Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
  • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
• • 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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
• • 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
  • C08J5/247—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using fibres of at least two types
• • 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
  • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
• • 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
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/46—Manufacturing multilayer circuits
  • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
  • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/07—Parts immersed or impregnated in a matrix
  • B32B2305/076—Prepregs
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/08—PCBs, i.e. printed circuit boards
• • 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
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • 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
  • H05K1/032—Organic insulating material consisting of one material
  • H05K1/0346—Organic insulating material consisting of one material containing N
• • 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
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/17—Post-manufacturing processes
  • H05K2203/176—Removing, replacing or disconnecting component; Easily removable component

Definitions

• the present invention relates to a prepreg, a metal-clad laminate, and a printed wiring board.
• Polyphenylene ether resin has excellent high-frequency characteristics (dielectric characteristics) such as dielectric constant and dielectric loss, and is used as an insulating material for printed wiring boards of electronic devices such as mobiles that use high frequency bands (). For example, see Patent Document 1).
• high molecular weight PPE has a high melting point and does not have sufficient adhesion to a base material or other members. Therefore, when a prepreg used for manufacturing a normal multi-layer printed wiring board is formed using PPE, the melt viscosity of the prepreg becomes high, and molding defects such as voids and fading occur during multi-layer molding, resulting in reliability. It is difficult to obtain a multi-layer printed wiring board with a high viscosity, and there is a problem that the adhesion to a base material or the like is insufficient.
• the present invention has been made to solve at least a part of the above-mentioned problems, and can be realized as any of the following aspects.
• One aspect of the prepreg according to the present invention is It contains a base material and a polymer having a structural unit represented by at least one of the following formulas (1-1), (1-2) and (1-3).
• R 1 is independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogen having 1 to 20 carbon atoms. It is a salt of a hydrocarbon group, a nitro group, a cyano group, a 1st to 3rd order amino group, or a 1st to 3rd order amino group.
• n is an integer of 0 to 2 independently of each other.
• R 1s When n is 2, the plurality of R 1s may be the same or different, and may be bonded in any combination to form a part of the ring structure.
• a 1 and A 2 are independently -O-, -S-, or -N (R 2 )-.
• R2 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms.
• X is a divalent organic group.
• the divalent organic group represented by X in the formulas (1-1) to (1-3) may contain a group represented by the following formula (2-1).
• Ar 1 and Ar 2 are independently substituted or unsubstituted aromatic hydrocarbon groups.
• R 8 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms.
• y is an integer from 0 to 5. When y is 2 or more, the plurality of Ls may be the same or different.
• R 6 and R 7 are independently single bonds, methylene groups, or alkylene groups having 2 to 4 carbon atoms. ]
• the prepreg of any of the above embodiments may further contain a curable compound.
• the prepreg of any of the above embodiments may further contain a curing aid, a flame retardant, and an inorganic filler.
• the base material may be glass cloth, and the dielectric constant of the glass cloth may be 6.8 or less.
• One aspect of the metal-clad laminate according to the present invention is It is obtained by laminating and curing a prepreg of any one of the above embodiments and a metal foil.
• One aspect of the printed wiring board according to the present invention is It is characterized in that a part of the metal foil is removed from the metal-clad laminate of the above aspect.
• the prepreg according to the present invention it is possible to manufacture a metal-clad laminated board or a multilayer printed wiring board having high reliability and excellent adhesion to a base material or the like.
• the numerical range described by using "XY” means that the numerical value X is included as the lower limit value and the numerical value Y is included as the upper limit value.
• the prepreg according to an embodiment of the present invention has a substrate and a weight having a structural unit represented by at least one of the following formulas (1-1), (1-2) and (1-3). Containing with coalescence.
• R 1 is independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogen having 1 to 20 carbon atoms. It is a salt of a hydrocarbon group, a nitro group, a cyano group, a 1st to 3rd order amino group, or a 1st to 3rd order amino group.
• n is an integer of 0 to 2 independently of each other. When n is 2, the plurality of R 1s may be the same or different, and may be bonded in any combination to form a part of the ring structure.
• a 1 and A 2 are independently -O-, -S-, or -N (R 2 )-.
• R2 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms.
• X is a divalent organic group.
• Base material includes various glass cloths such as roving cloth, cloth, chopped mat, and surfacer mat; boron fiber, alumina fiber, silicon nitride fiber, asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fibers. Cloth; woven or non-woven fabric obtained from liquid crystal fibers such as all aromatic polyamide fiber, all aromatic polyester fiber, polybenzoxazole fiber; natural fiber cloth such as cotton cloth, linen cloth, felt; carbon fiber cloth, kraft paper, cotton paper , Natural cellulose-based base material such as cloth obtained from paper-glass mixed fiber; polytetrafluoroethylene porous film and the like. These base materials may be used alone or in combination of two or more.
• the dielectric constant of the glass cloth is preferably 6.8 or less, more preferably 5.1 or less, and even more preferably 4.9 or less. Since the base material is glass cloth, the heat resistance of the laminated board can be further improved, and the thermal expansion rate tends to be further reduced. When the dielectric constant of the glass cloth is 6.8 or less, the increase in the dielectric constant of the laminated plate tends to be further suppressed.
• the "dielectric constant of the glass cloth” is a value at 1 GHz measured by the cavity resonance method described later using a sample processed into a lump instead of a cloth.
• the proportion of the solid content of the resin composition in the prepreg according to the present embodiment is preferably 30 to 80% by mass, more preferably 40 to 70% by mass.
• the proportion of the solid content of the resin composition in the prepreg according to the present embodiment is preferably 30 to 80% by mass, more preferably 40 to 70% by mass.
• the insulation reliability tends to be further improved when the prepreg is used for an electronic substrate or the like.
• the above ratio is 80% by mass or less, it tends to be excellent in mechanical properties such as workability and flexural modulus when used for an electronic substrate or the like.
