WO2014084310A1 - Composé siloxane modifié par amino, résine imide modifiée, composition de résine thermodurcissable, préimprégné, film apprêté par une résine, plaque stratifiée, carte de circuit imprimé multicouche et emballage semi-conducteur - Google Patents

Composé siloxane modifié par amino, résine imide modifiée, composition de résine thermodurcissable, préimprégné, film apprêté par une résine, plaque stratifiée, carte de circuit imprimé multicouche et emballage semi-conducteur Download PDF

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WO2014084310A1
WO2014084310A1 PCT/JP2013/082054 JP2013082054W WO2014084310A1 WO 2014084310 A1 WO2014084310 A1 WO 2014084310A1 JP 2013082054 W JP2013082054 W JP 2013082054W WO 2014084310 A1 WO2014084310 A1 WO 2014084310A1
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resin
resin composition
compound
amino
thermosetting resin
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PCT/JP2013/082054
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English (en)
Japanese (ja)
Inventor
智彦 小竹
駿介 長井
慎太郎 橋本
慎一郎 安部
正人 宮武
高根沢　伸
村井　曜
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日立化成株式会社
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Priority to JP2014549892A priority Critical patent/JP6375951B2/ja
Publication of WO2014084310A1 publication Critical patent/WO2014084310A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to an amino-modified siloxane compound having an aromatic azomethine suitable for semiconductor packages and printed wiring boards, a modified imide resin using the same, a thermosetting resin composition, a prepreg, a film with a resin, a laminate, and a multilayer print
  • the present invention relates to a wiring board and a semiconductor package.
  • liquid crystalline polymers such as polyesters, polyamides, polycarbonates, polythiols, polyethers, and polyazomethines are thermosetting resins that are excellent in low thermal expansion, dielectric properties, and heat resistance.
  • workability and moldability are insufficient, and a problem that solubility in an organic solvent is insufficient and handling is difficult.
  • Non-Patent Document 1 Since D'Aleio found polyazomethine, which is a liquid crystalline oligomer (see Non-Patent Document 1), many cases relating to resins using polyazomethine have been reported (see, for example, Patent Documents 1 to 7).
  • Patent Document 1 discloses various polyazomethines, and Patent Documents 2 to 7 disclose polyazomethines having specific structures.
  • Patent Document 8 discloses thermosetting polyazomethine resins containing unsaturated groups, and describes that these resins exhibit high heat resistance.
  • JP 51-138800 A JP-A-60-181127 JP-A-60-101123 JP 2003-073470 A JP-A-63-193925 Japanese Patent Laid-Open No. 01-069631 Japanese Patent Laid-Open No. 01-079233 Japanese Patent Laid-Open No. 05-140067
  • the polyazomethines described in Patent Documents 1 to 7 may have insufficient heat resistance and formability when applied as a copper clad laminate or an interlayer insulating material.
  • the thermosetting polyazomethine resin described in Patent Document 8 still lacks improvement in heat resistance and toughness, and even when these are applied as a copper clad laminate or an interlayer insulating material, the heat resistance and reliability are also improved. , Workability and the like may be insufficient.
  • the object of the present invention is a modified imide resin or thermosetting which exhibits excellent low curing shrinkage, low thermal expansion, good dielectric properties, and high elastic modulus when applied to various applications.
  • Amino-modified siloxane compound capable of realizing a functional resin composition, the modified imide resin and a thermosetting resin composition, a prepreg using the same, a film with a resin, a laminate, a multilayer printed wiring board, and a semiconductor package It is.
  • the present inventors have found that the above object can be achieved by using an amino-modified siloxane compound having an aromatic azomethine.
  • the present invention is based on such knowledge.
  • the present invention provides an amino-modified siloxane compound having the following aromatic azomethine, a modified imide resin using the amino-modified siloxane compound, a thermosetting resin composition containing the amino-modified siloxane compound, a prepreg, and a film with a resin
  • the present invention provides a laminated board, a multilayer printed wiring board, and a semiconductor package.
  • Aromatic azomethine compound (A) having at least one aldehyde group in one molecule and siloxane compound (B) having at least two primary amino groups at the molecular end can be reacted with an aromatic in the molecular structure.
  • An amino-modified siloxane compound having azomethine is
  • [2] Obtained by reacting an amino-modified siloxane compound having an aromatic azomethine in the molecular structure according to [1] and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule.
  • a modified imide resin having an aromatic azomethine obtained by reacting an amino-modified siloxane compound having an aromatic azomethine in the molecular structure according to [1] and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule.
  • each R 1 independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent
  • each R 2 independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • thermosetting resin composition comprising the amino-modified siloxane compound having an aromatic azomethine according to [1] and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule.
  • thermosetting resin composition according to [4] further comprising an amine compound (D) having an acidic substituent represented by the following general formula (1).
  • each R 1 independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent
  • each R 2 independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.
  • thermosetting resin composition according to [4] or [5] further containing a thermoplastic elastomer (E).
  • a modified imide resin or thermosetting resin composition that exhibits excellent low curing shrinkage and low thermal expansion, good dielectric properties, and high elastic modulus when applied to various applications.
  • An amino-modified siloxane compound, a modified imide resin and a thermosetting resin composition that can be realized, a prepreg, a film with a resin, a laminate, a multilayer printed wiring board, and a semiconductor package using the same can be provided.
  • a modified imide resin or a thermosetting resin composition using an amino-modified siloxane compound having an aromatic azomethine of the present invention is obtained by impregnating and coating a base material and a support.
  • a laminated film produced by laminating and forming a film with resin and the prepreg in particular, has low curing shrinkage, low thermal expansion, excellent dielectric properties, and high elastic modulus, and is used as a multilayer printed wiring board and semiconductor package. Useful.
  • the amino-modified siloxane compound having an aromatic azomethine of the present invention is an aromatic amine compound (i) having at least two primary amino groups in one molecule, and an aromatic aldehyde having at least two aldehyde groups in one molecule.
  • the aromatic azomethine means a compound in which at least one aromatic is bonded to a Schiff base (—N ⁇ CH—).
  • aromatic amine compound (i) having at least two primary amino groups in one molecule of the present invention examples include p-phenylenediamine and m-phenylenediamine.
  • 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4 has high reactivity at the time of reaction and can achieve higher heat resistance.
  • '-Diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4- Aminophenoxy) phenyl) propane is preferred.
  • 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-3,3 ′ are inexpensive and have solubility in solvents.
  • -Diethyl-diphenylmethane, bis (4- (4-aminophenoxy) phenyl) propane is more preferred.
