  • Ra, Rb, q and r in the following general formula (8) are the same as described above, m is the number of repeating units, and indicates an integer value of 1 to 20.
  • the structure represented by the following general formula (8) may also be included in the structure of the above general formula (6).
  • the average number of repeating units n is a low melting point (low softening point), a low melt viscosity, and handleability.
  • the average number of repeating units n (average value) is 0.5 to 20, preferably 0.7 to 10.0, and more preferably 0.95 to 10.0 in order to make the value excellent. , 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. Is.
  • the solvent solubility is excellent as compared with the maleimides used so far, which is a preferable embodiment. If n is less than 0.5, the content ratio of the refractory substance in the structure of maleimide (A) becomes high, the solvent solubility is inferior, and the high molecular weight component contributing to brittleness. Since the ratio is low, the brittleness of the obtained cured product is lowered, and the flexibility and flexibility may be lowered, which is not preferable.
  • n exceeds 20
  • the heat resistance will be inferior
  • the amount of high molecular weight components will be too large, the fluidity will be lowered when molding the cured product, and the handleability will be inferior. It is not preferable.
  • the value of n is preferably 0.5 to 10.0, more preferably 0.95 to 10.0, from the viewpoint of high thermal deformation temperature, high glass transition temperature, and the like.
  • compound (a) is not particularly limited, but is typically p- and m-diisopropenylbenzene, p- and. m-bis ( ⁇ -hydroxyisopropyl) benzene, 1- ( ⁇ -hydroxyisopropyl) -3-isopropenylbenzene, 1- ( ⁇ -hydroxyisopropyl) -4-isopropenylbenzene or a mixture thereof is used.
  • nuclear alkyl group substituents of these compounds such as diisopropenyltoluene and bis ( ⁇ -hydroxyisopropyl) toluene can also be used, and further nuclear halogen substituents such as chlorodiisopropenylbenzene and chlorobis ( ⁇ ). -Hydroxyisopropyl) benzene and the like can also be used.
  • examples of the compound (a) include 2-chloro-1,4-diisopropenylbenzene, 2-chloro-1,4-bis ( ⁇ -hydroxyisopropyl) benzene, and 2-bromo-1,4-di.
  • the substituent contained in the compound (a) is not particularly limited, and the above-exemplified compound can be used. However, in the case of a substituent having a large steric hindrance, it is compared with a substituent having a small steric hindrance. Stacking of the obtained maleimides is less likely to occur, and crystallization of the maleimides is less likely to occur, that is, the solvent solubility of the maleimides is improved, which is a preferable embodiment.
  • compound (b) in addition to aniline, for example, dimethylaniline, diethylaniline, diisopropylaniline, ethylmethylaniline, chloro Aniline, dichloroaniline, toluidine, xylidine, phenylaniline, nitroaniline, aminophenol, cyclohexylaniline and the like can be used.
  • methoxyaniline, ethoxyaniline, phenoxyaniline, naphthoxyaniline, aminothiol, methylthioaniline, ethylthioaniline and phenylthioaniline can be exemplified.
  • the compound (b) is not particularly limited, and the above-exemplified compound can be used, and methyl as a substituent, for example, 2,6-dimethylaniline.
  • the benzene ring and the 5-membered ring of maleimide take a twisted conformation due to the steric hindrance of the methyl group, which makes stacking difficult, so that the crystallinity is lowered, the solvent solubility is improved, and this is a preferable embodiment. ..
  • the steric hindrance is too large, there is a concern that the reactivity of maleimide during synthesis may be hindered. Therefore, for example, it is preferable to use the compound (b) having an alkyl group having 2 to 4 carbon atoms.
  • the compound (a) and the compound (b) are converted into moles of the compound (b) with respect to the compound (a).
  • the compound (compound (b) / compound (a)) is subjected to a charging reaction (first step) at a ratio of preferably 0.1 to 2.0, more preferably 0.2 to 1.0
  • the compound (1st step) is further subjected to b) is further added in an amount of preferably 0.5 to 20.0, more preferably 0.7 to 5.0 in terms of molar ratio to the compound (a) previously added, and reacted (second step).
  • a maleimide (A) having an indan skeleton can be obtained.
  • the compound (b) is preferably added as a molar ratio (compound (b) / compound (a)) to the compound (a) added earlier, preferably 0.10 to 0.49. , More preferably 0.15 to 0.40, and even more preferably 0.20 to 0.39, so that the content ratio of the low molecular weight high melting point compound having a wide molecular weight distribution is low and high. Since the proportion of the molecular weight component is high, it is preferable to obtain an intermediate amine compound and maleimide which are excellent in solvent solubility and can contribute to flexibility and brittleness resistance.