• the prepreg according to the present embodiment has at least one repeating unit among the repeating units represented by the following general formulas (1-1), (1-2) and (1-3) as a polymer. It contains a polymer (hereinafter, also referred to as "specific polymer").
• R 1 is independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogen having 1 to 20 carbon atoms. It is a salt of a hydrocarbon group, a nitro group, a cyano group, a 1st to 3rd order amino group, or a 1st to 3rd order amino group.
• n is an integer of 0 to 2 independently of each other. When n is 2, the plurality of R 1s may be the same or different, and may be bonded in any combination to form a part of the ring structure.
• a 1 and A 2 are independently -O-, -S-, or -N (R 2 )-.
• R2 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms.
• X is a divalent organic group.
• halogen atom represented by R 1 examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 include a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. And so on.
• Examples of the monovalent chain hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group.
• Alkyl groups such as ethenyl group, propenyl group, butenyl group, pentenyl group and the like; alkynyl groups such as ethynyl group, propynyl group, butyl group, pentynyl group and the like can be mentioned.
• Examples of the monovalent alicyclic hydrocarbon group include a monocyclic cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group; and a polycyclic cycloalkyl group such as a norbornyl group and an adamantyl group; Examples thereof include a monocyclic cycloalkenyl group such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group and a cyclohexenyl group; and a polycyclic cycloalkenyl group such as a norbornenyl group.
• Examples of the monovalent aromatic hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group and an anthryl group; and an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group and a naphthylmethyl group. And so on.
• examples thereof include a group in which a part or all of the atom is replaced with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• the substituent in the secondary amino group and the tertiary amino group represented by R 1 is not particularly limited, and for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms exemplified as the group represented by R 1 is used. Can be mentioned.
• the cation constituting the cation moiety in the salt of the primary to tertiary amino group represented by R 1 is not particularly limited, and a known cation such as Na + can be used.
• R 1 is a halogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a monovalent halogenated hydrocarbon having 1 to 6 carbon atoms from the viewpoint of improving the polymerization reactivity and solubility of the monomer.
• a salt of a group, a nitro group, a cyano group, a 1- to tertiary amino group, or a 1- to tertiary amino group is preferable, and a fluorine atom, a chlorine atom, a methyl group, a nitro group, a cyano group, a tert-butyl group, a phenyl group, Amino groups are more preferred. From the same viewpoint, as n, 0 or 1 is preferable, and 0 is more preferable.
• R2 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms.
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 2 include a monovalent hydrocarbon group having 1 to 20 carbon atoms exemplified as the group represented by R 1 . .. Further, in R 2 , a part or all of the hydrogen atom of the hydrocarbon group may be substituted with an ester group or a sulfonyl group.
• R2 a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferable from the viewpoint of improving the polymerization reactivity of the monomer. Further, when A 1 and A 2 are both ⁇ N (R 2 ) ⁇ , the two R 2s may be the same or different.
• the position of the other bond with respect to one of the repeating units is not particularly limited, but the meta position is preferable in order to improve the polymerization reactivity of the monomer giving the repeating unit.
• the repeating unit from the viewpoint of improving the polymerization reactivity of the monomer and the viewpoint of improving the solubility in various organic solvents, the repeating unit represented by the above general formula (1-2) having a pyrimidine skeleton. The unit is preferred.
• Examples of the monomer giving such a repeating unit include 4,6-dichloropyrimidine, 4,6-dibromopyrimidine, 2,4-dichloropyrimidine, 2,5-dichloropyrimidine, and 2,5-dibromopyrimidine.
• a 1 and A 2 in the above formulas (1-1), (1-2), and (1-3) are independently represented by -O-, -S-, or -N (R 2 )-. be.
• a 1 and A 2 are —O—, they are preferable in terms of flexibility, solubility and heat resistance.
• a 1 and A 2 are ⁇ N (R 2 ) ⁇ , it is preferable in terms of adhesion and the like.
• R 2 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and may contain an ester group or a sulfonyl group.
• the specific polymer is a divalent organic group represented by the above X in the above formulas (1-1), (1-2) and (1-3), and is a group represented by the following formula (2-1). Is preferably contained.
• Ar 1 and Ar 2 are independently substituted or unsubstituted aromatic hydrocarbon groups.
• R 8 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms.
• y is an integer from 0 to 5. When y is 2 or more, the plurality of Ls may be the same or different.
• R 6 and R 7 are independently single bonds, methylene groups, or alkylene groups having 2 to 4 carbon atoms. ]
• aromatic hydrocarbon group represented by Ar 1 and Ar 2 an aromatic hydrocarbon group having 6 or more and 30 or less carbon atoms is preferable, and any one of a phenyl group, a naphthyl group and an anthryl group is preferable. Is more preferable, and a phenyl group or a naphthyl group is particularly preferable.
• each of the aromatic hydrocarbon groups represented by Ar 1 and Ar 2 may have 1 to 8 substituents.
• the number of substituents of the aromatic hydrocarbon groups represented by Ar 1 and Ar 2 is preferably 0 to 8 and more preferably 0 to 4, respectively, from the viewpoint of improving the polymerization reactivity of the monomers. 0 to 2 is particularly preferable.
• the substituent is not particularly limited, but is a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and carbon.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
• the monovalent hydrocarbon group having 1 to 20 carbon atoms for example, the monovalent hydrocarbon group having 1 to 20 carbon atoms exemplified as the group represented by R1 in the above formulas (1-1) to (1-3). Hydrocarbon groups and the like.
• Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms include those having 1 to 20 carbon atoms exemplified as the group represented by R1 in the above formulas (1-1) to (1-3). Examples thereof include a group in which a part or all of hydrogen atoms of a monovalent hydrocarbon group are replaced with halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• alkoxy group having 1 to 20 carbon atoms examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group and the like.
• alkylthio group having 1 to 20 carbon atoms examples include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group and the like.