  • 4,4′-diamino-3,3′-diethyl-diphenylmethane and bis (4- (4-aminophenoxy) phenyl) propane are particularly preferred from the viewpoint of low thermal expansion and dielectric properties.
  • p-phenylenediamine, m-phenylenediamine, 3-methyl-1,4-diaminobenzene, and 2,5-dimethyl-1,4-diaminobenzene capable of increasing the elastic modulus are also preferable.
  • aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule of the present invention examples include terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde. 2,2′-bipyridine-4,4′-dicarboxaldehyde and the like.
  • terephthalaldehyde is particularly preferable because it can be further reduced in thermal expansion, has high reactivity during the reaction, is excellent in solvent solubility, and is easily available commercially.
  • the siloxane compound (B) (hereinafter sometimes referred to as component (B)) having at least two primary amino groups at the molecular ends of the present invention includes the following general formula (2).
  • R 3 and R 4 each independently represents an alkyl group, a phenyl group or a substituted phenyl group, and n is an integer of 1 to 100.
  • n is an integer of 1 to 100, more preferably an integer of 2 to 50.
  • a commercial item can be used as a component (B).
  • Examples of commercially available products include “KF-8010” (amino group equivalent 430), “X-22-161A” (amino group equivalent 800), “X-22-161B” (amino group equivalent 1500), “KF— 8012 "(amino group equivalent 2200),” KF-8008 "(amino group equivalent 5700),” X-22-9409 "(amino group equivalent 700),” X-22-1660B-3 "(amino group equivalent 2200) (Shin-Etsu Chemical Co., Ltd.), “BY-16-853U” (amino group equivalent 460), “BY-16-853” (amino group equivalent 650), “BY-16-853B” (amino group equivalent) 2200) (above, manufactured by Toray Dow Corning Co., Ltd.).
  • X-22-161A, X-22-161B, KF-8012, X-22-1660B-3, BY-16- 853B is preferable, and X-22-161A and X-22-161B, which have excellent compatibility and can increase the elastic modulus, are more preferable.
  • an aromatic amine compound (i) having at least two primary amino groups in one molecule Aromatic azomethine compound (A) having at least one aldehyde group in one molecule by subjecting aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule to dehydration condensation reaction in an organic solvent (Hereinafter sometimes referred to as component (A)).
  • an amino-modified siloxane compound having an aromatic azomethine is obtained by subjecting the component (A) and a siloxane compound (B) having at least two primary amino groups at the molecular ends to a dehydration condensation reaction in an organic solvent. Can do.
  • this reaction has a feature that the molecular weight of the aromatic azomethine can be easily controlled in the molecule of the amino-modified siloxane compound having the aromatic azomethine of the present invention, and the resin composition containing this has a high elastic modulus. Is particularly effective.
  • examples of the organic solvent used when the component (i) and the component (ii) are subjected to a dehydration condensation reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether.
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • ether solvents such as tetrahydrofuran
  • aromatic solvents such as toluene, xylene and mesitylene
  • nitrogen atoms such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone
  • solvents sulfur atom-containing solvents such as dimethyl sulfoxide, and ester solvents such as ⁇ -butyrolactone. These may be used alone or in admixture of two or more.
  • propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, dimethylacetamide, ⁇ -butyrolactone and the like are preferable.
  • propylene glycol monomethyl ether and toluene are more preferable because they are highly volatile and hardly remain as a residual solvent during the production of the prepreg.
  • this reaction is a dehydration condensation reaction, water is produced as a by-product.
  • a reaction catalyst can be optionally used as necessary.
  • the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid, amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. . These may be used alone or in admixture of two or more. In order to allow the dehydration condensation reaction to proceed efficiently, for example, an acidic catalyst such as p-toluenesulfonic acid is preferred.
  • the amount of component (i) and component (ii) used is, for example, the number of primary amino groups of component (i) [the amount of component (i) used / the primary amino group equivalent of component (i)] It is desirable to use it in a range of 0.1 to 5.0 times the number of aldehyde groups in ii) [amount of component (ii) used / aldehyde group equivalent of component (ii)].
  • a decrease in the molecular weight of the aromatic azomethine compound obtained by this reaction tends to be suppressed.
  • the amount of the organic solvent used is preferably 25 to 2000 parts by mass, for example, 40 to 1000 parts by mass with respect to 100 parts by mass of the total of the resin components of component (i) and component (ii). More preferably, the amount is 40 to 500 parts by mass.
  • the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility tends to be suppressed. Further, when the amount is 2000 parts by mass or less, there is a tendency that a long time is required for the reaction.
  • Component (A) is obtained by charging the above raw materials, organic solvent, and, if necessary, a reaction catalyst in a reaction kettle and stirring for 0.1 to 10 hours, if necessary, while heating and keeping warm to cause a dehydration condensation reaction.
  • the reaction temperature at this time is preferably 70 to 150 ° C., for example, and more preferably 100 to 130.
  • the reaction temperature By setting the reaction temperature to 70 ° C. or higher, the reaction rate tends to be low.
  • a high-boiling solvent is not required as the reaction solvent, and when the prepreg is produced, the residual solvent hardly remains and the heat resistance tends to be reduced.
  • an amino-modified siloxane having an aromatic azomethine is obtained by subjecting the component (A) obtained by the above reaction and a siloxane compound (B) having at least two amino groups at the molecular ends to a dehydration condensation reaction in an organic solvent.
  • a compound can be obtained.
  • the amount of component (A) and component (B) used is, for example, the number of primary amino groups in component (B) [the amount of component (B) used / the primary amino group equivalent of component (B)] It is desirable that the number of aldehyde groups in A) is 1.0 to 10.0 times the number of aldehyde groups [amount of component (A) used / aldehyde equivalent of component (A)]. By setting it to 1.0 times or more, a decrease in solubility in a solvent tends to be suppressed. Moreover, a favorable elastic modulus is obtained in the thermosetting resin containing the amino modified siloxane compound which has aromatic azomethine by setting it as 10.0 times or less.
  • the amount of the organic solvent used is preferably 25 to 2000 parts by weight, for example, 40 to 1000 parts by weight with respect to 100 parts by weight of the total of the resin components of component (A) and component (B). More preferably, the amount is 40 to 500 parts by mass.
  • the amount of the organic solvent used is 25 parts by mass or more, the lack of solubility tends to be small. Moreover, by setting it as 2000 mass parts or less, reaction does not require a long time.
  • An amino-modified siloxane compound having an aromatic azomethine is prepared by charging the above raw materials, an organic solvent, and if necessary, a reaction catalyst in a reaction kettle and stirring and dehydrating and condensing for 0.1 to 10 hours while heating and holding as necessary. can get.