  • Examples of the acid catalyst used in the reaction include inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid and other organic acids, and active white clay.
  • Acidic white clay, silica alumina, zeolite, solid acids such as strongly acidic ion exchange resins, heteropolyhydrochloride, etc. can be mentioned, but solid acids that can be easily removed by filtration after the reaction are from the viewpoint of hand linkability. When other acids are used, it is preferable to neutralize with a base and wash with water after the reaction.
  • the blending amount of the acid catalyst is such that the acid catalyst is blended in the range of 5 to 40 parts by mass with respect to 100 parts by mass of the compound (a) and the compound (b), which are the raw materials to be charged first. From the viewpoint of handleability and economy, 5 to 30 parts by mass is preferable.
  • the reaction temperature may usually be in the range of 100 to 300 ° C., but is preferably 150 to 230 ° C. in order to suppress the formation of isomer structures and avoid side reactions such as thermal decomposition.
  • the reaction time the reaction does not proceed completely in a short time, and side reactions such as a thermal decomposition reaction of the product occur in a long time. Therefore, under the reaction temperature conditions, usually, the total reaction time is increased. It is in the range of 2 to 48 hours, preferably in the range of 2 to 24 hours in total, more preferably in the range of 4 to 24 hours in total, and further preferably in the range of 4 to 12 hours in total. A total of 8 to 12 hours is more preferable for reducing the low molecular weight component and increasing the high molecular weight component.
  • aniline or a derivative thereof also serves as a solvent
  • a solvent capable of azeotropic dehydration such as toluene, xylene, or chlorobenzene is used.
  • the solvent may be distilled off, and then the reaction may be carried out within the above reaction temperature range.
  • the maleimide (A) used in the present invention is prepared by charging an intermediate amine compound represented by the above general formula (6) obtained by the above method into a reactor, dissolving it in an appropriate solvent, and then using maleic anhydride and a catalyst. It can be obtained by reacting in the presence of, and after the reaction, removing unreacted maleic anhydride and other impurities by washing with water or the like, and removing the solvent by reducing the pressure. Moreover, you may use a dehydrating agent at the time of a reaction.
  • the maleimide (A) used in the present invention has the skeleton of the general formula (1) and includes a structure represented by the general formula (7) having an indane skeleton, but has a q of 3 or less and an amino group.
  • the structure corresponding to the above general formula (8) that is, the structure represented by the following general formula (9) is also represented by the above general formula (1). Included as a structure to be.
  • 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 maleimization reaction for synthesizing maleimide (A) include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone, N, N-dimethylformamide, N, Aprotonic solvents such as 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, benzene, toluene and xylene. Examples thereof include aromatic solvents such as, and these may be used alone or in combination.
  • ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and
  • the intermediate amine compound and maleic anhydride are preferably blended in the range of 1 to 1.5, more preferably the equivalent ratio of maleic anhydride to the amino equivalent of the intermediate amine compound.
  • Examples of the catalyst used in the maleimization reaction include acetates such as nickel, cobalt, sodium, calcium, iron, lithium and manganese, inorganic salts such as chlorides, bromides, sulfates and nitrates, phosphoric acid, hydrochloric acid and sulfuric acid.
  • Inorganic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, organic acids such as fluoromethanesulfonic acid, active clay, acidic clay, silica alumina, zeolite, solids such as strongly acidic ion exchange resin. Acids, heteropolyhydrochloric acid and the like can be mentioned, but toluenesulfonic acid is particularly preferable.
  • Examples of the dehydrating agent used in the maleimidization reaction include lower aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, oxides such as phosphorus pentoxide, calcium oxide and barium oxide, and inorganic acids such as sulfuric acid. , Porous ceramics such as molecular sieves, etc., but acetic anhydride can be preferably used.
  • the amount of the catalyst and dehydrating agent used in the maleimidization reaction is not particularly limited, but usually 0.0001 to 1.0 mol, preferably 0, of the catalyst is based on 1 equivalent of the amino group of the intermediate amine compound. It can be used in an amount of 0.01 to 0.5 mol, more preferably 0.01 to 0.3 mol, and a dehydrating agent of 1 to 3 mol, preferably 1 to 1.5 mol.