• the substituent in the secondary amino group and the tertiary amino group is not particularly limited, and examples thereof include a monovalent hydrocarbon group having 1 to 20 carbon atoms exemplified as the group represented by R1 .
• the cations constituting the cation moiety in the carboxy group salt, the sulfonic acid group salt, the phosphonic acid group salt, the phosphoric acid group salt, the hydroxy group salt, and the 1st to 3rd tertiary amino group salt are not particularly limited. It can be a known cation such as Na + .
• the substituents of the aromatic hydrocarbon groups represented by Ar 1 and Ar 2 are halogen atoms and monovalent hydrocarbon groups having 1 to 3 carbon atoms, respectively, from the viewpoint of improving the polymerization reactivity of the monomers.
• Phosphate group hydroxy group, 1-3 amino group, carboxy group salt, sulfonic acid group salt, phosphonic acid group salt, phosphate group salt, hydroxy group salt, or 1-3 amino group Is preferable, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a fluoromethyl group, a methoxy group, a methylthio group, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group and a hydroxy group.
• a primary to tertiary amino group, a carboxy group salt, a sulfonic acid group salt, a phosphonic acid group salt, a phosphoric acid group salt, a hydroxy group salt, or a 1 to 3 tertiary amino group salt is preferable.
• a and b are preferably 0 to 8, more preferably 0 to 4, and particularly preferably 0 to 2, respectively.
• c and d are preferably 0 to 2, respectively, and more preferably 0 or 1.
• Examples of the divalent organic group having 1 to 20 carbon atoms represented by L include a methylene group, an alkylene group having 2 to 20 carbon atoms, a methylene halide group, and a halogenated alkylene group having 2 to 20 carbon atoms, 2
• the cardo structure of valence and the like can be mentioned.
• Examples of the alkylene group having 2 to 20 carbon atoms represented by L include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a sec-butylene group, a tert-butylene group, a neopentylene group and 4-. Examples thereof include a methyl-pentane-2-diyl group and a nonan-1,9-diyl group.
• Examples of the halogenated methylene group represented by L include a group in which a part or all of the hydrogen atom of the methylene group is replaced with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• halogenated alkylene group having 2 to 20 carbon atoms represented by L for example, a part or all of the hydrogen atom of the alkylene group having 2 to 20 carbon atoms exemplified as the group represented by L is a fluorine atom and chlorine. Examples thereof include a group substituted with a halogen atom such as an atom, a bromine atom and an iodine atom.
• the divalent cardo structure represented by L includes a divalent group derived from fluorene (that is, a group excluding two hydrogen atoms in fluorene) and a divalent group derived from phenolphthalene (that is, phenol).
• Groups excluding two hydrogen atoms in phthalein), groups represented by the following formula (L1), and the like can be mentioned.
• a part or all of the hydrogen atom is replaced with a monovalent chain hydrocarbon group having 1 to 20 carbon atoms. Further, a part or all of the hydrogen atom including the substituent may be substituted with a fluorine atom.
• R c is a divalent alicyclic hydrocarbon group having 5 to 30 ring members.
• Examples of the divalent alicyclic hydrocarbon group having 5 to 30 ring members represented by R c include a monocyclic alicyclic hydrocarbon group having 5 to 15 ring members and a single ring having 5 to 15 ring members. Examples thereof include a fluorinated alicyclic hydrocarbon group, a polycyclic alicyclic hydrocarbon group having 7 to 30 ring members, and a polycyclic fluorinated alicyclic hydrocarbon group having 7 to 30 ring members.
• Examples of the monocyclic alicyclic hydrocarbon group having 5 to 15 ring members include cyclopentane-1,1-diyl group, cyclohexane-1,1-diyl group, and 3,3,5-trimethylcyclohexane-1.
• the monocyclic fluorinated alicyclic hydrocarbon group having 5 to 15 ring members may be, for example, a part of the hydrogen atom of the group exemplified as the alicyclic hydrocarbon group having 5 to 15 ring members. Examples thereof include groups in which all are substituted with a fluorine atom.
• polycyclic alicyclic hydrocarbon group having 7 to 30 ring members examples include norbornane, norbornene, adamantan, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [5.2.1. 0 2,6 ]
• Polycyclic fats such as heptane, pinan, kanfan, decalin, norbornene, perhydroanthracene, perhydroazulen, cyclopentanohydrophenantrene, bicyclo [2.2.2] -2-octene
• a group excluding two hydrogen atoms bonded to one carbon atom of a cyclic hydrocarbon, and a part or all of the hydrogen atoms of these groups are monovalent chain hydrocarbon groups having 1 to 20 carbon atoms. Examples include substituted groups.
• the polycyclic fluorinated alicyclic hydrocarbon group having 7 to 30 ring members may be, for example, a part of the hydrogen atom of the group exemplified as the polycyclic alicyclic hydrocarbon group having 7 to 30 ring members. Examples thereof include groups in which all are substituted with fluorine atoms.
• L from the viewpoint of structural stability of the polymer, single bond, -O-, -S-, -C (O)-, -S (O)-, -S (O) 2- , -C ( O) -NH-, -C (O) -O-, methylene group, alkylene group having 2 to 5 carbon atoms, methylene halide group, alkylene group having 2 to 10 carbon atoms, or a divalent cardo structure.
• y is preferably 0 to 4, more preferably 0 to 3.
• Examples of the alkylene group having 2 to 4 carbon atoms represented by R 6 and R 7 include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a sec-butylene group and a tert-butylene group. Can be mentioned.
• R 6 and R 7 single bonds, methylene groups, or ethylene groups are preferable from the viewpoint of improving the polymerization reactivity of the monomers, respectively.
• Y is an integer from 0 to 5. From the viewpoint of improving the solubility of the polymer and imparting flexibility, it is preferably 1 or more. Further, when y is 2 or more, the plurality of Ls may be the same or different.
