Classifications

• • 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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate

Definitions

• the present invention relates to a curable composition excellent in heat resistance and dielectric properties in a cured product, a cured product of the curable composition, a printed wiring board using the curable composition, a semiconductor sealing material, and a build-up film.
• an invention relating to a resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) a smear suppressing component, and (D) an inorganic filler is provided.
• A an epoxy resin
• B an active ester compound
• C a smear suppressing component
• D an inorganic filler
• the non-volatile component of the said resin composition is 100 mass%
• the said (B) active ester compound, the said (C) smear suppression component, and the said (D) inorganic filler are respectively predetermined
• the (C) smear suppressing component is rubber particles.
• Patent Document 1 describes that a cured product of the resin composition can achieve a low dielectric loss tangent. It is also described that smear (resin residue) in the via hole after the cured product is drilled and roughened.
• the (B) active ester compound described in Patent Document 1 is a compound having one or more active ester groups in one molecule, and lowers the dielectric loss tangent of the cured product of the resin composition. Are listed.
• Patent Document 1 describes that the use of an active ester compound can lower the dielectric loss tangent of the resulting cured product. However, it has been found that such a cured product may not always have sufficient heat resistance.
• the present inventors have conducted intensive research to solve the above problems. As a result, it was found that a curable composition containing an aromatic ester compound having a specific molecular structure, a maleimide compound, and an epoxy compound has excellent heat resistance and dielectric properties in the cured product, and completed the present invention. I came to let you.
• Ar 1 is a substituted or unsubstituted first aromatic ring group
• Ar 2 is each independently a substituted or unsubstituted second aromatic ring group
• at least one of Ar 1 and Ar 2 has a polymerizable unsaturated bond-containing substituent, and n is an integer of 2 or 3.
• a semiconductor sealing material and a build-up film are provided.
• a curable composition excellent in heat resistance and dielectric properties in a cured product, a cured product of the curable composition, a printed wiring board using the curable composition, a semiconductor sealing material, and a build-up film can be provided.
• the aromatic ester compound (A) used in the present invention has the following structural formula (1)
• Ar 1 is a substituted or unsubstituted first aromatic ring group
• Ar 2 is each independently a substituted or unsubstituted second aromatic ring group; At this time, at least one of Ar 1 and Ar 2 has a polymerizable unsaturated bond-containing substituent, and n is an integer of 2 or 3.
• n is an integer of 2 or 3.
• the aromatic ester compound (A) is liquid at room temperature (25 ° C.) from the viewpoint of excellent handling properties when adjusted as a curable composition described later, heat resistance of the cured product, and dielectric properties. Or its softening point is preferably in the range of 40 ° C to 200 ° C.
• Ar 1 in the chemical formula (1) is a substituted or unsubstituted first aromatic ring group.
• n in the chemical formula (1) is an integer of 2 or 3
• two or three of the hydrogen atoms of the aromatic ring constituting the first aromatic ring group are represented by “—C ( O) OAr 2 ”.
• Ar 1 preferably has 3 to 30 carbon atoms.
• the first aromatic ring group is not particularly limited, but is monocyclic such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine and the like.
• Aromatic compounds with 2 or 3 hydrogen atoms removed condensed aromatics such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine
• aromatic compounds in which 2 or 3 hydrogen atoms are removed such as those in which 2 or 3 hydrogen atoms are removed from an aromatic compound.
• aromatic compounds for example, ring-aggregated aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc.
• ring-aggregated aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc.
• diphenylmethane diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenyl
• diphenylmethane diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenyl
• alkylene such as pyridylmethane, fluorene and diphenylcyclopentane.
• Ar 1 is preferably a substituted or unsubstituted benzene ring or a naphthalene ring, and more preferably a substituted or unsubstituted benzene ring because a cured product having more excellent dielectric properties can be obtained.
• the first aromatic ring group according to Ar 1 may have a substituent.
• the “substituent of the first aromatic ring group” is substituted with at least one hydrogen atom of the aromatic ring constituting the first aromatic ring group.
• Specific examples of the substituent of the first aromatic ring group are not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom.
• the alkyl group is not particularly limited, but is methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert -Pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, cyclohexyl group and the like.
• the alkoxy group is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
• the alkyloxycarbonyl group is not particularly limited, but a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, Examples thereof include a sec-butyloxycarbonyl group and a tert-butyloxycarbonyl group.
• the alkylcarbonyloxy group is not particularly limited, but a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, and sec-butylcarbonyloxy group, tert-butylcarbonyloxy group and the like.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Ar 1 may have a polymerizable unsaturated bond-containing substituent.