  • the reaction conditions for maleimide formation the intermediate amine compound and maleic anhydride are charged, and the temperature range is 10 to 100 ° C., preferably 30 to 50 ° C. for 0.5 to 12 hours, preferably 1 to 8 hours.
  • the catalyst can be added and the reaction can be carried out in a temperature range of 90 to 130 ° C., preferably 105 to 120 ° C. for 2 to 24 hours, preferably 4 to 10 hours to reduce low molecular weight components. 6-10 hours are more preferred for increasing the high molecular weight components.
  • unreacted maleic anhydride and other impurities are removed by washing with water or the like, and heat aging also reduces the low molecular weight component and increases the high molecular weight component.
  • the maleimide (A) has a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) calculated from gel permeation chromatography (GPC) measurement because it is excellent in low dielectric constant and low dielectric loss tangent. It 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, and even more preferably 1.2 to 5.0. It is more preferably 1.2 to 4.0, further preferably 1.3 to 3.8, particularly preferably 1.3 to 3.6, and most preferably 1.3 to 3.6. It is 3.4.
  • the curable resin composition of the present invention is characterized by containing a polyphenylene ether compound (B) (hereinafter, may be referred to as "component (B)"). Since the polyphenylene ether (PPE) contained in the structure of the polyphenylene ether compound (B) is excellent in dielectric properties such as dielectric constant and dielectric loss tangent, it is sufficient even in a high frequency band (high frequency region) from MHz band to GHz band. Since it is possible to prepare a curable resin composition capable of obtaining a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a low dielectric constant, it can be used as a molding material for high frequencies and is useful.
  • the maleimide (A) having the indane skeleton acts as a curing agent, can form a three-dimensional crosslink, and can obtain a cured product having excellent heat resistance, which is a preferable embodiment.
  • a cured product using a maleimide resin is inferior in brittleness, but the brittleness tends to be improved by the reaction with the polyphenylene ether compound (B), which is preferable.
  • the epoxy resin (C) described in detail below it also acts as a curing agent and improves the adhesion to copper, which is useful in, for example, manufacturing a circuit board using a copper foil.
  • the polyphenylene ether compound (B) is not particularly limited, but has, for example, a structure represented by the following general formula (10) or (11).
  • Rd in the general formulas (10) and (11) are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and cycloalkyl groups having 3 to 5 carbon atoms. , Alkoxy group with 1 to 5 carbon atoms, thioether group with 1 to 5 carbon atoms, alkylcarbonyl group with 2 to 5 carbon atoms, alkyloxycarbonyl group with 2 to 5 carbon atoms, alkylcarbonyloxy group with 2 to 5 carbon atoms , Alkoxysulfonyl groups having 1 to 5 carbon atoms and the like. Further, s is an integer value of 1 to 30, and t and u also indicate an integer value of 1 to 30.
  • the alkyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a propyl group. Be done.
  • the alkenyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-pentenyl group, and an isopropenyl group.
  • the cycloalkyl group having 3 to 5 carbon atoms is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a methylcyclobutyl group.
  • the alkoxy group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and a pentyloxy group.
  • the thioether group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, and a pentylthio group.
  • the alkylcarbonyl group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, an isopropylcarbonyl group, and a butylcarbonyl group.
  • the alkyloxycarbonyl group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, and a butyloxycarbonyl group.
  • the alkylcarbonyloxy group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, and a butylcarbonyloxy group.
  • the alkylsulfonyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, and a pentylsulfonyl group.
  • the Rd is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a cycloalkyl group having 3 to 5 carbon atoms, and preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. It is more preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom or a methyl group.
  • Y in (11) above includes a divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups.
  • the aromatic compound having two phenolic hydroxyl groups is not particularly limited, but is not particularly limited, but is catechol, resorcinol, hydroquinone, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-.
  • examples thereof include dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol B, bisphenol BP, bisphenol C, bisphenol F, tetramethylbisphenol A and the like.
  • hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol E, and bisphenol F are preferable, and 4,4'-biphenol and bisphenol A are preferable.
  • Tetramethylbisphenol A is more preferable.
  • Y is an aromatic having two phenolic hydroxyl groups. It is a divalent aromatic group derived from a group compound.
  • the terminal structure of the structure is generally an aryloxy group having a phenolic hydroxyl group.
  • the phenolic hydroxyl group may be modified to other structural sites.