• the content ratio of the repeating units represented by the above general formulas (1-1), (1-2) and (1-3) in the specific polymer is 100 mol% of the total of all the repeating units in the specific polymer. , 1 to 95 mol% is preferable, and 5 to 80 mol% is more preferable.
• the method for synthesizing the specific polymer is not particularly limited, and a known method can be used.
• the product can be synthesized by heating it in an organic solvent together with an alkali metal or the like.
• the lower limit of the weight average molecular weight (Mw) of the specific polymer is preferably 500, more preferably 1,000, even more preferably 2,000, and particularly preferably 3,000. preferable.
• the upper limit of the weight average molecular weight (Mw) is preferably 600,000, more preferably 300,000, and particularly preferably 200,000.
• the lower limit of the glass transition temperature (Tg) of the specific polymer is preferably 70 ° C, more preferably 80 ° C.
• the upper limit of the glass transition temperature (Tg) is preferably 320 ° C., more preferably 300 ° C. from the viewpoint of workability.
• Examples of these specific polymers include the polymers described in JP-A-2015-209511, International Publication No. 2016/143447, JP-A-2017-197725, JP-A-2018-024827, and the like.
• the prepreg according to the present embodiment contains a specific polymer, it is possible to manufacture a printed wiring board having low dielectric loss characteristics for reducing crosstalk between wirings and low dielectric loss characteristics for suppressing signal loss. can. Further, since the prepreg according to the present embodiment contains a specific polymer, a highly reliable multilayer printed wiring board can be obtained without causing molding defects such as voids and fading during multilayer molding, and a base such as glass cloth can be obtained. Adhesion to the material is also good.
• the method for producing a prepreg according to an embodiment of the present invention comprises a step of impregnating or coating a substrate with a composition containing the above-mentioned specific polymer (hereinafter, also referred to as “resin composition”).
• resin composition a composition containing the above-mentioned specific polymer
• the above-mentioned prepreg is contained in the resin composition after, for example, impregnating a base material such as glass cloth into the resin composition or applying the resin composition to the base material such as glass cloth. It can be produced by drying and removing the solvent.
• Examples of the method of impregnating or applying the resin composition to the base material include a method using a dip, a roll, a die coat, a bar coat, and the like, and spraying.
• the method for drying and removing the solvent is not particularly limited, and examples thereof include a method of heating and / or drying with a hot air dryer or the like.
• the prepreg produced by such a method may include a base material and a resin composition or a semi-cured product of the resin composition.
• a prepreg include those in which a fibrous base material is present in a semi-cured product. That is, this prepreg comprises a semi-cured product of the resin composition and a fibrous base material present in the semi-cured product.
• the semi-cured product is a state in which the resin composition is partially cured to the extent that it can be further cured. That is, the semi-cured product is a semi-cured (B-staged) resin composition. For example, when the resin composition is heated, the viscosity gradually decreases first, then curing starts, and the viscosity gradually increases. In such a case, the semi-curing state includes a state between the time when the viscosity starts to increase and the time before it is completely cured.
• the prepreg obtained by using the resin composition may include a semi-cured product of the resin composition as described above, or a prepreg before curing the resin composition.
• You may. That is, it may be a prepreg comprising a semi-cured product (B-stage resin composition) of the resin composition and a base material, or a pre-cured resin composition (A-stage resin composition) and a base material. It may be a prepreg including.
• Resin composition in addition to the above-mentioned specific polymer, the resin composition may contain other polymers, curable compounds, curing aids, flame retardants, inorganic fillers, solvents and the like.
• the content ratio of the specific polymer in the resin composition is preferably 5% by mass or more, more preferably 10% by mass, when the total of the specific polymer, other polymers and the curable compound is 100% by mass. % Or more, more preferably 15% by mass or more, and particularly preferably 20% by mass or more. Further, the content ratio of the specific polymer in the resin composition is preferably 100% by mass or less, more preferably 100% by mass, when the total of the specific polymer, other polymers and the curable compound is 100% by mass. It is 80% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. When the content ratio of the specific polymer is within the above range, it may be possible to manufacture a multilayer printed wiring board having excellent reliability and low dielectric properties and excellent adhesion to a substrate or the like.
• a known material having a low dielectric constant and a low dielectric loss tangent property such as polyimide, polyarylate, and polyarylene ether can be appropriately contained.
• polyarylene ether is particularly preferable because it has excellent compatibility with the above-mentioned specific polymer and a transparent appearance can be obtained when it is made into a mixed varnish.
• the lower limit of the weight average molecular weight (Mw) of the other polymers is preferably 500, more preferably 800, and particularly preferably 1,000.
• the upper limit of the weight average molecular weight (Mw) is preferably 50,000, more preferably 30,000, even more preferably 10,000, and particularly preferably 6,000.
• the content ratio of the other polymers in the resin composition is 100% by mass when the total of the specific polymer, the other polymers and the curable compound is 100% by mass. It is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. Further, the content ratio of the other polymer in the resin composition is preferably 75% by mass or less, more preferably, when the total of the specific polymer, the other polymer and the curable compound is 100% by mass. Is 60% by mass or less, and particularly preferably 50% by mass or less.
• the curable compound is a compound that is cured by irradiation with heat or light (for example, visible light, ultraviolet rays, near infrared rays, far infrared rays, electron beams, etc.), and may require a curing aid described later. ..
• examples of such curable compounds include epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, urethane compounds, oxetane compounds, methylol compounds and propargyl compounds. Can be mentioned. These may be used alone or in combination of two or more.
• the epoxy compound, cyanate ester compound, vinyl compound, silicone compound, oxazine compound, maleimide compound, and allyl compound from the viewpoint of compatibility with the above-mentioned specific polymer, heat resistance, and the like. It is preferably one kind, and more preferably at least one kind among an epoxy compound, a cyanate ester compound, a vinyl compound, an allyl compound, and a maleimide compound.
• Examples of the epoxy compound include compounds represented by the following formulas (c1-1) to (c1-6).