• Specific examples of the polymerizable unsaturated bond-containing substituent include an alkenyl group and an alkynyl group.
• the alkenyl group is not particularly limited, but vinyl group, allyl group, propenyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-hexenyl group, 2 -Hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-octenyl group, 2-octenyl group, 1-undecenyl group, 1-pentadecenyl group, 3-pentadecenyl group, 7-pentadecenyl group, 1 -Octadecenyl, 2-octadecenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, 1,3-butadienyl, 1,4-butadienyl, hexa-1,3-dienyl, hexa-2,5-die
• the alkynyl group is not particularly limited, but includes ethynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1,3-butadiynyl group and the like. Can be mentioned.
• the polymerizable unsaturated bond-containing substituent may further have a substituent.
• the “substituent of the polymerizable unsaturated bond-containing substituent” is substituted with at least one hydrogen atom constituting the polymerizable unsaturated bond-containing substituent.
• Specific examples of the substituent of the polymerizable unsaturated bond-containing substituent include an alkyloxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom.
• examples of the alkyloxycarbonyl group, alkylcarbonyloxy group, and halogen atom include those described above.
• the polymerizable unsaturated bond-containing substituent is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms.
• a substituted or unsubstituted alkenyl group having 2 to 5 carbon atoms vinyl group, allyl group, propenyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, A 2-butenyl group, a 3-butenyl group, and a 1,3-butadienyl group are particularly preferable, and an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group are most preferable.
• Preferred structures of Ar 1 include the following formulas (2-1) to (2-17).
• formulas (2-1) to (2-11) are preferable, and the formulas (2-1), (2-2), (2-6), (2-7), (2- 9) is more preferred, and formulas (2-1), (2-2), (2-6), and (2-7) are more preferred.
• formulas (2-1), (2-2), (2-6), and (2-7) are more preferred.
• Ar 2 is each independently a substituted or unsubstituted second aromatic ring group. As is clear from the description of the chemical formula (1), one of the hydrogen atoms of the aromatic ring constituting the second aromatic ring group is substituted with “—OC (O) Ar 1 ”. Become. Ar 2 preferably has 3 to 30 carbon atoms.
• the second aromatic ring group is not particularly limited, but is monocyclic such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine and the like.
• Aromatic compounds with one hydrogen atom removed from condensed aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine Examples thereof include those obtained by removing one hydrogen atom from an aromatic compound such as one obtained by removing one hydrogen atom.
• aromatic compounds for example, ring-aggregated aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc.
• ring-aggregated aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc.
• Ar 2 is preferably a substituted or unsubstituted benzene ring or naphthalene ring because a cured product having more excellent dielectric properties can be obtained.
• a benzene ring is preferable.
• the obtained cured product is more heat resistant and excellent in balance with low dielectric properties. From the viewpoint, a naphthalene ring is preferable.
• the second aromatic ring group according to Ar 2 may have a substituent.
• the “substituent of the second aromatic ring group” is substituted with at least one hydrogen atom of the aromatic ring constituting the second aromatic ring group.
• the substituent for the second aromatic ring group include, but are not limited to, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom.
• examples of the alkyl group, alkoxy group, alkyloxycarbonyl group, alkylcarbonyloxy group, and halogen atom include those described above.
• Ar 2 may have the above-described polymerizable unsaturated bond-containing substituent.
• the said polymerizable unsaturated bond containing substituent may have independently, or may have it in combination of 2 or more types.
• Preferred structures of Ar 2 include the following formulas (3-1) to (3-17).
• the formulas (3-1) to (3-11) are preferable, the formulas (3-1), (3-6), and (3-9) are more preferable, and the formula (3 -1) and (3-6) are more preferable.
• At least one of the hydrogen atoms of the aromatic rings in the formulas (3-1) to (3-17) may be substituted with an unsaturated bond-containing group.
• Ar 1 is the above formula (2-1), (2-2), (2-6), (2-7), (2-9), and Ar 2 is the above formula ( 3-1), (3-6), and (3-9) are more preferable, and Ar 1 is represented by the above formulas (2-1), (2-2), (2-6), (2-7) And Ar 2 is preferably the above formulas (3-1) and (3-6), Ar 1 is the above formula (2-1), and Ar 2 is the above formula (3-1). (3-6) is particularly preferable.
• At least one of Ar 1 and Ar 2 described above has a polymerizable unsaturated bond-containing substituent. That is, only Ar 1 may have a polymerizable unsaturated bond-containing substituent, only Ar 2 may have a polymerizable unsaturated bond-containing substituent, or Ar 1 and Ar 2 may be Both may have a polymerizable unsaturated bond-containing substituent.
• Ar 1 is More preferably, it does not have a polymerizable unsaturated bond-containing substituent, and all Ar 2 have a polymerizable unsaturated bond-containing substituent.
• the presence of a polymerizable unsaturated bond-containing substituent in Ar 2 is preferable because the balance between heat resistance and dielectric loss tangent is excellent.
• n is an integer of 2 or 3. That is, the aromatic ester compound (A) has two or three ester bonds that bind two aromatic rings.
• a more preferred form of the aromatic ester compound (A) represented by the chemical formula (1) includes a compound represented by the following chemical formula (1-1) or (1-2).