  • Examples of the structural site 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, or a phenolic hydroxyl group reacted with an epoxy compound. Examples thereof include the obtained structural parts. Among them, a phenolic hydroxyl group or the polymerizable unsaturated bond-containing group is preferable because the curable composition has an excellent balance between the dielectric property and the heat resistance of the cured product.
  • the polyphenylene ether compound (B) used in the present invention can also be used as an alloyed polymer with polystyrene or the like.
  • the alloyed polymer include an alloyed polymer of poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene, and a poly (2,6-dimethyl-1,4-phenylene) ether and styrene-butadiene copolymer. And alloyed polymers with.
  • the polyphenylene ether compound (B) used in the present invention includes a polyphenylene ether compound obtained by decomposing and rearranging a polyphenylene ether compound and a phenolic compound in the presence of a reaction initiator, and polybutadiene.
  • a polyphenylene ether compound obtained by decomposing and rearranging a polyphenylene ether compound and a phenolic compound in the presence of a reaction initiator, and polybutadiene Various modified polyphenylene ether compounds, such as polymer-modified polyphenylene ether compounds, can be used as long as the properties of the present invention are not impaired, and these can 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 even more preferably 1400 to 3000. If the weight average molecular weight of the compound (B) is within the above range, a cured product having a well-balanced dielectric property and heat resistance can be obtained more reliably, which is a preferable embodiment.
  • the weight average molecular weight (Mw) here may be one measured by a general molecular weight measuring method, and specific examples thereof include a value measured using the above-mentioned GPC.
  • the curable resin composition of the present invention is characterized by containing an epoxy resin (C) (hereinafter, may be referred to as "component (C)").
  • the epoxy resin (C) is useful because it can prepare a curable resin composition which has good fluidity at the time of preparation of the curable resin composition and can obtain a cured product having excellent adhesion. .. Further, when the polyphenylene ether compound (B) and the epoxy resin (C) are used, the adhesion to copper is improved, which is useful in, for example, manufacturing a circuit board using a copper foil.
  • the epoxy resin (C) is not particularly limited, and is, for example, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, an ⁇ -naphthol novolac type epoxy resin, a ⁇ -naphthol novolac type epoxy resin, and a bisphenol A novolac type epoxy resin.
  • Novolak type epoxy resin such as biphenyl novolac type epoxy resin
  • aralkyl type epoxy resin such as phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin
  • 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, tetrabromo bisphenol A type epoxy resin, etc.
  • Biphenyl type epoxy resin biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, biphenyl type epoxy resin such as epoxy resin having biphenyl skeleton and diglycidyloxybenzene skeleton; naphthalene type epoxy resin; binaphthol type epoxy resin; binaphthyl type epoxy Resin: Dicyclopentadiene type epoxy resin such as dicyclopentadienephenol type epoxy resin; glycidylamine such as tetraglycidyldiaminodiphenylmethane type epoxy resin, triglycidyl-p-aminophenol type epoxy resin, glycidylamine type epoxy resin of diaminodiphenylsulfone Type epoxy resin; diglycidyl ester type epoxy resin such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resin, glycidyl ester type epoxy resin of hexahydrophthalic anhydr
  • a curing agent other than the polyphenylene ether compound (B) can be added to the curable resin composition of the present invention as long as the curing of the present invention is not impaired.
  • the polyphenylene ether compound (B) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more, based on 100% by mass of the total amount of the curing agent. It is preferable, and 90% by mass or more is most preferable.
  • Examples of the curing agent other than the polyphenylene ether compound (B) include amine compounds, amide compounds, acid anhydride compounds, phenolic compounds, cyanate ester compounds, and unsaturated double bond-containing substituents. Examples include compounds and diene-based polymers. These curing agents may be used alone or in combination of two or more.
  • diaminodiphenylmethane as amine compound, diethylenetriamine, triethylenetetramine, diaminodiphenyl sulfone, isophoronediamine, imidazo - Le, BF 3 - amine complex, guanidine derivatives and the like.
  • amide compound examples include a polyamide resin synthesized from a dimer of dicyandiamide and linolenic acid and ethylenediamine.
  • Examples of the acid anhydride-based compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, and hexahydrophthalic anhydride. Examples thereof include methylhexahydrophthalic anhydride.
  • phenolic compound examples include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), and resorcin novolac resin.
  • cyanate ester compound examples 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 sulfide type cyanate ester resin, and phenylene ether type cyanate ester resin. , Naftyrene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac 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 novolac type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolak
  • examples thereof include type cyanate ester resin, naphthol-cresol co-condensed novolak type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate ester resin, biphenyl modified novolac type cyanate ester resin, and anthracene type cyanate ester resin.