• the compound represented by the following formula (c1-6) is an epoxy group-containing NBR particle "XER-81" manufactured by JSR Corporation.
• the epoxy compound polyglycidyl ether of dicyclopentadiene-phenol polymer, phenol novolac type liquid epoxy compound, epoxidized product of styrene-butadiene block copolymer, 3', 4'-epoxycyclohexylmethyl-3,4 -Epoxycyclohexanecarboxylate and the like can also be mentioned.
• n is 0 to 5000
• m is independently 0 to 5000.
• Examples of the cyanate ester compound include compounds represented by the following formulas (c2-1) to (c2-7).
• n is independently 0 to 30.
• Examples of the vinyl compound include compounds represented by the following formulas (c3-1) to (c3-5).
• n 1 to 5000.
• silicone compound examples include compounds represented by the following formulas (c4-1) to (c4-16).
• R in the formula (c4-1) if any of the following is selected and a compound having a vinyl group is selected, it can be treated as the vinyl compound, and a compound having an oxetane group is selected. If so, it can also be treated as the oxetane compound.
• R is an organic group independently selected from an alkyl group, an alicyclic saturated hydrocarbon group, an aryl group, and an alkenyl group
• n is an organic group. It is an integer of 0 to 1000 (preferably an integer of 0 to 100).
• Examples of the oxazine compound include compounds represented by the following formulas (c5-1) to (c5-5).
• maleimide compound examples include compounds represented by the following formulas (c6-1) to (c6-5).
• allyl compound examples include compounds represented by the following formulas (c7-1) to (c7-6).
• this allyl compound a compound having two or more (particularly 2 to 6, further 2 to 3) allyl groups is preferable.
• Examples of the oxetane compound include compounds represented by the following formulas (c8-1) to (c8-3).
• methylol compound examples include the methylol compounds described in JP-A-2006-178059 and JP-A-2012-226297.
• melamine-based methylol compounds such as polymethylolated melamine, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxymethyl melamine;
• Glycoluryl-based methylol compounds such as tetrabutoxymethylglycol uryl; 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetra Oxospiro [5.5] undecane, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) propyl] -2,4,8,10-tetraoxospiro [5] .5]
• examples thereof include compounds obtained by methylo
• Examples of the propagyl compound include compounds represented by the following formulas (c9-1) to (c9-2).
• the content ratio of the curable compound in the resin composition is preferably 100% by mass when the total of the specific polymer, other polymers and the curable compound is 100% by mass. It is 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more.
• the content ratio of the curable compound in the resin composition is preferably 75% by mass or less, more preferably 75% by mass or less, when the total of the specific polymer, other polymers and the curable compound is 100% by mass. It is 60% by mass or less, and particularly preferably 50% by mass or less.
• the curing aid examples include polymerization initiators such as radical initiators and thermal / photoreaction initiators (photoradical generators, photoacid generators, photobase generators).
• the radical initiator contained in the resin composition preferably has a one-minute half-life temperature of 150 ° C. or higher and 190 ° C. or lower.
• the 1-minute half-life temperature of the radical initiator is more preferably 160 ° C. or higher and 190 ° C. or lower, further preferably 165 ° C. or higher and 190 ° C. or lower, and particularly preferably 170 ° C. or higher and 190 ° C. or lower.
• the "1 minute half-life temperature" is a temperature at which the time during which the radical initiator decomposes and the amount of active oxygen thereof is halved is 1 minute.
• the 1-minute half-life temperature is such that the organic peroxide is dissolved in a radical-inactive solvent such as benzene to a concentration of 0.05 mol / L to 0.1 mol / L, and the organic peroxide solution is prepared. It is a value confirmed by the method of thermal decomposition in a nitrogen atmosphere.
• the resin composition containing the specific polymer When the resin composition containing the specific polymer is subjected to heat-pressurization molding because the radical initiator has a one-minute half-life temperature of 150 ° C. or higher, the specific polymer is sufficiently melted and then cross-linked and cured. Cross-linking of the sex compound will be initiated. Therefore, a resin composition containing such a radical initiator is preferable because it has excellent moldability.
• the 1-minute half-life temperature of the radical initiator is 190 ° C. or lower, the decomposition rate of the radical initiator under normal heating and pressure molding conditions (for example, the maximum ultimate temperature of 200 ° C.) is sufficient.
• the cross-linking reaction of the cross-linking curable compound can be efficiently and slowly carried out by using a target small amount (for example, the following range) of the radical initiator. This makes it possible to manufacture a good prepreg with few appearance defects.
• radical initiators examples include 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperoxasiacetate, di-tert-butyl peroxide, and tert-butyl.
• ⁇ , ⁇ '-bis (tert-butylperoxy-m-isopropyl) benzene, and 2,5 from the viewpoint of being able to give a cured product having excellent heat resistance and a low dielectric constant and dielectric loss tangent.
• -Dimethyl-2,5-di (tert-butylperoxy) hexane is preferred.
• polymerization initiators such as thermal / photoreaction initiators (photoradical generators, photoacid generators, photobase generators) include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, and di.
• thermal / photoreaction initiators include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, and di.
• examples thereof include sulfonyldiazomethane compounds, disulfonylmethane compounds, oximsulfonate compounds, hydrazinesulfonate compounds, triazine compounds, nitrobenzyl compounds, benzylimidazole compounds, organic halides, octylate metal salts, disulfones and the like.
• these curing aids may be used alone or in combination of two or more. It may also be used in combination with a radical initiator.
• the curing aid includes an amine-based curing agent, an acid-based or acid anhydride-based curing agent, a basic active hydrogen compound, imidazoles, and a polymercaptan-based curing agent.
• Phenol resin, urea resin, melamine resin, isocyanate-based curing agent, Lewis acid and the like can be used.
• amine-based curing agent examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis (hexamethylene) triamine, and 1,3,6-trisaminomethylhexane.