• R 1 is a polymerizable unsaturated bond-containing substituent.
• R 2 is each independently an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom.
• h is 2 or 3
• i is each independently an integer of 1 or more
• j is independently 0 or an integer of 1 or more
• i + j is an integer of 5 or less.
• k is 2 or 3
• l is independently an integer of 1 or more
• m is independently 0 or an integer of 1 or more
• l + m is an integer of 7 or less.
• R 1 or R 2 may be the same as or different from each other.
• R 1 and R 2 may be substituted on any carbon atom forming a naphthalene ring.
• R 1 particularly preferable examples include an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group as described above.
• i is preferably 1 or 2, and more preferably 1.
• R 1 particularly preferable examples include an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group as described above.
• l is preferably 1 or 2, and more preferably 1.
• the specific structure of the aromatic ester compound (A) represented by the above chemical formula (1) is not particularly limited, and examples thereof include compounds represented by the following chemical formulas (4-1) to (4-43). It is done.
• the chemical formulas (4-1) to (4-43) are preferable, and the chemical formulas (4-1) to (4-3), (4-10) ) To (4-13), (4-18) to (4-39), and more preferred are chemical formulas (4-1) to (4-3), (4-12), (4-13) , (4-19) to (4-21), (4-23) to (4-26), (4-29), (4-30), (4-32) to (4-39). More preferably, the chemical formulas are (4-1), (4-2), (4-12), (4-13), (4-26), (4-32), and (4-37). Is particularly preferred.
• the method for producing the aromatic ester compound (A) is not particularly limited, and can be produced by a known method as appropriate.
• the method for producing an aromatic ester compound (A) includes a polycarboxylic acid compound having a substituted or unsubstituted first aromatic ring group or a derivative thereof, and a substituted or unsubstituted second aromatic.
• At this time, at least one of the polycarboxylic acid compound or a derivative thereof and the phenol compound has a substituted or unsubstituted polymerizable unsaturated bond-containing substituent.
• polycarboxylic acid compound or derivative thereof has a substituted or unsubstituted aromatic ring group, and preferably has 3 to 30 carbon atoms.
• examples of the “derivative of the polycarboxylic acid compound” include an acid halide of carboxylic acid.
• the first aromatic ring group and the substituent of the first aromatic ring group are the same as those described above.
• polycarboxylic acid compounds or derivatives thereof include compounds represented by the following chemical formulas (5-1) to (5-15).
• R 1 is a hydroxy group or a halogen atom.
• R 2 is a polymerizable unsaturated bond-containing substituent. At this time, the polymerizable unsaturated bond-containing substituent is the same as described above.
• p is 2 or 3.
• Q is 0 or an integer of 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and still more preferably 0.
• the position of the substituent on the aromatic ring in the above chemical formula is described on the same aromatic ring for convenience.
• R 1 OC and R 2 are different benzenes. It may be substituted on the ring, indicating that the number of substituents in one molecule is p and q.
• polycarboxylic acid compounds or derivatives thereof are not particularly limited, but benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, 2-allylterephthalic acid; trimellitic acid, 5-allyltrimellitic Benzene tricarboxylic acid such as acid; naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 3-allylnaphthalene-1, Naphthalenedicarboxylic acid such as 4-dicarboxylic acid and 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acid such as 2,4,5-pyridinetricarboxylic acid; 1,3,5-triazine-2,4 , 6-tricarboxylic acid and other triazine
• benzenedicarboxylic acid and benzenetricarboxylic acid are preferable, and isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzenetricarboxylic acid, 1,3,5-benzenetricarbonyl Trichloride is more preferable, and isophthalic acid chloride, terephthalic acid chloride, and 1,3,5-benzenetricarbonyl trichloride are further preferable.
• polycarboxylic acid compounds or derivatives thereof may be used alone or in combination of two or more.
• the phenol compound has a substituted or unsubstituted aromatic ring group, and preferably has 3 to 30 carbon atoms.
• the second aromatic ring group and the substituent of the second aromatic ring group are the same as those described above.
• Specific phenol compounds include compounds represented by the following chemical formulas (6-1) to (6-17).
• R 2 is a polymerizable unsaturated bond-containing substituent.
• the polymerizable unsaturated bond-containing substituent is the same as described above.
• q is 0 or an integer of 1 or more, preferably 1 to 3, more preferably 1 or 2, and further preferably 1.
• the bonding position on the aromatic ring is arbitrary.
• any ring is substituted.
• phenol compounds are not particularly limited, but include phenol; naphthol; 2-allylphenol, 3-allylphenol, 4-allylphenol, 4-methyl-2-allylphenol, 6-methyl-2-allylphenol, Allylphenols such as eugenol; propenylphenols such as 2- (1-propenyl) phenol and isoeugenol; butenylphenols such as 2- (3-butenyl) phenol and 2- (1-ethyl-3-butenyl) phenol; cardanol Long-chain alkenylphenols such as 2-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-1-naphthol, and 3-allyl-1-naphthol.
• allylphenol and allylnaphthol are preferable, and 2-allylphenol, 4-methyl-2-allylphenol, 6-methyl-2-allylphenol, 2-allyl-1-naphthol, and 1-allyl- 2-naphthol is more preferable, and 2-allylphenol, 2-allyl-1-naphthol, and 1-allyl-2-naphthol are more preferable.
• 2-allylphenol having a benzene ring skeleton is preferable from the viewpoint of high handling property and low viscosity of the aromatic ester compound (A).
• the resulting cured product is more heat resistant and has low dielectric properties.