  • the compound having an unsaturated double bond-containing substituent is not particularly limited as long as it is a compound having two or more unsaturated bond-containing substituents in the molecule, but the unsaturated bond-containing substituent may be used.
  • Examples thereof include compounds having an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group and the like.
  • the diene-based polymer examples include non-modified diene-based polymers that have not been modified by polar groups.
  • the polar group is a functional group that affects the dielectric property, 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.
  • the diene polymer a homopolymer of butadiene in which 50% or more of the butadiene units in the polymer chain are 1,2-bonds and a derivative thereof can also be used.
  • a curing accelerator can be appropriately used in combination with the curable resin composition of the present invention, if necessary.
  • Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.
  • phosphorus compounds tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.
  • phosphorus compounds tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.
  • -[5.4.0]-Undesen (DBU) is preferred.
  • the curable resin composition of the present invention is characterized by containing maleimide (A) having an indane skeleton, a polyphenylene ether compound (B), and an epoxy resin (C). Since the maleimide (A) has an indan skeleton, the maleimide (A) has excellent solvent solubility, easy preparation of a curable resin composition, and excellent handleability as compared with the conventional maleimide. Since the proportion of polar functional groups in the structure is small, a cured product having excellent dielectric properties can be obtained.
  • the polyphenylene ether (PPE) in the structure can contribute to dielectric properties such as dielectric constant and dielectric loss tangent, and the epoxy resin (C) can be cured.
  • the fluidity of the sex resin composition at the time of preparation becomes good, and a cured product having excellent adhesion can be obtained.
  • the maleimide (A) and the epoxy resin (C) are reacted with the polyphenylene ether compound (B) acting as a curing agent to cause three-dimensional cross-linking, which is excellent in heat resistance.
  • a cured product can be obtained, which is a preferable embodiment.
  • a cured product using a maleimide resin is inferior in brittleness, but the reaction with the polyphenylene ether compound (B) improves brittleness and further improves adhesion to copper, for example. It is useful in manufacturing circuit boards and the like that use copper foil.
  • the component (A): (component (B) + component (C)) is 90:10. It is preferably from 10:90, more preferably from 80:20 to 20:80, even more preferably from 65:35 to 35:65, and particularly preferably from 55:45 to 45:55. is there.
  • heat resistance, low dielectric constant, and low dielectric loss tangent can be obtained, which is preferable.
  • the compounding 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, but the obtained cured product characteristics are good. Therefore, the component (B): component (C) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and even more preferably 65:35 to 35 :. 65. By adjusting the compounding ratio within the above range, heat resistance, low dielectric constant, and low dielectric loss tangent can be obtained, which is preferable.
  • the curable resin composition of the present invention contains alkenyl group-containing compounds such as bismaleimides other than the maleimide (A), allyl ether compounds, allyl amine compounds, and triallyl cyanurate, as long as the object is not impaired.
  • alkenylphenol compound, a vinyl group-containing polyolefin compound and the like can also be added.
  • other thermosetting resins such as a thermosetting polyimide resin, a phenol resin, an active ester resin, a benzoxazine resin, and a cyanate resin can also be appropriately blended depending on the intended purpose.
  • a non-halogen flame retardant that does not substantially contain a halogen atom can be blended in order to exhibit flame retardancy within a range that does not impair the purpose.
  • the non-halogen flame retardant include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, and the like, and these are used alone or in combination. be able to.
  • An inorganic filler can be added to the curable resin composition of the present invention, if necessary.
  • the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like.
  • fused silica When the blending amount of the inorganic filler is particularly large, it is preferable to use fused silica.
  • the molten silica can be used in either a crushed form or a spherical shape, but in order to increase the blending amount of the molten silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical one.
  • the filling rate is preferably high in consideration of flame retardancy, and is particularly preferably 20% by mass or more with respect to the total amount of the curable resin composition.
  • a conductive filler such as silver powder or copper powder can be used.
  • the curable resin composition of the present invention can be added with various compounding agents such as a silane coupling agent, a mold release agent, a pigment, and an emulsifier, if necessary.
  • the cured product of the present invention is preferably formed by subjecting the curable resin composition to a curing reaction.
  • the curable resin composition is obtained by uniformly mixing each of the above-mentioned components, and can be easily made into a cured product by the same method as a conventionally known method.
  • Examples of the cured product include molded products such as laminates, cast products, adhesive layers, coating films, and films.