• Examples include ring-containing aliphatic polyamines; aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and diaminodiethyldiphenylmethane, and derivatives thereof.
• amine-based curing agents include, for example, Mannich-modified amines obtained by reacting polyamines with aldehydes and / or phenols; amine adduct (polyamine epoxy resin adduct), polyamine-ethylene oxide adduct, polyamine-propylene oxide.
• Adduct cyanoethylated polyamines, ketimine which is a reaction product of aliphatic polyamines and ketones; tetramethylguanidine, triethanolamine, piperidine, pyridine, benzyldimethylamine, picolin, 2- (dimethylaminomethyl) phenol, dimethylcyclohexylamine, Dimethylbenzylamine, dimethylhexylamine, dimethylaminophenol, dimethylamino-p-cresol, N, N'-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, 2,4,6-tris (dimethyl) Secondary amines or tertiary amines such as aminomethyl) phenol, 1,8-diazabicyclo [5.4.0] -7-undecene; reaction of dimer acid with polyamines such as diethylenetriamine and triethylenetetramine. Examples thereof include liquid polyamides.
• Examples of the acid-based or acid anhydride-based curing agent include polycarboxylic acids such as adipic acid, azelaic acid, and decandicarboxylic acid; phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimericte), and glycerol.
• Aromatic acid anhydrides such as tris (anhydrotrimeritate), pyromellitic anhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid anhydride; maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride , Methyltetrahydrohydroan phthalic acid, methylnadic acid anhydride, alkenyl succinic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenetetracarboxylic acid anhydride, methylhymic anhydride, trialkyltetrahydrophthalic acid, Cyclic aliphatic acid anhydrides such as poly (phenylhexadecanedianhydride) anhydrides; polyadipic acid anhydrides, polyazelineic acid anhydrides, polysevacinic acid anhydrides, dodecenyl anhydride succin
• Examples of the basic active hydrogen compound include dicyandiamide and organic acid dihydrazide.
• imidazoles examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole and 1-cyanoethyl.
• polymercaptan-based curing agent examples include a partial epoxy adduct of 2,2'-bismercaptoethyl ether; thio such as pentaerythritol tetrathioglycolate, dipentaerythritol hexathioglycolate, and trimethylolpropanetristhioglycolate.
• Esters of glycolic acid examples thereof include compounds containing a mercapto group such as polysulfide rubber having a mercapto group at the terminal.
• isocyanate-based curing agent examples include isocyanate compounds such as toluene diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate; and blocked isocyanate compounds obtained by reacting an isocyanate group with a blocking agent such as phenol, alcohol, and caprolactam to mask them. Will be.
• Lewis acid examples include diaryliodonium salt and triarylsulfonium salt.
• the curing aid includes an onium salt compound, a sulfone compound, a sulfonic acid ester compound, a sulfonimide compound, a disulfonyldiazomethane compound, a disulfonylmethane compound, and an oxime.
• photoacid generators such as organic halides and disulfones can also be used.
• the curing aid includes zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetone, nickel octylate, manganese octylate and the like.
• Phenolic compounds such as organic metal salts, phenol, xylenol, cresol, resorcin, catechol, octylphenol, nonylphenol, alcohols such as 1-butanol, 2-ethylhexanol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2 -Phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl Derivatives of imidazoles such as -4-methyl-5-hydroxymethylimidazole and carboxylic acids of these imidazoles or adducts of acid anhydrides thereof, benzyldimethylamine, 4-methyl-N, N-dimethylbenzylamine.
• phosphine compounds phosphine oxide compounds and other phosphorus compounds
• a photoacid generator or a photobase generator described as a curing aid when the resin composition contains an epoxy compound can also be used.
• a compound (polymerizer) that generates a cation or a radically active species by heat or light can be used as the curing aid.
• the cationic polymerizer include diaryliodonium salt and triarylsulfonium salt.
• the radical polymerizer include benzoin compounds such as benzoin acetophenone, acetophenone compounds such as 2,2-dimethoxy-2-phenylacetophenone, sulfur compounds such as 2,4-diethylthioxanthone, and azobisisobutyronitrile.
• examples thereof include azo compounds such as 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and organic peroxides such as dicumyl peroxide.
• the curing aids include acetophenone, propiophenone, benzophenone, xanthol, benzaldehyde, anthracinone, triphenylamine, carbazole, 3-methylacetophenone, and 4, -Methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'- Dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoinmethyl ether, benzoinbutyl ether, bis (4-dimethylaminophenyl
• the curing aids include platinum black, secondary platinum chloride, platinum chloride acid, a reaction product of platinum chloride acid and monovalent alcohol, and platinum chloride acid and olefin.
• Platinum group metal catalysts such as compounds with similar compounds, platinum-based catalysts such as platinum bisacetoacetate; palladium-based catalysts; rhodium-based catalysts; zinc benzoate, and zinc octylate can be used.
• the curing aid includes phenol and its derivatives, cyanate ester, blended acid such as p-toluenesulfonic acid, adipic acid, and p-toluenesulfon.
• Acid esters, aromatic amine compounds such as 4,4'-diaminodiphenyl sulfone and melamine, bases such as 2-ethyl-4-methylimidazole, boron trifluoride, Lewis acid and the like can also be used.
• a photoacid generator or a photobase generator described as a curing aid when the resin composition contains an epoxy compound can also be used.
• the curing aids include imidazole, 1-methylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole, N, N-diisopropylethylamine, 1 , 4-Dimethylpiperazine, quinoline, triazole, benzotriazole, bases such as DBU, phosphorus compounds such as triphenylphosphine, azobisisobutyronitrile and the like can be used. Further, a photoacid generator or a photobase generator described as a curing aid when the resin composition contains an epoxy compound can also be used.
• the curing aid includes an azo initiator such as azobisisobutyronitrile, dimethyl 2,2'-azobisisobutyrate, a ketone peroxide, and a per.