  • the reaction temperature is, for example, preferably 70 to 150 ° C., more preferably 100 to 130.
  • the reaction temperature By setting the reaction temperature to 70 ° C. or higher, the reaction rate tends not to be too slow.
  • the reaction temperature is set to 150 ° C. or lower, a high-boiling solvent is not required for the reaction solvent, and when the prepreg is produced, the residual solvent hardly remains and good heat resistance tends to be obtained.
  • the amino-modified siloxane compound having an aromatic azomethine obtained by the above reaction can be confirmed by performing IR measurement.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) is 1000 or more, good low curing shrinkage and low thermal expansion tend to be obtained. Moreover, it exists in the tendency for favorable compatibility and an elasticity modulus to be obtained as it is 300,000 or less.
  • the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and converted by a calibration curve produced using standard polystyrene.
  • an auto sampler (AS-8020 manufactured by Tosoh Corporation), a column oven (860-C0 manufactured by JASCO Corporation), an RI detector (830-RI manufactured by JASCO Corporation), a UV / VIS detector (Japan) Spectroscopic industry 870-UV), HPLC pump (JASCO Corporation 880-PU) is used.
  • TSKgel SuperHZ2000, 2300 manufactured by Tosoh Corporation is used as the column used, and measurement is possible by using a measurement temperature of 40 ° C., a flow rate of 0.5 ml / min, and a solvent of tetrahydrofuran.
  • modified imide resin The modified imide resin of the present invention is obtained by reacting the aforementioned amino-modified siloxane compound of the present invention with a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. .
  • the modified imide resin preferably has an acidic substituent, and the acidic substituent is derived from the acidic substituent of the amine compound (D) represented by the following general formula (1).
  • the acidic substituent can be introduced by reacting the amine compound (D). By having such an acidic substituent, good low thermal expansibility can be obtained.
  • each R 1 independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent
  • each R 2 independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • x is an integer of 1 to 5
  • y is an integer of 0 to 4
  • the sum of x and y is 5.
  • the modified imide resin can be produced in a “pre-reaction” when producing a thermosetting resin composition described later.
  • thermosetting resin composition comprises an amino-modified siloxane compound having an aromatic azomethine and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. is there.
  • maleimide compounds (C) having at least two N-substituted maleimide groups in one molecule include bis (4-maleimidophenyl) methane and polyphenylmethane.
  • a component (C) may be used independently, or 2 or more types may be mixed and used for it.
  • bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, 2,2-bis (4- (4- (4- Maleimidophenoxy) phenyl) propane is preferred, and bis (4-maleimidophenyl) methane and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are more preferred and inexpensive from the viewpoint of solubility in solvents.
  • Bis (4-maleimidophenyl) methane is particularly preferred from a certain point.
  • the amount of the amino-modified siloxane compound having an aromatic azomethine is preferably, for example, 1 to 30 parts by mass per 100 parts by mass of the total resin components. It is more preferable to set it as a mass part from the point of copper foil adhesiveness and chemical resistance.
  • the amount of component (C) used is, for example, preferably from 30 to 99 parts by weight, and preferably from 40 to 95 parts by weight per 100 parts by weight of the sum of the resin components in terms of low thermal expansion and high elastic modulus. More preferred
  • thermosetting resin composition of the present invention comprises an amino-modified siloxane compound having an aromatic azomethine and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. . Moreover, it can also be used as modified imide resin which has the said compound pre-reacted and has aromatic azomethine. By performing such a pre-reaction, the molecular weight can be controlled, and further low curing shrinkage and low thermal expansion can be improved.
  • This pre-reaction is performed by reacting an amino-modified siloxane compound having aromatic azomethine with a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule while heating and keeping in an organic solvent. It is preferable to synthesize an imide resin.
  • the reaction temperature when reacting an amino-modified siloxane compound having an aromatic azomethine in an organic solvent with a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule is, for example, 70 to 150. ° C is preferable, and 100 to 130 ° C is more preferable.
  • the reaction time is, for example, preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
  • the amount of the amino-modified siloxane compound having component (C) and aromatic azomethine is, for example, the number of maleimide groups of component (C) [the amount of component (C) used / maleimide group equivalent of component (C) ]
  • the primary amino group number of amino-modified siloxane compound having aromatic azomethine the amount of amino-modified siloxane compound having aromatic azomethine used / primary amino group equivalent of amino-modified siloxane compound having aromatic azomethine
  • a range that is 10.0 times larger is preferable. By setting it to 2.0 times or more, gelation and a decrease in heat resistance tend to be suppressed. Moreover, it exists in the tendency for the solubility to an organic solvent and the fall of heat resistance to be suppressed by setting it as 10.0 times or less.
  • the amount of component (C) used in the pre-reaction is, for example, preferably 50 to 3000 parts by weight, and 100 to 1500 parts by weight with respect to 100 parts by weight of the resin component of the amino-modified siloxane compound while maintaining the above relationship. Is more preferable.
  • the amount is 50 parts by mass or more, a decrease in heat resistance tends to be suppressed.
  • low thermal expansibility can be kept favorable by setting it as 3000 mass parts or less.
  • organic solvent used in this pre-reaction examples include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and acetic acid.
  • alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
  • acetic acid examples include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether
  • ketone solvents such as acetone
  • Ester solvents such as ethyl ester and ⁇ -butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide And sulfur atom-containing solvents such as These organic solvents can be used alone or in combination of two or more.
  • organic solvents for example, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and ⁇ -butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone has low toxicity and is highly volatile and hardly remains as a residual solvent.
  • cyclohexanone has low toxicity and is highly volatile and hardly remains as a residual solvent.
  • Propylene glycol monomethyl ether, and dimethylacetamide are particularly preferable.
  • the amount of the organic solvent used is, for example, 100 parts by mass of the total resin component of the modified siloxane compound having aromatic azomethine and the maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, and particularly preferably 40 to 500 parts by mass.
  • the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility tends to be suppressed.
  • the amount is 2000 parts by mass or less, the reaction does not take a long time.
  • reaction catalyst can be optionally used for this pre-reaction.
  • the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, phosphorus-based catalysts such as triphenylphosphine, and alkali metal amides such as lithium amide, sodium amide, and potassium amide. Etc. These reaction catalysts can be used alone or in combination of two or more.
  • the amount of the modified imide resin having an aromatic azomethine obtained from the pre-reaction is preferably 50 to 100 parts by mass, for example, 100 to 100 parts by mass per 100 parts by mass of the total resin components. More preferably. By setting the blending amount of the modified imide resin having aromatic azomethine to 50 parts by mass or more, good low thermal expansibility and high elastic modulus can be obtained.