  • the curing (heat curing) reaction is easily carried out without a catalyst, but if a faster reaction is desired, a polymerization initiator such as an organic peroxide or an azo compound, a phosphine compound, or a tertiary compound is used.
  • a polymerization initiator such as an organic peroxide or an azo compound, a phosphine compound, or a tertiary compound is used.
  • a basic catalyst such as amine is effective.
  • there are benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, etc. and the blending amount is 0.05 to 5% by mass of the entire curable resin composition. preferable.
  • the prepreg of the present invention preferably has a reinforcing base material and a semi-cured product of the curable resin composition impregnated in the reinforcing base material.
  • a method for producing the prepreg a known method can be used, but a reinforcing group in which the reinforcing base material is impregnated with a resin varnish obtained by dissolving (diluting) the curable resin composition in an organic solvent and impregnated with the resin varnish.
  • a prepreg can be obtained by semi-curing (or uncuring) the curable resin composition by heat-treating the material.
  • organic solvent examples include toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone (MEK), methyl isobutyl ketone, dioxane, tetrahydrofuran and the like. , Alone, or as a mixed solvent of two or more kinds.
  • the reinforcing base material impregnated with the resin varnish is woven fabric or non-woven fabric made of glass fiber, polyester fiber, polyamide fiber or other inorganic fiber, organic fiber, matte, paper or the like, and these may be used alone or in combination. Can be used.
  • the mass ratio of the curable resin composition and the reinforcing base material in the prepreg is not particularly limited, but usually, the curable resin composition (resin content in the prepreg) is 20 to 60% by mass. It is preferable to prepare.
  • the conditions for the heat treatment of the prepreg are appropriately selected depending on the type and amount of the organic solvent, catalyst, and various additives used, but are usually 3 to 30 minutes at a temperature of 80 to 220 ° C. It is done under such conditions.
  • the cured product obtained by the curable resin composition of the present invention is excellent in heat resistance and dielectric properties, it can be suitably used for heat-resistant members and electronic members.
  • it can be suitably used for circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up boards, adhesives, resist materials, and the like.
  • it can be suitably used for a matrix resin of a fiber reinforced resin, and is particularly suitable as a prepreg having high heat resistance.
  • the maleimide (A) having the indane skeleton contained in the curable resin composition can be made into a paint because it exhibits excellent solubility in various solvents.
  • the heat-resistant members and electronic members thus obtained can be suitably used for various purposes.
  • the circuit board is preferably obtained by laminating the prepreg and the copper foil and heat-pressing molding.
  • the above prepregs are laminated by a conventional method, copper foils are appropriately laminated, and the temperature is 170 to 300 ° C. under a pressure of 1 to 10 MPa.
  • a method of heat-pressing molding for 10 minutes to 3 hours can be mentioned.
  • the semiconductor encapsulant preferably contains the curable resin composition.
  • the curable resin composition is further mixed with a curing accelerator as an optional component and a compounding agent such as an inorganic filler. If necessary, a method of sufficiently melting and mixing the mixture with an extruder, a feeder, a roll, or the like until the mixture becomes uniform can be mentioned.
  • fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, and silicon nitride having higher thermal conductivity than fused silica It is preferable to use high-filling silicon or the like, or use fused silica, crystalline silica, alumina, silicon nitride, or the like.
  • an inorganic filler in the range of 30 to 95 parts by mass per 100 parts by mass of the curable resin composition, and among them, flame retardancy, moisture resistance, solder crack resistance improvement, and linear expansion
  • 70 parts by mass or more is more preferable, and 80 parts by mass or more is further preferable.
  • the semiconductor device preferably includes a cured product obtained by heat-curing the semiconductor encapsulant.
  • the semiconductor encapsulant is cast, or molded using a transfer molding machine, an injection molding machine, or the like, and further. Examples thereof include a method of heat curing at 50 to 250 ° C. for 2 to 10 hours.
  • step 1 the curable resin composition in which rubber, a filler and the like are appropriately mixed is applied to a circuit board on which a circuit is formed by a spray coating method, a curtain coating method or the like, and then cured.
  • step 2 if necessary, a circuit board coated with the curable resin composition is drilled with a predetermined through-hole portion or the like, treated with a roughening agent, and the surface thereof is washed with hot water. Unevenness is formed on the substrate, and a metal such as copper is plated.