• 2-allyl-1-naphthol having a naphthalene ring skeleton, 1-allyl-2-naphthol and the like are preferable from the viewpoint of excellent balance.
• the above-mentioned phenol compounds may be used alone or in combination of two or more.
• the amount of the polycarboxylic acid compound or derivative thereof and the phenol compound used is not particularly limited.
• the carboxy group and / or acyl halide group of the polycarboxylic acid compound or derivative thereof relative to the number of moles of the hydroxy group of the phenol compound is not limited.
• the molar ratio of the number of derived groups [(derived group such as carboxy group and / or acyl halide group) / (hydroxy group)] is preferably 0.8 to 3.0, preferably 0.9 to 2 0.0 is more preferable, and 1.0 to 1.2 is more preferable.
• reaction conditions are not particularly limited, and known methods can be adopted as appropriate.
• the pH during the reaction is not particularly limited, but is preferably 11 or more.
• the pH can be adjusted by using an acid such as hydrochloric acid, sulfuric acid, nitric acid or acetic acid; a base such as sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia.
• the reaction temperature is not particularly limited, and is preferably 20 to 100 ° C., more preferably 40 to 80 ° C.
• the reaction pressure is not particularly limited, and is preferably a normal pressure.
• the reaction time is not particularly limited, and is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.
• the maleimide compound (B) used in the present invention may be any compound having a maleimide group in the molecule, and other specific structures are not particularly limited, and a wide variety of compounds can be used. Among them, a compound having two or more maleimide groups in one molecule is preferable because of excellent curability of the curable composition, heat resistance in the cured product, and dielectric properties. Specific examples include a bismaleimide compound having two maleimide groups in one molecule and a polymaleimide compound having three or more maleimide groups in one molecule. A maleimide compound (B) may be used individually by 1 type, and may use 2 or more types together.
• maleimide compound (B) examples include compounds represented by the following structural formula (7).
• X is a divalent organic group.
• R 3 is any one of a hydrogen atom, an aliphatic hydrocarbon group, and a halogen atom, and a plurality of R 3 present in the formula may be the same as each other. And may be different.
• R 3 in the structural formula (7) is any one of a hydrogen atom, an aliphatic hydrocarbon group, and a halogen atom.
• the aliphatic hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a cycloalkyl group such as a cyclohexyl group; a vinyl group, an allyl group, Examples thereof include polymerizable unsaturated bond-containing groups such as propenyl group, isopropenyl group, and 1-propenyl group.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the specific structure of X in the structural formula (7) is not particularly limited, and may be any structural part.
• X is an aromatic ring-containing structure site, since it becomes a curable composition that is further excellent in heat resistance and dielectric properties in the cured product.
• Specific examples of the aromatic ring-containing structural moiety include those represented by any of the following structural formulas (X-1) to (X-10).
• R 4 is independently a polymerizable unsaturated bond-containing group, an alkyl group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group.
• R 5 is any one of a hydrogen atom, an alkyl group, a halogenated alkyl group, and a halogen atom.
• Y is any one of an alkylene group, a halogenated alkylene group, a carbonyl group, a carbonyloxy group, a sulfonyl group, an oxygen atom, and a sulfur atom.
• a plurality of Y present in the formula (X-4) may be the same or different.
• Z is a carbon atom or a nitrogen atom.
• Z in the formula (X-8) is a carbon atom.
• i is 0 or an integer of 1 to 4
• l is an integer of 0 or 1 to 6
• m is an integer of 0 or 1 to 5
• n is an integer of 0 or 1 to 7
• o is an integer of 0 or 1 to 3 is there.
• j and k are integers of 2 or more.
• the point of attachment and the position of the substituent on the naphthalene ring may be on any carbon atom that forms the naphthalene ring.
• R 4 in the structural formulas (X-1) to (X-10) is any of a polymerizable unsaturated bond-containing group, an alkyl group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group.
• Examples of the polymerizable unsaturated bond in the polymerizable unsaturated bond-containing group include a carbon-carbon double bond and a carbon-carbon triple bond.
• polymerizable unsaturated bond-containing group having a carbon-carbon double bond examples include, for example, vinyl group, vinyloxy group, (meth) allyl group, (meth) allyloxy group, 1-propenyl group, 1 -Butenyl group, 2-butenyl group, 3-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-octenyl group, 2-octenyl group, 1 -Undecenyl group, 1-pentadecenyl group, 3-pentadecenyl group, 7-pentadecenyl group, 1-octadecenyl group, 2-octadecenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, 1,3-butadienyl group, 1,4 -Butadie
• Specific examples of those having a carbon-carbon triple bond include, for example, ethynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1,3 -Butadiynyl group and the like.
• alkyl group examples include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; and a cycloalkyl group such as a cyclohexyl group.
• alkoxy group examples include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group.
• halogen atom examples include a fluorine atom, a chlorine atom, and a bromine atom.
• aryl group examples include a phenyl group, a naphthyl group, an anthryl group, and a structural site in which the polymerizable unsaturated bond-containing group, an alkyl group, an alkoxy group, a halogen atom, or the like is substituted on the aromatic nucleus.