  • thermosetting resin composition comprising the amino-modified siloxane compound having an aromatic azomethine of the present invention and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule, and
  • the modified imide resin having an aromatic azomethine obtained by the reaction alone has good thermosetting reactivity, but if necessary, a curing agent and a radical initiator can be used in combination. By using a curing agent and a radical initiator, heat resistance, adhesiveness, and mechanical strength can be improved.
  • curing agent used in combination examples include dicyandiamide, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4′-diaminodiphenylsulfone, phenylenediamine, and xylenediamine.
  • Aromatic amines such as hexamethylenediamine and 2,5-dimethylhexamethylenediamine, and guanamine compounds such as melamine and benzoguanamine. These may be used alone or in admixture of two or more.
  • radical initiator examples include organic peroxides such as acyl peroxides, hydroperoxides, ketone peroxides, organic peroxides having a t-butyl group, and peroxides having a cumyl group. Can be used. These may be used alone or in admixture of two or more. Among these, for example, aromatic amines are preferable from the viewpoint of good reactivity and heat resistance.
  • thermosetting resin composition of the present invention can contain an amine compound (D) having an acidic substituent represented by the following general formula (1).
  • each R 1 independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent
  • each R 2 independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.
  • Examples of the amine compound (D) having an acidic substituent include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m -Aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc. .
  • m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5- Dihydroxyaniline is preferred.
  • m-aminophenol and p-aminophenol are more preferable.
  • the amount of component (D) used is, for example, preferably from 0.5 to 30 parts by weight, and more preferably from 1 to 20 parts by weight per 100 parts by weight of the total of the resin components, from the viewpoint of low thermal expansion. preferable.
  • thermosetting resin composition of the present invention comprises an amino-modified siloxane compound having an aromatic azomethine, a maleimide compound (C) having at least two N-substituted maleimide groups in a molecule, and an amine compound having an acidic substituent ( D) may be contained.
  • the compound can be pre-reacted and used as a modified imide resin having an acidic substituent and an aromatic azomethine. By performing such a pre-reaction, the molecular weight can be controlled, and further low curing shrinkage and low thermal expansion can be improved.
  • This pre-reaction involves synthesizing a modified imide resin having an acidic substituent by reacting an amino-modified siloxane compound having an aromatic azomethine, component (C), and component (D) while keeping the temperature in an organic solvent.
  • the reaction temperature at the time of reacting the amino-modified siloxane compound having aromatic azomethine, component (C), and component (D) in an organic solvent is preferably, for example, 70 to 150 ° C., and preferably 100 to 130 ° C. More preferably.
  • the reaction time is, for example, preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
  • the amount of amino-modified siloxane compound having aromatic azomethine, component (C), and component (D) is, for example, the number of maleimide groups in component (C) [the amount of component (C) used / component ( C) maleimide group equivalent] is an amino-modified siloxane compound having an aromatic azomethine and the number of primary amino groups in component (D) [amount of amino-modified siloxane compound having an aromatic azomethine / amino-modified siloxane compound having an aromatic azomethine
  • the primary amino group equivalent + the amount of component (D) used / the primary amino group equivalent of component (D)] is desirably in a range of 2.0 to 10.0 times. By setting it to 2.0 times or more, gelation and a decrease in heat resistance tend to be suppressed. Moreover, it exists in the tendency for the solubility to an organic solvent and the fall of heat resistance to be suppressed by setting it as 10.0 times or less.
  • the amount of the component (C) used in the pre-reaction is preferably 50 to 3000 parts by weight with respect to 100 parts by weight of the resin component of the amino-modified siloxane compound having an aromatic azomethine while maintaining the above relationship, 100 to 1500 parts by mass is more preferable.
  • the amount of component (D) used in the pre-reaction is, for example, preferably from 1 to 1000 parts by weight, more preferably from 5 to 500 parts by weight, based on 100 parts by weight of the resin component of the amino-modified siloxane compound.
  • the content is 1 part by mass or more, a decrease in heat resistance tends to be suppressed.
  • low thermal expansibility can be kept favorable by setting it as 1000 mass parts or less.
  • organic solvent used in this pre-reaction examples include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and acetic acid.
  • alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
  • acetic acid examples include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether
  • ketone solvents such as acetone
  • Ester solvents such as ethyl ester and ⁇ -butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide And sulfur atom-containing solvents such as These organic solvents can be used alone or in combination of two or more.
  • organic solvents for example, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and ⁇ -butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone has low toxicity and is highly volatile and hardly remains as a residual solvent.
  • cyclohexanone has low toxicity and is highly volatile and hardly remains as a residual solvent.
  • Propylene glycol monomethyl ether, and dimethylacetamide are particularly preferable.
  • the amount of the organic solvent used is, for example, 25 to 2000 parts by mass with respect to 100 parts by mass of the total of the amino-modified siloxane compound having aromatic azomethine, the component (C), and the resin component of component (D).
  • the amount is preferably 40 to 1000 parts by weight, more preferably 40 to 500 parts by weight.
  • the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility tends to be suppressed.
  • the amount is 2000 parts by mass or less, the reaction does not take a long time.
  • reaction catalyst can be optionally used for this pre-reaction.
  • the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, phosphorus-based catalysts such as triphenylphosphine, and alkali metal amides such as lithium amide, sodium amide, and potassium amide. Etc. These can be used alone or in combination of two or more.
  • the amount of the modified imide resin having an acidic substituent and an aromatic azomethine obtained by the pre-reaction is preferably 50 to 100 parts by mass, for example, per 100 parts by mass of the total resin components, and preferably 60 to More preferably, it is 90 parts by mass.
  • the blending amount of the modified imide resin having an acidic substituent and an aromatic azomethine is 50 parts by mass or more, good low thermal expansibility and high elastic modulus tend to be obtained.
  • An amino-modified siloxane compound having an aromatic azomethine of the present invention comprising a maleimide compound (C) having at least two N-substituted maleimide groups in a molecule, and an amine compound (D) having an acidic substituent.
  • a thermosetting resin composition and a modified imide resin having an aromatic substituent and an aromatic azomethine obtained by pre-reacting the above compound alone have good thermosetting reactivity, but if necessary, a curing agent and radical initiation An agent may be used. By using a curing agent and a radical initiator in combination, heat resistance, adhesiveness, and mechanical strength can be improved.
  • curing agent used in combination examples include dicyandiamide, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4′-diaminodiphenylsulfone, phenylenediamine, and xylenediamine.