  • step 3 the operations of steps 1 and 2 are sequentially repeated as desired, and the resin insulating layer and the conductor layer having a predetermined circuit pattern are alternately built up to form a build-up substrate.
  • the through-hole portion may be drilled after the resin insulating layer of the outermost layer is formed.
  • the build-up substrate in the present invention is roughened by heat-pressing a resin-containing copper foil obtained by semi-curing the resin composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 300 ° C. It is also possible to produce a build-up substrate by omitting the steps of forming a surface and plating.
  • the build-up film of the present invention preferably contains the curable resin composition.
  • a curable resin composition is applied on a support film and then dried to form a resin composition layer on the support film. The method can be mentioned.
  • the curable resin composition of the present invention is used as a build-up film, the film is softened under the temperature conditions of lamination (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and is applied to the circuit board at the same time as laminating the circuit board.
  • the diameter of the through hole of the circuit board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to enable resin filling in this range.
  • a varnished resin composition is prepared by blending an organic solvent, and then the varnished resin composition is applied to the surface of the support film (Y). Then, the organic solvent is further dried by heating, hot air blowing, or the like to form the resin composition layer (X).
  • organic solvent used here examples include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol.
  • ketones such as acetone, methyl ethyl ketone and cyclohexanone
  • acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol.
  • Carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used, and the non-volatile
  • the thickness of the resin composition layer (X) to be formed usually needs to be equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer included in the circuit board is usually in the range of 5 to 70 ⁇ m, the thickness of the resin composition layer (X) is preferably 10 to 100 ⁇ m.
  • the resin composition layer (X) in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches.
  • the support film and protective film described above include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonates and polyimides, and metals such as release paper, copper foil and aluminum foil. Foil and the like can be mentioned.
  • the support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment.
  • the thickness of the support film is not particularly limited, but is usually 10 to 150 ⁇ m, and is preferably used in the range of 25 to 50 ⁇ m.
  • the thickness of the protective film is preferably 1 to 40 ⁇ m.
  • the support film (Y) is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the resin composition layer constituting the build-up film is heat-cured, it is possible to prevent the adhesion of dust and the like in the curing step. When peeling after curing, the support film is usually subjected to a mold release treatment in advance.
  • a multilayer printed circuit board can be manufactured from the build-up film obtained as described above.
  • the resin composition layer (X) is protected by a protective film, the resin composition layer (X) is peeled off, and then the resin composition layer (X) is directly contacted with the circuit board on one or both sides of the circuit board.
  • laminating is performed by a vacuum laminating method.
  • the laminating method may be a batch method or a continuous method using a roll. If necessary, the build-up film and the circuit board may be preheated if necessary before laminating.
  • the crimping temperature (lamination temperature) is preferably 70 to 140 ° C., and the crimping pressure is 1 to 11 kgf / cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N / m 2 ). It is preferable to laminate under a reduced air pressure of 20 mmHg (26.7 hPa) or less.
  • Examples of the method for obtaining the conductive paste from the curable resin composition of the present invention include a method for dispersing the conductive particles in the composition.
  • the conductive paste can be used as a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of conductive particles used.
  • Softening point measurement method The softening point (° C.) of the intermediate amine compound obtained in the synthetic example shown below was measured in accordance with JIS K7234 (ring ball method).
  • the amine equivalent of the intermediate amine compound was measured by the following measuring method. Approximately 2.5 g of the sample intermediate amine compound, 7.5 g of pyridine, 2.5 g of anhydrous acetic acid, and 7.5 g of triphenylphosphine were precisely weighed in a 500 mL Erlenmeyer flask with a stopper, and then a cooling tube was attached to the flask at 120 ° C. The mixture was heated under reflux for 150 minutes in the oil bath set in.
  • GPC measurement Measurement was performed using the following measuring devices and measurement conditions, and GPC charts (FIGS. 1 to 9) of maleimide obtained in the synthetic examples shown below were obtained. From the results of the GPC chart, the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) and the average number of repeating units "n" that contribute to the indan skeleton in maleimide are changed to the number average molecular weight (Mn). Based on this, it was measured and calculated.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Measuring device "HLC-8320 GPC” manufactured by Tosoh Corporation Column: Guard column “HXL-L” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G3000HXL” manufactured by Tosoh Corporation + Tosoh Corporation Made by “TSK-GEL G4000HXL” Detector: RI (Differential Refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Developing solvent Tetrahydrofuran Flow velocity 1.0 ml / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of the above-mentioned "GPC workstation EcoSEC-WorkStation".