• the aralkyl group is a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, or a structural site in which the polymerizable unsaturated bond-containing group, alkyl group, alkoxy group, halogen atom, or the like is substituted on these aromatic nuclei.
• R 4 is a vinyl group, a vinyloxy group, a (meth) allyl group, a (meth) allyloxy group, an alkyl group having 1 to 4 carbon atoms, a carbon atom because of excellent heat resistance and dielectric properties in a cured product. It is preferably any one of an alkoxy group having a number of 1 to 4, a halogen atom, and an aralkyl group having a polymerizable unsaturated bond-containing group.
• Y in the structural formulas (X-3) and (X-4) is any one of an alkylene group, a halogenated alkylene group, a carbonyl group, a carbonyloxy group, a sulfonyl group, an oxygen atom, and a sulfur atom.
• the number of carbon atoms in the alkylene group and halogenated alkylene group is not particularly limited, but is preferably in the range of 1 to 4 carbon atoms.
• J in the structural formula (X-2) is preferably 2 or 3.
• k in the structural formula (X-4) is preferably 2 or 3.
• R 5 in the structural formulas (X-6) and (X-7) is any one of a hydrogen atom, an alkyl group, a halogenated alkyl group, and a halogen atom.
• the number of carbon atoms in the alkyl group and halogenated alkyl group is not particularly limited, but is preferably in the range of 1 to 4 carbon atoms.
• bismaleimide compound examples include those represented by the following structural formulas (7-1) to (7-19).
• polymaleimide compound having three or more maleimide groups in one molecule include compounds represented by any of the following structural formulas (8-1) to (8-3).
• R 3 represents a hydrogen atom, an aliphatic hydrocarbon group, either a halogen atom, it may be a plurality of R 3 are identical to each other present in the formula may be different .
• R 4 Are each independently a polymerizable unsaturated bond-containing group, an alkyl group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, i is 0 or an integer of 1 to 4, o is 0 or 1 to 3
• V is an alkylene group having 1 to 4 carbon atoms, an arylmethylene group, an alkylenearylenealkylene group, an alkylenebiphenylenealkylene group, a cycloalkylene group, an oxygen atom, a sulfur atom, or a carbonyl group.
• ⁇ 5 is any one of a hydrogen atom, an alkyl group, a halogenated alkyl group, and a halogen atom
• Z is a carbon atom or a nitrogen atom
• t is an integer of 2 or more
• p is an integer of 3 to 6.
• maleimide compounds (B) commercially available ones may be used as they are.
• BMI series BMI-1000, 2000, 2300, 3000, 4000, 6000, 7000, 8000, manufactured by Daiwa Kasei Kogyo Co., Ltd.). , TMH, etc.
• the bismaleimide compounds are preferable from the viewpoints of curability and viscosity of the curable composition, heat resistance in the cured product, dielectric properties, and the like. Further, it is preferable that X in the structural formula (6) is any one of the structural formulas (X-1) to (X-4), and (X-3) or (X-4). More preferred.
• the blending ratio of the aromatic ester compound (A) and the maleimide compound (B) is not particularly limited, and is appropriately adjusted according to the desired cured product performance and the like.
• the maleimide compound (B) is added in an amount of 5 to 300 parts by mass with respect to 100 parts by mass of the aromatic ester compound (A) because the curable composition has an excellent balance between heat resistance and dielectric properties in the cured product. It is preferably used in the range, more preferably in the range of 20 to 200 parts by mass.
• the epoxy resin (C) used in the present invention will be described.
• the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol sulfide type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, poly Hydroxynaphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, Phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac Type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novo
• a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A novolac type epoxy resin, a polyhydroxynaphthalene type epoxy resin, a triphenylmethane type epoxy resin, Tetraphenylethane type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin Resins, xanthene type epoxy resins and the like are particularly preferable from the viewpoint of obtaining a cured product having excellent heat resistance.
• dicyclopentadiene-phenol addition reaction type epoxy resin dicyclopentadiene-phenol addition reaction type epoxy resin, naphthol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy in that a cured product having excellent dielectric properties can be obtained.
• naphthol-phenol co-condensed novolak epoxy resin naphthol-cresol co-condensed novolac epoxy resin
• biphenyl-modified phenolic epoxy resin phenolic epoxy type epoxy resin in which phenol skeleton and biphenyl skeleton are linked by bismethylene group
• biphenyl Modified naphthol-type epoxy resin an valent naphthol-type epoxy resin in which a naphthol skeleton and a biphenyl skeleton are linked by a bismethylene group
• Epoxy resin compound glycidyl group-containing aromatic ring and an alkoxy group-containing aromatic ring are connected by formaldehyde
• an aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin is preferably a naphthylene ether type epoxy resin.
• the blending ratio of each component in the curable composition of the present invention is not particularly limited, and it is preferable to adjust appropriately according to the desired physical properties of the cured product.For example, the physical property balance of the cured product is better.
• the maleimide compound (B) is contained in an amount of 5 to 300 parts by mass and the epoxy compound (C) is contained in an amount of 5 to 300 parts by mass with respect to 100 parts by mass of the aromatic ester compound (A).