  • Aromatic amines such as hexamethylenediamine and 2,5-dimethylhexamethylenediamine, and guanamine compounds such as melamine and benzoguanamine.
  • radical initiator examples include organic peroxides such as acyl peroxides, hydroperoxides, ketone peroxides, organic peroxides having a t-butyl group, and peroxides having a cumyl group. Can be used. These may be used alone or in admixture of two or more. Among these, for example, aromatic amines are preferable from the viewpoint of good reactivity and heat resistance.
  • thermosetting resin composition of the present invention can contain a thermoplastic elastomer (E).
  • the thermoplastic elastomer (E) include, for example, a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamide elastomer, an acrylic elastomer, and a silicone elastomer.
  • elastomers and derivatives thereof include a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. These can be used individually by 1 type or in mixture of 2 or more types.
  • the component (E) one having a reactive functional group at the molecular end or molecular chain can be used.
  • the reactive functional group include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an amide group, an isocyanato group, an acryl group, a methacryl group, and a vinyl group.
  • styrene elastomers for example, styrene elastomers, olefin elastomers, polyamide elastomers, and silicone elastomers are preferable from the viewpoint of heat resistance and insulation reliability, and styrene elastomers from the viewpoint of dielectric properties. And olefin-based elastomers are particularly preferred.
  • the reactive functional group possessed in the molecular terminal or molecular chain of these components (E) is preferably, for example, an epoxy group, a hydroxyl group, a carboxyl group, an amino group, and an amide group in terms of adhesion to the metal foil.
  • an epoxy group, a hydroxyl group, and an amino group are particularly preferable.
  • the amount of component (E) used is, for example, preferably from 0.1 to 50 parts by weight, and more preferably from 2 to 30 parts by weight, based on 100 parts by weight of the total resin components. It is more preferable because the compatibility of the resin is good, and the cured product has low curing shrinkage, low thermal expansion, and excellent dielectric properties.
  • thermosetting resin composition of the present invention may contain at least one thermosetting resin (F) (hereinafter sometimes referred to as component (F)) selected from epoxy resins and cyanate resins.
  • component (F) epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, and bisphenol.
  • F novolac type epoxy resin stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, triphenolphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy Resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and diglycidyl esters of polycyclic aromatics such as anthracene And Tel compounds and phosphorus-containing epoxy resin obtained by introducing a phosphorus compound thereof.
  • biphenyl aralkyl type epoxy resins and naphthalene type epoxy resins are preferable from the viewpoint of heat resistance and flame retardancy.
  • cyanate resin of component (F) examples include, for example, bisphenol type cyanate resins such as novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin, and some of these. Examples include triazine prepolymers. These may be used alone or in admixture of two or more. Among these, for example, a novolac type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy.
  • a curing agent can be used for these components (F) as necessary.
  • the curing agent include, for example, polyfunctional phenol compounds such as phenol novolak, cresol novolak, aminotriazine novolak resin, amine compounds such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, phthalic anhydride, pyromellitic anhydride, maleic anhydride
  • acids anhydrides such as acid and maleic anhydride copolymers. These 1 type can be used individually or in mixture of 2 or more types.
  • the amount of component (F) used is, for example, preferably 1 to 50 parts by mass per 100 parts by mass of the total resin components, and 3 to 35 parts by mass from the viewpoint of heat resistance and chemical resistance. Is more preferable.
  • the thermosetting resin composition of the present invention can contain an inorganic filler (G).
  • the inorganic filler (G) include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, and stannic acid.
  • component (G) examples include zinc, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, glass powder such as E glass, T glass, and D glass, and hollow glass beads. These may be used alone or in admixture of two or more.
  • silica is particularly preferable in terms of dielectric properties, heat resistance, and low thermal expansion.
  • examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water.
  • examples of the dry process silica include crushed silica, fumed silica, fused spherical silica and the like depending on the production method. Among these, fused spherical silica is preferable because of its low thermal expansion and high fluidity when filled in a resin.
  • the average particle size is preferably 0.1 to 10 ⁇ m, and more preferably 0.3 to 8 ⁇ m.
  • the average particle size of the fused spherical silica is preferably 0.1 to 10 ⁇ m, and more preferably 0.3 to 8 ⁇ m.
  • the average particle diameter is the particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles as 100%, and the laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device.
  • the content of the component (G) is, for example, preferably 20 to 500 parts by mass, more preferably 50 to 350 parts by mass with respect to 100 parts by mass of the total resin components.
  • the content of component (G) is, for example, preferably 20 to 500 parts by mass, more preferably 50 to 350 parts by mass with respect to 100 parts by mass of the total resin components.
  • the thermosetting resin composition of the present invention can contain a curing accelerator (H).
  • a curing accelerator (H) examples include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and tris.
  • Organometallic salts such as acetylacetonate cobalt (III), imidazoles and derivatives thereof, organophosphorus compounds such as phosphines and phosphonium salts, secondary amines, tertiary amines, and quaternary ammonium salts Is mentioned.
  • These 1 type can be used individually or in mixture of 2 or more types.
  • zinc naphthenate, imidazole derivatives, and phosphonium salts are preferable from the viewpoint of the promoting effect and the storage stability.
  • the content of the component (H) is, for example, preferably 0.01 to 3.0 parts by mass, more preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the total resin components. preferable. By setting the content of the component (H) to 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the total of the resin components, the acceleration effect and the storage stability can be kept good.
  • thermoplastic resin organic filler, flame retardant, ultraviolet absorber, antioxidant, photopolymerization initiator, fluorescent whitening agent, and adhesion improver may be used without departing from the object.
  • Etc. can be used. These may be used alone or in combination of two or more.
  • thermoplastic resin examples include polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin.
  • the organic filler examples include a resin filler made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, acrylate ester resin, methacrylate ester resin, conjugated diene resin, and the like.
  • the flame retardant examples include halogen-containing flame retardants containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphorous flame retardants such as red phosphorus, sulfamic acid Nitrogen flame retardants such as guanidine, melamine sulfate, melamine polyphosphate and melamine cyanurate, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, and inorganic flame retardants such as antimony trioxide.
  • halogen-containing flame retardants containing bromine and chlorine triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds
  • phosphorous flame retardants such as red phosphorus, sulfamic acid
  • Nitrogen flame retardants such as guanidine, melamine sulfate
  • examples of UV absorbers include benzotriazole UV absorbers
  • examples of antioxidants include hindered phenols and hindered amines
  • examples of photopolymerization initiators include benzophenones, benzyl ketals, and thioxanthone.