  • the mixture was cooled to 140 ° C., 145.4 g (1.2 mol) of 2,6-dimethylaniline was charged, the temperature was raised to 220 ° C., and the reaction was carried out for 3 hours.
  • the mixture is air-cooled to 100 ° C., diluted with 300 g of toluene, activated clay is removed by filtration, and low molecular weight substances such as a solvent and an unreacted compound are distilled off under reduced pressure to obtain the following general formula (A-2). ) Was obtained, and 278.4 g of the intermediate amine compound represented by) was obtained.
  • the amine equivalent was 294 and the softening point was 65 ° C.
  • toluene was used so that the non-volatile content was 10, 20, 30, 40, 50, 60, and 70% by mass using each maleimide obtained in the above synthesis example and comparative example.
  • a solution and a methyl ethyl ketone (MEK) solution were prepared.
  • the vials containing the maleimides obtained in the above synthesis examples and comparative examples were left at room temperature (25 ° C.) for 60 days and uniformly dissolved in each solution in each non-volatile composition (insoluble). (No substance) was evaluated as ⁇ , and when it was not dissolved (with insoluble substance), it was evaluated as ⁇ (visually).
  • the non-volatile content is 20% by mass or more, it is practically preferable if it can be dissolved in a solvent.
  • Examples 10, 15-18, and Comparative Examples 2-4 ⁇ Uniformity of film appearance>
  • 14.81 g of methyl ethyl ketone (MEK) was mixed and dissolved at the ratios shown in Table 2 to obtain a curable resin composition.
  • MEK methyl ethyl ketone
  • cured product (molded product) was prepared by subjecting the curable resin composition to the following conditions. Curing conditions: After heating at 200 ° C. for 2 hours, the mixture was further heat-cured at 250 ° C. for 2 hours. Plate thickness of cured product (molded product) after molding: 2.4 mm Various physical properties and properties of the obtained cured product were evaluated by the following methods. The evaluation results are shown in Table 4.
  • ⁇ Glass transition temperature (Tg)> A cured product having a thickness of 2.4 mm was cut into a size of 5 mm in width and 54 mm in length, and this was used as a test piece. This test piece is used as a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "DMS6100” manufactured by Hitachi High-Tech Science Co., Ltd., deformation mode: double-sided bending, measurement mode: sinusoidal vibration, frequency 1 Hz, heating rate 3 ° C./min) The temperature at which the change in viscoelasticity was maximized (the rate of change in tan ⁇ was the largest) was evaluated as the glass transition temperature Tg (° C.). From the viewpoint of heat resistance, the glass transition temperature Tg is preferably 135 ° C. or higher, more preferably 140 ° C. or higher.
  • thermogravimetric decomposition property A cured product with a thickness of 2.4 mm is cut into small pieces and measured in a nitrogen atmosphere at a temperature rise rate of 5 ° C./min using a thermogravimetric analyzer (thermogravimetric analyzer "TGA / DSC1" manufactured by METTTLER TOREDO). The temperature at which the weight was reduced by 5% was evaluated as the thermogravimetric decomposition temperature (Td5) (° C.).
  • the dielectric constant and the dielectric loss tangent were measured at.
  • the dielectric constant and the dielectric loss tangent the dielectric constant is preferably 2.75 or less, more preferably 2.70 or less, from the viewpoint of reducing transmission loss as an electronic material.
  • the dielectric loss tangent is preferably 0.020 or less, more preferably 0.018 or less.
  • the curable resin composition of the present invention can be suitably used for heat-resistant members and electronic members because the cured product is excellent in heat resistance and dielectric properties, and in particular, a semiconductor encapsulant, a circuit board, and a build. It can be suitably used for up films, build-up substrates, etc., adhesives and resist materials. Further, it can be suitably used for a matrix resin of a fiber reinforced resin, and is suitable as a prepreg having high heat resistance.

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WO2022102782A1 (ja) * 2020-11-16 2022-05-19 昭和電工マテリアルズ株式会社 マレイミド樹脂組成物、プリプレグ、積層板、樹脂フィルム、プリント配線板及び半導体パッケージ
WO2022102756A1 (ja) * 2020-11-12 2022-05-19 味の素株式会社 樹脂組成物
WO2022145377A1 (ja) * 2020-12-28 2022-07-07 昭和電工マテリアルズ株式会社 樹脂組成物、プリプレグ、積層板、樹脂フィルム、プリント配線板及び半導体パッケージ

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