• the maleimide compound (B) is preferably contained in an amount of 20 to 200 parts by mass
• the epoxy compound (C) is preferably contained in an amount of 20 to 200 parts by mass.
• the curable resin composition of the present invention may be used in combination with an epoxy resin curing agent.
• epoxy resin curing agents that can be used here include curing agents such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds.
• examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivatives.
• the amide compound include dicyandiamide, Examples include polyamide resins synthesized from dimer of linolenic acid and ethylenediamine.
• acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride.
• phenolic compounds include phenol novolac resins, cresol novolac resins, Aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol -Cresol co-condensed novolak resin, biphenyl-modified phenol resin (
• phenol novolac resins cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, phenol aralkyls.
• Resins, naphthol aralkyl resins, naphthol novolak resins, naphthol-phenol co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, and aminotriazine-modified phenol resins are preferred because of their excellent flame retardancy .
• the amount used is preferably in the range of 10 to 50% by mass with respect to the resin component of the composition from the viewpoint of dielectric properties.
• a curing accelerator can be used together as appropriate.
• Various curing accelerators can be used, and examples thereof include phosphorus compounds, amine compounds, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.
• dimethylaminopyridine and imidazole are preferable from the viewpoint of excellent heat resistance, dielectric characteristics, solder resistance, and the like.
• triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo- [5 is used for amines. 4.0] -undecene (DBU) is preferred.
• Examples of the phosphorus compounds include organic phosphine compounds such as triphenylphosphine, tributylphosphine, triparatolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organic phosphite compounds such as trimethylphosphite and triethylphosphite; ethyltriphenylphosphonium bromide , Benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphinetriphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, butylphenyl Phosphonium dicyanamide,
• Examples of the amine compound include triethylamine, tributylamine, N, N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5,4, 0] -undecene-7 (DBU), 1,5-diazabicyclo [4,3,0] -nonene-5 (DBN) and the like.
• DMAP diethylamine
• tributylamine N, N-dimethyl-4-aminopyridine
• DBU 2,4,6-tris (dimethylaminomethyl) phenol
• DBU 1,8-diazabicyclo [5,4, 0] -undecene-7
• DBN 1,5-diazabicyclo [4,3,0] -nonene-5
• imidazole examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl.
• Imidazole 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methyl With imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl- Examples include 2-methyl-3-benzylimidazolium chloride and 2-methylimidazoline.
• the curable composition of the present invention may contain other components in addition to the aromatic ester compound (A), the maleimide compound (B), and the epoxy compound (C).
• the other component which the curable composition of this invention can contain is not limited to what was illustrated below, You may contain components other than these.
• resin components include, but are not limited to, polyester resins other than the aromatic ester compound (A), imide resins other than the maleimide compound (B), cyanate ester resins, benzoxazine resins, and triazine-containing cresols.
• These other resins may be used alone or in combination of two or more.
• the polyester resin other than the aromatic ester compound (A) is not particularly limited, but generally has high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds.
• a compound having two or more ester groups in one molecule is preferably used.
• the polyester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
• a polyester resin obtained from a carboxylic acid compound or a halide thereof and a hydroxy compound is preferred, and a polyester resin obtained from a carboxylic acid compound or a halide thereof and a phenol compound and / or a naphthol compound is more preferred.
• the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like, or a halide thereof.
• phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m -Cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin Benzenetriol, dicyclopentadiene-phenol addition resin, and the like.
• polyester resin specifically, a polyester resin containing a dicyclopentadiene-phenol addition structure, a polyester resin containing a naphthalene structure, a polyester resin that is an acetylated product of phenol novolac, a polyester resin that is a benzoylated product of phenol novolac, and the like are preferable.
• polyester resins containing a dicyclopentadiene-phenol addition structure and polyester resins containing a naphthalene structure are more preferred in that they are excellent in improving the peel strength.
• examples of the polyester resin containing a dicyclopentadiene-phenol addition structure include compounds represented by the following general formula (iv).
• R b represents a phenyl group or a naphthyl group, d represents 0 or 1, and h represents an average of 0.05 to 2.5 repeating units.
• Rb is preferably a naphthyl group, d is preferably 0, and h is preferably 0.25 to 1.5.
• cyanate ester resin 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 M type cyanate ester resin, bisphenol P type cyanate ester resin, Bisphenol Z type cyanate ester resin, bisphenol AP type cyanate ester resin, bisphenol sulfide type cyanate ester resin, phenylene ether type cyanate ester resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, Polyhydroxynaphthalene-type cyanate ester resin, phenol novola Type cyanate ester resin, cresol novolac type cyanate ester resin, triphenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-