  • examples of photopolymerization initiators and fluorescent brighteners include stilbene derivative fluorescent brighteners, and adhesion improvers such as urea compounds such as urea silane and silane, titanate and aluminate cups. A ring agent etc. are mentioned.
  • thermosetting resin composition containing the amino-modified siloxane compound having an aromatic azomethine of the present invention is used in a prepreg, finally, the varnish state in which each component is dissolved or dispersed in an organic solvent and It is preferable to do.
  • organic solvent used here examples include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and butyl acetate.
  • alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and butyl acetate.
  • Ester solvents such as propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide And a sulfur atom-containing solvent. These can be used individually by 1 type or in mixture of 2 or more types.
  • methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity.
  • the final thermosetting resin composition in the varnish is, for example, preferably 40 to 90% by mass, more preferably 50 to 80% by mass of the entire varnish.
  • “resin component” means an amino-modified siloxane compound, a modified imide resin (having an acidic substituent derived from the acidic substituent of the amine compound (D) represented by the general formula (1) described above). Modified imide resin), maleimide compound (C), amine compound (D) having an acidic substituent, thermoplastic elastomer (E), thermosetting resin (F), and reaction products thereof.
  • the “thermosetting resin composition” refers to a resin component containing an inorganic filler and a curing accelerator.
  • the prepreg of the present invention is obtained by impregnating a base material with the above-described thermosetting resin composition of the present invention. .
  • the prepreg of the present invention will be described in detail.
  • the prepreg of the present invention can be produced by impregnating the thermosetting resin composition of the present invention into a substrate and semi-curing (B-stage) by heating or the like.
  • a method to make a base material impregnate the thermosetting resin composition of this invention For example, the method of immersing a base material in a resin varnish, the method of apply
  • the method of immersing the base material in the resin varnish is preferable.
  • the impregnation property of the resin composition with respect to a base material can be improved.
  • the well-known thing used for the laminated board for various electrical insulation materials can be used, for example.
  • the material include inorganic fibers such as E glass, D glass, S glass and Q glass, organic fibers such as polyimide, polyester and tetrafluoroethylene, and mixtures thereof.
  • carbon fiber or the like can be used in the case of a fiber reinforced base material.
  • These base materials have, for example, the shapes of woven fabric, non-woven fabric, robink, chopped strand mat and surfacing mat, and the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, can be used alone. Alternatively, two or more kinds of materials and shapes can be combined.
  • the thickness of the base material can be, for example, about 0.03 to 0.5 mm, and the surface treated with a silane coupling agent or the like or mechanically subjected to a fiber opening treatment has heat resistance and It is suitable in terms of moisture resistance and processability.
  • the prepreg of the present invention has, for example, a base so that the amount of the thermosetting resin composition attached to the substrate is 20 to 90% by mass in terms of the content of the thermosetting resin composition of the prepreg after drying. After impregnating or coating the material, it can usually be obtained by drying by heating at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage).
  • the film with a resin of the present invention is obtained by forming a layer of the thermosetting resin composition of the present invention on a support.
  • the thermosetting resin composition obtained by this invention is made into a varnish state, and various coaters are used.
  • the resin composition layer can be formed by applying to a support and further drying by heating or blowing hot air.
  • the resin-coated film of the present invention can be produced by being semi-cured (B-staged) by heating or the like.
  • This semi-cured state is a state in which the adhesive force between the resin composition layer of the resin-coated film and the circuit board is secured when the film with resin and the circuit board are laminated and cured, and embedded in the circuit board. It is preferable that the property (fluidity) is ensured.
  • the coater used when the thermosetting resin composition of the present invention is applied on a support is not particularly limited, and for example, a die coater, a comma coater, a bar coater, a kiss coater, a roll coater, etc. can be used. . These can be appropriately selected depending on the thickness of the resin composition layer. As a drying method, heating, hot air blowing, or the like can be used.
  • the drying conditions after applying the thermosetting resin composition to the support are, for example, such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. dry.
  • the amount of the organic solvent in the varnish varies depending on the boiling point of the organic solvent.
  • the resin composition layer can be obtained by drying a varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. It is formed. It is preferable to set suitable drying conditions as appropriate by simple experiments in advance.
  • the thickness of the resin composition layer formed on the support is usually not less than the thickness of the conductor layer of the circuit board.
  • the thickness of the conductor layer is preferably, for example, 5 to 70 ⁇ m, more preferably 5 to 50 ⁇ m, and even more preferably 5 to 30 ⁇ m in order to reduce the thickness of the multilayer printed wiring board.
  • the support in the film with resin is made of, for example, polyolefin such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and the like.
  • PET polyethylene terephthalate
  • polyester such as polyethylene naphthalate, polycarbonate, polyimide, and the like.
  • the film include metal foil such as release paper, copper foil, and aluminum foil. Note that the support and the protective film described later may be subjected to a release treatment in addition to the mat treatment and the corona treatment.
  • the thickness of the support is, for example, preferably 10 to 150 ⁇ m, more preferably 25 to 50 ⁇ m.
  • a protective film can be further laminated on the surface of the resin composition layer on which the support is not provided.
  • the protective film may be the same as or different from the material of the support.
  • the thickness of the protective film is, for example, 1 to 40 ⁇ m.
  • the laminated board of the present invention is obtained by laminating the above-mentioned resin-coated film.
  • it can be manufactured by laminating a film with resin on one side or both sides of a circuit board, a prepreg, a base material and the like using a vacuum laminator and curing by heating as necessary.
  • the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like.
  • a circuit board means here that the circuit pattern was formed in the one or both surfaces of the above boards.
  • a printed wiring board in which a plurality of conductor layers and insulating layers are alternately laminated and having a circuit pattern formed on one side or both sides of the outermost layer of the printed wiring board is also included in the circuit board here.
  • the surface of the conductor layer may be subjected to a roughening process in advance by a blackening process or the like.
  • the film with resin has a protective film
  • preheat the film with resin and the circuit board as necessary Crimp to circuit board while pressing and heating.
  • a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used.
  • Lamination conditions are, for example, that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 0.1 to 1.1 MPa, and the lamination is performed under a reduced pressure of air pressure 20 mmHg (26.7 hPa) or less. Is preferred.
  • the laminating method may be a batch method or a continuous method using a roll.
  • the resin composition layer After laminating the resin-coated film on the circuit board, after cooling to around room temperature and then peeling the support, the resin composition layer is heat-cured after peeling the support (hereinafter, after heat-curing)
  • the resin composition layer may be referred to as an insulating layer).
  • the thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 150 to 220 ° C. for 20 to 180 minutes, more preferably 160 to 200 ° C. It is selected in the range of 30 to 120 minutes at ° C. Moreover, you may peel a support body, after thermosetting a resin composition layer.
  • Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary.
  • drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.
  • a conductor layer is formed on the insulating layer by dry plating or wet plating.
  • dry plating for example, a known method such as vapor deposition, sputtering, or ion plating can be used.
  • wet plating first, the surface of the cured insulating resin composition layer is permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid. Roughening treatment is performed with an oxidizing agent such as to form an uneven anchor.
  • an aqueous sodium hydroxide solution such as potassium permanganate and sodium permanganate is particularly preferably used.
  • a conductor layer is formed by a method combining electroless plating and electrolytic plating.
  • a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating.
  • a subsequent pattern formation method for example, a known subtractive method or semi-additive method can be used.
  • the laminate of the present invention is obtained by laminating the above-described prepreg of the present invention.
  • the prepreg of the present invention can be produced, for example, by laminating 1 to 20 sheets and laminating with a structure in which a metal foil such as copper or aluminum is disposed on one or both sides.
  • the molding conditions for laminating the laminate can be, for example, the method of a laminate for an electrical insulating material and a multilayer plate, for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. Molding can be performed in a range of up to 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours.
  • the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a laminated board.
  • the multilayer printed wiring board of this invention is manufactured using the said laminated board.
  • the circuit board can be obtained by wiring processing the conductor layer of the laminate of the present invention by an ordinary etching method. Then, a plurality of laminated boards processed by wiring through the above-described prepreg are laminated and subjected to hot press processing to be multi-layered at once. Thereafter, a multilayer printed wiring board can be manufactured through formation of through holes or blind via holes by drilling, laser processing, etc., and formation of interlayer wiring by plating or conductive paste.
  • the semiconductor package of the present invention is obtained by mounting a semiconductor element on the multilayer printed wiring board.
  • the semiconductor package of the present invention is manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position of the printed wiring board.
  • the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
  • it measured by the following method about the shrinkage
  • the glass transition temperature, the coefficient of thermal expansion, the copper foil adhesion, the solder heat resistance with copper, the bending elastic modulus, and the dielectric properties were measured and evaluated by the following methods.
  • Tg glass transition temperature
  • a copper-clad laminate is immersed in a copper etching solution to form a copper foil having a width of 3 mm to produce an evaluation substrate, and copper is tested using a tensile tester. The adhesion (peel strength) of the foil was measured.
  • a bending elastic modulus copper-clad laminate was immersed in a copper etching solution to prepare a 25 mm ⁇ 50 mm evaluation board from which the copper foil was removed, and a 5-ton tensilon manufactured by Orientec Co., Ltd. was used, and the crosshead speed was 1 mm / min. Measured at a span distance of 20 mm.
  • Dielectric properties (dielectric constant and dielectric loss tangent) A 100 mm ⁇ 2 mm evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was used, and a cavity resonator device (manufactured by Kanto Electronics Application Development Co., Ltd.) was used to obtain a ratio at a frequency of 1 GHz. The dielectric constant and dielectric loss tangent were measured.
  • Production Example 1 Production of amino-modified siloxane compound (I-1) having aromatic azomethine
  • a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser.
  • terephthalaldehyde 17.1 g
  • propylene glycol monomethyl ether 45.0 g were added, reacted at 115 ° C. for 4 hours, and then raised to 130 ° C.
  • Production Example 2 Production of amino-modified siloxane compound (I-2) having aromatic azomethine
  • a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser.
  • 2,8.7-dimethyl-1,4-diaminobenzene 8.7 g
  • terephthalaldehyde 21.3 g
  • propylene glycol monomethyl ether 45.0 g were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C.
  • the solution was dehydrated by normal pressure concentration to obtain an aromatic azomethine compound-containing solution (resin component: 60% by mass).
  • X-22-161B manufactured by Shin-Etsu Chemical Co., Ltd., trade name: 413.8 g and propylene glycol monomethyl ether: 645.7 g were added to the reaction solution, reacted at 115 ° C. for 4 hours, The mixture was heated up to 0 ° C. and dehydrated by atmospheric concentration to obtain a modified siloxane compound (I-2) -containing solution (Mw: 25000, resin component: 90% by mass) having an aromatic azomethine.
  • I-2 modified siloxane compound
  • Examples 1 to 18 and Comparative Examples 1 to 6 Amino-modified siloxane compound-containing solution (I-1, I-2) having an aromatic azomethine obtained in Production Examples 1 and 2 and a modified imide resin-containing solution having an aromatic azomethine obtained in Production Example 3 ( J-1) and a modified imide resin-containing solution (K-1) having an acidic substituent and an aromatic azomethine obtained in Production Example 4, an aromatic amine compound (i) and an aromatic aldehyde compound ( ii), siloxane compound (B), maleimide compound (C), amine compound (D) having an acidic substituent, thermoplastic elastomer (E), thermosetting resin (F), inorganic filler (G), curing acceleration Using agent (H) and methyl ethyl ketone as a diluent solvent, mixing was carried out at the blending ratio (parts by mass) shown in Tables 1 to 4 to obtain a varnish having a resin content of 65% by mass.
  • the varnish was applied to a 16 ⁇ m polyethylene terephthalate film with a film applicator (PI-1210, manufactured by Tester Sangyo Co., Ltd.) so that the resin thickness after drying was 35 ⁇ m, and then at 160 ° C. for 10 minutes. Heat drying was performed to obtain a semi-cured resin powder.
  • a film applicator PI-1210, manufactured by Tester Sangyo Co., Ltd.
  • This resin powder was put into a mold of a Teflon (registered trademark) sheet, the glossy surface of 12 ⁇ m electrolytic copper foil was placed up and down, and pressed at a pressure of 2.0 MPa and a temperature of 240 ° C. for 60 minutes. The foil was removed to obtain a resin plate. Further, the varnish was impregnated and applied to an E glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a thermosetting resin composition content of 48 mass%. Four prepregs were stacked, 12 ⁇ m electrolytic copper foils were placed one above the other, and pressed at a pressure of 3.0 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate. Tables 1 to 4 show the measurement and evaluation results of the obtained resin plates and copper-clad laminates.
  • Aromatic amine compounds (i) KAYAHARD AA: 3,3′-diethyl-4,4′-diaminodiphenylmethane [manufactured by Nippon Kayaku Co., Ltd., trade name]
  • Siloxane compound (B) X-22-161B terminal amino-modified siloxane (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Maleimide compound (C) ⁇ BMI: Bis (4-maleimidophenyl) methane (trade name, manufactured by Kay Kasei Co., Ltd.)