• Peroxides such as oxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 , 1'-Acetophenone such as hydroxycyclohexylphenyl ketone, benzoin, benzophenone such as benzoin ethyl ether, benzophenone such as benzophenone, phosphorus such as acylphosphine oxide, sulfur such as thioxanthone, benzyl, 9,10-fe A benzyl-based or peroxycarbonate-based curing aid such as nanthrenquinone can be used. Further, a photoacid generator or a photobase generator described as a curing aid when the resin composition contains an epoxy compound can also be used.
• the resin composition contains an oxetane compound or a methylol compound as a curable compound
• a light or thermal cation generator can be used as the curing aid.
• Examples of the photocation generator include onium salt compounds, halogen-containing compounds, sulfonic acid compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds, and specifically, paragraphs [0074] to [0074] of JP-A-2014-186300. 0079], and examples thereof include the compounds described in [0079].
• halogen-containing compound examples include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound.
• preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane; phenyl-bis (trichloromethyl) -s-triazine.
• the content ratio of the curing aid is preferably in the range where the resin composition can be cured well and a cured product can be obtained.
• the specific content ratio of the curing aid is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, when the total mass of the resin composition is 100% by mass. ..
• the resin composition preferably contains a flame retardant.
• the flame retardant include inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide and zinc borate; hexabromobenzene, decabromodiphenylethane, 4,4-dibromobiphenyl, ethylenebistetrabromophthalimide and the like.
• Aromatic bromine compounds such as resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate; phenoxyphosphazenes such as hexaphenoxycyclotriphosphazene, cyanophenoxy (phenoxy) cyclotriphosphazene, crezoyloxy (phenoxy) cyclotriphosphazene.
• phosphorus compounds such as resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate
• phenoxyphosphazenes such as hexaphenoxycyclotriphosphazene, cyanophenoxy (phenoxy) cyclotriphosphazene, crezoyloxy (phenoxy) cyclotriphosphazene.
• flame retardants include flame retardants. These flame retardants may be used alone or in combination of two or more.
• the flame retardant is preferably an inorganic flame retardant, a non-halogen-based phosphorus-based compound, or a phosphazene-based compound from the viewpoint of further excellent reliability and low dielectric properties after curing of the resin composition.
• the content ratio of the flame retardant in the resin composition is a specific polymer, other polymers and curability from the viewpoint of maintaining the flame retardancy of UL standard 94V-0 level. It is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more with respect to 100 parts by mass of the total of the compounds. Further, the content ratio of the flame retardant in the resin composition is 100 parts by mass in total of the specific polymer, other polymers and the curable compound from the viewpoint of keeping the dielectric constant and the dielectric loss tangent of the obtained printed wiring board low. On the other hand, it is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and particularly preferably 40 parts by mass or less.
• the resin composition may contain an inorganic filler.
• the material of the inorganic filler include silica, alumina, silicon nitride, boron nitride, and aluminum nitride.
• silica include natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, and hollow silica. Further, the surface of silica may be surface-treated with a silane coupling agent or the like.
• the content ratio of the inorganic filler may be 10 to 200 parts by mass with respect to 100 parts by mass in total of the specific polymer, other polymers and the curable compound. preferable.
• the resin composition may contain a solvent.
• the resin composition may be in the form of a varnish in which the solid content is dissolved or dispersed in a solvent. Since the above-mentioned specific polymer has good solubility in various solvents regardless of the size of the weight average molecular weight, various solvents can be used.
• solvent examples include amides such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone.
• System solvent Ester solvent such as ⁇ -butyrolactone and butyl acetate; Ketone solvent such as cyclopentanone, cyclohexanone, methyl ethyl ketone, benzophenone and 2-heptanone; Ether solvent such as 1,2-methoxyethane and diphenyl ether; 1- Polyfunctional solvents such as methoxy-2-propanol and propylene glycol methyl ether acetate; , Dialkoxybenzene (number of carbon atoms of alkoxy group: 1 to 4), trialkoxybenzene (number of carbon atoms of alkoxy group: 1 to 4), aromatic solvent such as benzoic acid ester; haloalkane such as methylene chloride and chloroform.
• Ester solvent such as ⁇ -butyrolactone and butyl acetate
• Ketone solvent such as cyclopentanone, cyclohexanone, methyl ethyl ketone, benzophen
• solvents may be used alone or in combination of two or more.
• aromatic solvents such as toluene, xylene and mesitylene
• ketone solvents such as methyl ethyl ketone, cyclopentanone, cyclohexanone and 2-heptanone
• N N-dimethylacetamide and N-methyl-2.
• -Amid solvent such as pyrrolidone; preferably chloroform.
• the content ratio of the solvent is preferably 2000 parts by mass or less, and more preferably 200 parts by mass or less with respect to 100 parts by mass of the resin composition excluding the solvent.
• the resin composition may contain additives such as a heat stabilizer, an antioxidant, a UV absorber, a surfactant, and a lubricant, if necessary.
• the metal-clad laminate according to the embodiment of the present invention is obtained by laminating the above-mentioned prepreg and a metal foil and curing them.
• the metal-clad laminate preferably has a form in which a cured product of a prepreg (also referred to as a “cured product complex”) and a metal foil are laminated and adhered to each other, and is preferably used as a material for an electronic substrate.
• the metal foil include aluminum foil and copper foil, and among these, copper foil is preferable because of its low electrical resistance.
• the cured product composite to be combined with the metal foil may be one or a plurality of sheets, and depending on the intended use, the metal foil is laminated on one side or both sides of the cured product composite and processed into a laminated plate.
• a method for producing a laminated board for example, a composite composed of a thermosetting resin composition and a base material (for example, the above-mentioned prepreg) is formed, and after laminating this with a metal foil, the thermosetting resin is produced. Examples thereof include a method of obtaining a laminated plate in which a cured product laminate and a metal foil are laminated by curing the composition.