• cyanate ester resins bisphenol A-type cyanate ester resins, bisphenol F-type cyanate ester resins, bisphenol E-type cyanate ester resins, and polyhydroxynaphthalene-type cyanate ester resins are particularly preferred in that a cured product having excellent heat resistance can be obtained.
• a naphthylene ether type cyanate ester resin or a novolak type cyanate ester resin is preferably used, and a dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferred in that a cured product having excellent dielectric properties can be obtained.
• the benzoxazine resin is not particularly limited.
• a reaction product of bisphenol F, formalin and aniline Fa type benzoxazine resin
• a reaction product of diaminodiphenylmethane, formalin and phenol Pd type
• Benzoxazine resin reaction product of bisphenol A, formalin and aniline
• reaction product of dihydroxydiphenyl ether, formalin and aniline reaction product of diaminodiphenyl ether, formalin and phenol
• the composition may include a solvent.
• the solvent has a function of adjusting the viscosity of the composition.
• the solvent include, but are not limited to, ketones such as acetone, methyl ethyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; cellosolve, butyl carbitol, and the like Examples thereof include carbitols, aromatic hydrocarbons such as toluene and xylene, amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.
• the amount of the solvent used is preferably 10 to 80% by mass and more preferably 20 to 70% by mass with respect to the total mass of the curable composition. It is preferable that the amount of the solvent used is 10% by mass or more because of excellent handling properties. On the other hand, when the amount of the solvent used is 80% by mass or less, it is preferable because the impregnation property with another substrate is excellent.
• the composition may include an additive.
• the additive include a curing accelerator other than the curing accelerator described for the epoxy resin, a flame retardant, and a filler.
• the curing accelerator is not particularly limited, and examples thereof include guanidine-based curing accelerators, urea-based curing accelerators, peroxides, and azo compounds.
• Guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5 , 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, Examples thereof include 1-ethyl biguanide, 1-butyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide and the like.
• urea curing accelerator examples include 3-phenyl-1,1-dimethylurea, 3- (4-methylphenyl) -1,1-dimethylurea, chlorophenylurea, 3- (4-chlorophenyl) -1,1. -Dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea and the like.
• peroxide and azo compound examples include dicumyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, and azobis.
• dicumyl peroxide 2-ethyl-4-methylimidazole, and dimethylaminopyridine are preferably used.
• the above-mentioned hardening accelerator may be used independently or may be used in combination of 2 or more type.
• the use amount of the curing accelerator is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the resin solid content of the curable composition. It is preferable that the use amount of the curing accelerator is 0.01 parts by mass or more because of excellent curability. On the other hand, when the use amount of the curing accelerator is 5 parts by mass or less, it is preferable because the moldability is excellent.
• the flame retardant is not particularly limited, and examples thereof include inorganic phosphorus flame retardants, organic phosphorus flame retardants, and halogen flame retardants.
• the inorganic phosphorus flame retardant is not particularly limited, and examples thereof include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphoric acid amides.
• the organophosphorus flame retardant is not particularly limited, but is methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) Phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl ) Phosphoric acid such as methacrylate acid phosphate Steal; diphenylphosphine such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dipheny
• the halogen flame retardant is not particularly limited, but brominated polystyrene, bis (pentabromophenyl) ethane, tetrabromobisphenol A bis (dibromopropyl ether), 1,2, -bis (tetrabromophthalimide), 2, Examples include 4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, tetrabromophthalic acid and the like.
• the above-mentioned flame retardants may be used alone or in combination of two or more.
• the amount of flame retardant used is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts per 100 parts by mass of resin solid content of the curable composition.
• the amount of the flame retardant used is 0.1 part by mass or more, it is preferable because flame retardancy can be imparted.
• the amount of flame retardant used is 50 parts by mass or less, it is preferable because flame retardancy can be imparted while maintaining dielectric properties.
• Examples of the filler include organic fillers and inorganic fillers.
• the filler has a function of improving elongation, a function of improving mechanical strength, and the like.
• the organic filler is not particularly limited, and examples thereof include polyamide particles.
• the inorganic filler is not particularly limited, but silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, nitriding Boron, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate , Calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black and the like.
• silica it is preferable to use silica.
• amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, or the like can be used as the silica.
• the filler may be surface-treated as necessary.
• the surface treatment agent that can be used in this case is not particularly limited, but an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, and a titanate coupling. An agent or the like can be used.