  • BMI-4000 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
  • Amine compound having acidic substituent (D) ⁇ P-Aminophenol (trade name, manufactured by Kanto Chemical Co., Inc.)
  • Thermosetting resin (F) PT-30 Novolac-type cyanate resin (Lonza Japan Co., Ltd., trade name)
  • NC-7000L ⁇ -naphthol / cresol novolac type epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd.)
  • Curing accelerator (H) Zinc (II) naphthenate 8% mineral spirit solution
  • G-8809L Isocyanate mask imidazole
  • TPP-MK Tetraphenylphosphonium tetra-p-tolylborate (trade name, manufactured by Hokuko Chemical Co., Ltd.)
  • amino-modified siloxane compound-containing solutions (I-1) and (I-2) having aromatic azomethines in Tables 1 to 4 modified imide resin-containing solutions (J-1) having aromatic azomethines, and acidic substituents
  • the amount (parts by mass) of the modified imide resin-containing solution having azomethine and aromatic azomethine indicates a value in terms of solid content of the resin component.
  • the curing shrinkage rate of the resin plate is small and excellent in low cure shrinkage. Also in the characteristics of the laminated plate, the thermal expansion rate, the copper foil Excellent adhesion, elastic modulus and dielectric properties. On the other hand, the comparative example has a large curing shrinkage rate of the resin plate, and also in the characteristics of the laminated plate, the thermal expansion coefficient, the copper foil adhesiveness, the elastic modulus, and the dielectric characteristics are any of the characteristics. Inferior.
  • a prepreg obtained by impregnating or coating a base material with a polyimide using an amino-modified siloxane compound having an aromatic azomethine of the present invention, or a thermosetting resin composition containing an amino-modified siloxane compound is applied to a support.
  • the film with resin obtained by coating and the laminate produced by laminating the prepreg have particularly low cure shrinkage, low thermal expansion, copper foil adhesion, high elastic modulus, and excellent dielectric properties. It is useful as a highly integrated semiconductor package and multilayer printed wiring board for electronic devices.

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Abstract

L'invention concerne un composé siloxane modifié par amino comprenant une azométhine aromatique dans une structure moléculaire obtenue en faisant réagir un composé siloxane (B) présentant au moins deux groupes amino primaires en l'extrémité moléculaire correspondante avec un composé azométhine aromatique (A) qui présente au moins un groupe aldéhyde par molécule et qui est obtenu en faisant réagir un composé amine aromatique (i) présentant au moins deux groupes amino primaires par molécule avec un composé aldéhyde aromatique (ii) présentant au moins deux groupes aldéhyde par molécule ; et une résine imide modifiée et une composition de résine thermodurcissable mettant en œuvre ledit composé siloxane modifié par amino.
PCT/JP2013/082054 2012-11-28 2013-11-28 Composé siloxane modifié par amino, résine imide modifiée, composition de résine thermodurcissable, préimprégné, film apprêté par une résine, plaque stratifiée, carte de circuit imprimé multicouche et emballage semi-conducteur WO2014084310A1 (fr)

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PCT/JP2013/082072 WO2014084318A1 (fr) 2012-11-28 2013-11-28 Composé siloxane, résine imide modifiée, composition de résine thermodurcissable, préimprégné, film équipé de résine, plaque stratifiée, carte de circuit imprimé multicouche et boîtier de semi-conducteur

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JP2014129521A (ja) * 2012-11-28 2014-07-10 Hitachi Chemical Co Ltd 変性シロキサン化合物、熱硬化性樹脂組成物、プリプレグ、樹脂付きフィルム、積層板、多層プリント配線板及び半導体パッケージ
JP2015224303A (ja) * 2014-05-28 2015-12-14 日立化成株式会社 熱硬化性樹脂組成物、プリプレグ、樹脂付フィルム、積層板、多層プリント配線板及び半導体パッケージ
JP2015224304A (ja) * 2014-05-28 2015-12-14 日立化成株式会社 熱硬化性樹脂組成物、プリプレグ、樹脂付フィルム、積層板、多層プリント配線板及び半導体パッケージ
JP2015224306A (ja) * 2014-05-28 2015-12-14 日立化成株式会社 熱硬化性樹脂組成物、プリプレグ、樹脂付フィルム、積層板、多層プリント配線板及び半導体パッケージ
JP2016030757A (ja) * 2014-07-25 2016-03-07 日立化成株式会社 熱硬化性樹脂組成物、これを用いるプリプレグ、樹脂付フィルム、積層板、多層プリント配線板及び半導体パッケージ
JP2016132738A (ja) * 2015-01-20 2016-07-25 日立化成株式会社 熱硬化性樹脂組成物、プリプレグ、樹脂付フィルム、積層板、多層プリント配線板及び半導体パッケージ
JPWO2014084318A1 (ja) * 2012-11-28 2017-01-05 日立化成株式会社 シロキサン化合物、変性イミド樹脂、熱硬化性樹脂組成物、プリプレグ、樹脂付きフィルム、積層板、多層プリント配線板及び半導体パッケージ
JP2017008174A (ja) * 2015-06-19 2017-01-12 日立化成株式会社 熱硬化性樹脂組成物、プリプレグ、積層板及び多層プリント配線板
JP2017132858A (ja) * 2016-01-26 2017-08-03 日立化成株式会社 熱硬化性樹脂組成物、プリプレグ、樹脂付きフィルム、積層板及び多層プリント配線板
JP2018130938A (ja) * 2017-02-17 2018-08-23 日立化成株式会社 プリプレグ、積層板、プリント配線板、コアレス基板、半導体パッケージ及びコアレス基板の製造方法
US10323126B2 (en) 2012-11-28 2019-06-18 Hitachi Chemical Company, Ltd. Siloxane compound, modified imide resin, thermosetting resin composition, prepreg, film with resin, laminated plate, multilayer printed wiring board, and semiconductor package
JP2019518813A (ja) * 2016-04-15 2019-07-04 エコール・シュペリュール・ドゥ・フィシック・エ・ドゥ・シミー・アンデュストリエル・ドゥ・ラ・ヴィル・ドゥ・パリ 交換可能な架橋点を有する架橋シリコーンを含むポリマー組成物、調製方法及び使用
JP2019192343A (ja) * 2018-04-18 2019-10-31 日立化成株式会社 層間絶縁層用樹脂フィルム、積層体、プリント配線板、半導体装置及び積層体の製造方法
EP3489308A4 (fr) * 2016-07-19 2019-12-18 Hitachi Chemical Company, Ltd. Composition de résine, plaque stratifiée, et carte de circuit imprimé multicouche
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