• One of the particularly preferable uses of the laminated board is a printed wiring board. It is preferable that at least a part of the metal foil is removed from the metal-clad laminated board of the printed wiring board.
• the printed wiring board according to the embodiment of the present invention is a metal foil laminated board from which a part of metal foil is removed.
• the printed wiring board according to the present embodiment can be typically formed by a method of pressure heating molding using the prepreg of the present invention described above. Examples of the base material include the same as those described above for the prepreg.
• the printed wiring board according to the present embodiment has excellent heat resistance and electrical characteristics (low dielectric constant and low dielectric loss tangent) by containing the above-mentioned specific polymer, and further has electrical characteristics due to environmental changes. It is possible to suppress fluctuations, and it also has excellent insulation reliability and mechanical properties.
• Weight average molecular weight (Mw) of polymer The weight average molecular weight (Mw) was measured using a GPC device (“HLC-8320 type” manufactured by Tosoh Corporation) under the following conditions. (Measurement condition) -Column: Tosoh's “TSKgel ⁇ -M” and Tosoh's “TSKgel guardc GmbHlumn ⁇ ” are concatenated.-Development solvent: N-methyl-2-pyrrolidone-Column temperature: 40 ° C.
• Tg Glass transition temperature of the polymer
• the glass transition temperature (Tg) is measured at a frequency of 1 Hz and a temperature rise rate of 10 ° C./min using a dynamic viscoelasticity measuring device (“DMS7100” manufactured by Seiko Instruments Inc.), and is the temperature at which the loss tangent is maximized. And said.
• the loss tangent is the value obtained by dividing the storage elastic modulus by the loss elastic modulus.
• Dielectric constant and dielectric loss tangent of the laminated plate and glass sample The dielectric constant and dielectric loss tangent of the laminated plate and glass sample at 1 GHz were measured by the cavity resonance method.
• a network analyzer N5230A, manufactured by Agilent Technologies
• a cavity resonator CP431 manufactured by Kanto Electronics Applied Development Co., Ltd. were used.
• a laminated plate or glass sample having a thickness of about 0.5 mm was cut into a size of about 2 mm in width and 80 mm in length so that the warp of the glass cloth was on the long side, and two same samples were prepared. .. Next, the two samples were placed in an oven at 105 ° C. ⁇ 2 ° C.
• N-methyl-2-pyrrolidone (368 g) was added, the salt was removed by filtration, and then this solution was added to methanol (9.1 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and collected, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer, and has a structure represented by the following formula (P-1). Polymer P-1 with units was obtained (yield; 20.5 g, yield; 90%, weight average molecular weight (Mw); 28,000, glass transition temperature (Tg); 206 ° C.).
• N-methyl-2-pyrrolidone (368 g) was added, the salt was removed by filtration, and then this solution was added to methanol (9.1 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and collected, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer, and has a structure represented by the following formula (P-11). Polymer P-11 with units was obtained (yield; 22.9 g, yield; 90%, weight average molecular weight (Mw); 30,000, glass transition temperature (Tg); 153 ° C.).
• a resin composition was prepared by mixing 5 parts (manufactured by Mitsubishi Chemical Corporation, product name "BMI 12") and 100 parts of cyclopentanone. After impregnating with NE glass cloth (style: 2116) (dielectric constant at 1 GHz, dielectric constant 4.8, dielectric loss tangent is 0.0015), excess varnish is scraped off by passing through a predetermined slit, and 70 using an oven.
• a copper-clad laminate was obtained by vacuum pressing with copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., model number "TQ-M4-VSP", surface roughness 110 nm) laminated on both sides of this prepreg.
• the mixture was heated and pressurized under the pressing conditions of 120 ° C./1.1 MPa/2 minutes, and further heated at 250 ° C. for 3 hours.
• the copper foil was removed from the copper-clad laminate by etching to obtain a laminate.
• Examples 2 to 20 Comparative Examples 1 to 4> Varnishes were prepared in the same manner as in Example 1 except that each material was used as shown in Tables 1 to 3 below. Further, a prepreg was produced by the same method as in Example 1. Further, using these prepregs, a copper-clad laminate and a laminate from which the copper foil was removed were obtained by the same method as in Example 1.
• the prepreg produced above was cut into a size of 100 mm ⁇ 150 mm, and when it was bent at 180 °, it was visually observed and evaluated whether or not problems such as cracks, cracks, chips, and peeling occurred.
• the evaluation criteria are as follows. The evaluation results are shown in Tables 1 to 3 below. (Evaluation criteria) A: Since no problems such as cracks, cracks, chips, and peeling are observed, it is judged to be suitable. B: Since any of the problems such as cracking, cracking, chipping, and peeling occurred, it is judged to be non-conforming.
• the present invention is not limited to the above embodiment, and various modifications are possible.
• the present invention includes substantially the same configurations as those described in the embodiments (eg, configurations with the same function, method and result, or configurations with the same purpose and effect).
• the present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration.
• the present invention also includes a configuration having the same action and effect as the configuration described in the above embodiment or a configuration capable of achieving the same object.
• the present invention also includes a configuration in which a known technique is added to the configuration described in the above embodiment.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Inorganic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Reinforced Plastic Materials (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=80491093

Family Applications (1)

Country Status (6)

Cited By (5)

Citations (3)

Family Cites Families (6)

• 2021
  • 2021-08-12 TW TW110129816A patent/TWI912346B/zh active
  • 2021-08-19 WO PCT/JP2021/030351 patent/WO2022050064A1/ja not_active Ceased
  • 2021-08-19 KR KR1020237006661A patent/KR20230059790A/ko active Pending
  • 2021-08-19 CN CN202180058075.3A patent/CN116209706A/zh active Pending
  • 2021-08-19 JP JP2022546221A patent/JP7816155B2/ja active Active
  • 2021-08-19 US US18/023,760 patent/US20230345631A1/en active Pending

Patent Citations (3)

Also Published As

Similar Documents

Legal Events