• Specific examples of the surface treatment agent include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilane. Silazane etc. are mentioned.
• the above-mentioned filler may be used independently or may be used in combination of 2 or more type.
• the average particle diameter of the filler is not particularly limited and is preferably 0.01 to 10 ⁇ m, more preferably 0.03 to 5 ⁇ m, and further preferably 0.05 to 3 ⁇ m.
• the “particle size” means the maximum length of the distance between two points on the particle outline.
• the “average particle size” is measured by a method of measuring the particle size of 100 arbitrary particles in one screen in an image obtained by a scanning electron microscope (SEM) and calculating the average value. Shall be adopted.
• the amount of the filler used is preferably 0.5 to 95 parts by mass and more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the resin solid content of the curable composition. It is preferable that the amount of the filler used is 0.5 parts by mass or more because low thermal expansion can be imparted. On the other hand, when the amount of the filler used is 95 parts by mass or less, it is preferable because the balance between characteristics and moldability is excellent.
• a cured product obtained by curing a curable composition containing the aromatic ester compound (A), the maleimide compound (B), and the epoxy compound (C). .
• the above-mentioned aromatic ester compound (A) has a polymerizable unsaturated bond-containing substituent, it can be polymerized by itself and a cured product can be obtained.
• the cured product may contain the above-described curing agent, additive, curing accelerator, and the like as necessary.
• the cured product has a low dielectric loss tangent and is more heat resistant by reacting with the maleimide compound (B) and the epoxy compound (C). Since it becomes the cured
• the heating temperature at the time of heat curing is not particularly limited, but is preferably 150 to 300 ° C, more preferably 175 to 250 ° C.
• Synthesis example 1 268 g (2.0 mol) of orthoallylphenol and 1200 g of toluene were charged in a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer, and the system was dissolved by substituting with nitrogen under reduced pressure. Next, 203 g (1.0 mol) of isophthalic acid chloride was charged, and the inside of the system was purged with nitrogen under reduced pressure to be dissolved. Thereafter, 0.6 g of tetrabutylammonium bromide was dissolved and the inside of the system was controlled to 60 ° C.
• This active ester resin (A-1) has an ester group equivalent of 199 g / eq, an allyl group equivalent of 199 g / eq, and an E-type viscosity (25 ° C.) of 6000 mPa.s. s.
• reaction solution separated into two layers was transferred to a separating funnel, and the lower aqueous layer was separated and removed, and then the organic layer was washed 5 times with 500 ml of distilled water. Next, methyl isobutyl ketone was completely distilled off under reduced pressure to obtain a reddish brown liquid reaction product. Next, this reaction product was transferred to a flask, heated to 150 ° C. and stirred for 2 hours to conduct a rearrangement reaction. As a result, an allylated form of 1-naphthol represented by the following structural formula was obtained. The hydroxyl equivalent of the allylated product of 1-naphthol was 195 g / eq.
• Synthesis Example 2-2 A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 390 g (2.0 mol) of 1-naphthol allylate and 1560 g of toluene obtained above, and the system was purged with nitrogen under reduced pressure. And dissolved. Next, 203 g (1.0 mol) of isophthalic acid chloride was charged, and the inside of the system was purged with nitrogen under reduced pressure to be dissolved. Thereafter, 0.8 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C.
• This active ester resin (A ′) had an ester group equivalent of 223 g / eq and a softening point of 150 ° C.
• Maleimide compound (B-1) 4,4′-diphenylmethane bismaleimide (“BMI-1000” manufactured by Daiwa Kasei Co., Ltd., maleimide group equivalent 179 g / equivalent)
• Epoxy resin (C-1) dicyclopentadiene phenol type epoxy resin (“EPICLONP-7200H” epoxy equivalent 277 g / equivalent by DIC Corporation)
• Epoxy resin (C-2) Bisphenol A type epoxy resin (“EPICLON 850S” epoxy equivalent 188 g / equivalent by DIC Corporation)
• DABPA diallyl bisphenol A ("DABPA” manufactured by Daiwa Kasei Co., Ltd., allyl group equivalent: 154 g / eq)
• DMAP dimethylaminopyridine
• the curable composition was poured into a 11 cm ⁇ 9 cm ⁇ 2.4 mm mold and molded using a press machine at 150 ° C. for 60 minutes, then at 175 ° C. for 90 minutes, and further at 200 ° C. for 90 minutes.
• the molded product was taken out from the mold and further cured at 230 ° C. for 4 hours to obtain a cured product.
• the cured product obtained above was heated and vacuum dried at 105 ° C. for 2 hours, and then stored in a room at 23 ° C. and 50% humidity for 24 hours.
• a “network analyzer E8362C” manufactured by Agilent Technologies the dielectric loss tangent of the test piece at 1 GHz was measured by the cavity resonance method.

Landscapes

• Engineering & Computer Science (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Power Engineering (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Computer Hardware Design (AREA)
• Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Laminated Bodies (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
• Epoxy Resins (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=68061401

Family Applications (1)

Country Status (4)

Cited By (1)

Citations (7)

Family Cites Families (4)

• 2019
  • 2019-03-14 JP JP2020509891A patent/JP7057905B2/ja active Active
  • 2019-03-14 WO PCT/JP2019/010506 patent/WO2019188333A1/ja active Application Filing
  • 2019-03-14 CN CN201980023293.6A patent/CN111971323B/zh active Active
  • 2019-03-22 TW TW108109968A patent/TWI794455B/zh active

Patent Citations (7)

Also Published As

Similar Documents

Legal Events