WO2014084318A1 - 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 - Google Patents

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 Download PDF

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WO2014084318A1
WO2014084318A1 PCT/JP2013/082072 JP2013082072W WO2014084318A1 WO 2014084318 A1 WO2014084318 A1 WO 2014084318A1 JP 2013082072 W JP2013082072 W JP 2013082072W WO 2014084318 A1 WO2014084318 A1 WO 2014084318A1
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group
compound
resin
siloxane compound
aromatic
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PCT/JP2013/082072
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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 JP2014549897A priority Critical patent/JP6747655B2/ja
Priority to KR1020157013901A priority patent/KR102166235B1/ko
Priority to CN201380061809.9A priority patent/CN104812805B/zh
Publication of WO2014084318A1 publication Critical patent/WO2014084318A1/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 a siloxane compound suitable for a semiconductor package or a printed wiring board, a modified imide resin using the same, a thermosetting resin composition, a prepreg, a film with a resin, a laminated board, a multilayer printed 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.
  • processability and moldability and difficulty in handling due to low solubility in organic solvents.
  • Non-Patent Document 1 Since D'Aleio found polyazomethine, which is a liquid crystalline oligomer (see Non-Patent Document 1), there have been reports of cases relating to resins using many polyazomethines (see Patent Documents 1 to 7).
  • Patent Document 1 discloses various polyazomethines, and Patent Documents 2 to 7 disclose polyazomethines having specific structures.
  • Patent Documents 8 and 9 disclose thermosetting polyazomethine resins containing unsaturated groups and describe 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 JP 2011-195476 A
  • the polyazomethines described in Patent Documents 1 to 7 may lack heat resistance and moldability 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 thermosetting polyazomethine resin described in Patent Document 9 has not been satisfactory in terms of low curing shrinkage and low thermal expansion.
  • the object of the present invention is a thermosetting resin composition that exhibits excellent low curing shrinkage, low thermal expansion, good dielectric properties, and high elastic modulus when applied to various applications.
  • the present inventors have found that the above object can be achieved by using a modified siloxane compound having an aromatic azomethine, and have reached the present invention.
  • the present invention is based on such knowledge.
  • the present invention provides the following siloxane compound, modified imide resin, thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed wiring board, and semiconductor package.
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group, a thiol group, an acetyl group, a hydroxyl group, a sulfonic acid group, or 1 to 3 carbon atoms.
  • an alkoxyl group having 1 to 3 carbon atoms, x and y are each independently an integer of 0 to 4.
  • A is a single bond or an azomethine group, an ester group, an amide group, an azoxy group, An azo group, an ethylene group or an acetylene group.
  • 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
  • An aromatic amine compound (A) having at least two primary amino groups in one molecule, an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule, and at least 2 at the molecular end The siloxane compound according to [2], which is obtained by reacting a siloxane compound (C) having an amino group.
  • each R 5 independently represents a hydroxyl group, carboxyl group or sulfonic acid group which is an acidic substituent
  • each R 6 independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • X is an integer from 1 to 5
  • y is an integer from 0 to 4, and the sum of x and y is 5.
  • each R 5 independently represents a hydroxyl group, carboxyl group or sulfonic acid group which is an acidic substituent
  • each R 6 independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • X is an integer from 1 to 5
  • y is an integer from 0 to 4, and the sum of x and y is 5.
  • [16] A laminate obtained by laminate-molding the prepreg according to [14].
  • [17] A laminate obtained by laminating the film with resin according to [15].
  • [18] A multilayer printed wiring board produced using the laminated board according to [16] or [17].
  • [19] A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to [18].
  • a siloxane compound capable of realizing a thermosetting resin composition that exhibits excellent low curing shrinkage, low thermal expansion, good dielectric properties, and high elastic modulus when applied to various applications.
  • a modified imide resin, a thermosetting resin composition, a prepreg using the resin, a film with a resin, a laminate, a multilayer printed wiring board, and a semiconductor package can be provided.
  • thermosetting resin composition containing a modified siloxane compound having an aromatic azomethine of the present invention, a prepreg obtained by impregnating and coating a base material, a film with a resin obtained by coating a support,
  • the laminate produced by laminating the prepreg has particularly low curing shrinkage, low thermal expansion, excellent dielectric properties, and high elastic modulus, and is useful as a multilayer printed wiring board and a semiconductor package.
  • the siloxane compound of the present invention includes a structure represented by the following general formula (1) and the following general formula (2).
  • a structure represented by the following general formula (1) can be obtained, for example, by reacting a compound having a structure represented by the following general formula (1) with a compound having a structure represented by the following general formula (2).
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group, a thiol group, an acetyl group, a hydroxyl group, a sulfonic acid group, or 1 to 3 carbon atoms.
  • an alkoxyl group having 1 to 3 carbon atoms, x and y are each independently an integer of 0 to 4.
  • A is a single bond or an azomethine group, an ester group, an amide group, an azoxy group, An azo group, an ethylene group or an acetylene group.
  • the siloxane compound of this invention contains aromatic azomethine.
  • the aromatic azomethine means a compound in which at least one aromatic is bonded to a Schiff base (—N ⁇ CH—).
  • the siloxane compound of the present invention is an aromatic amine compound (A) having at least two primary amino groups in one molecule (hereinafter sometimes referred to as an aromatic amine compound (A)).
  • Aromatic aldehyde compound (B) having two aldehyde groups hereinafter sometimes referred to as aromatic aldehyde compound (B)
  • siloxane compound (C) having at least two amino groups at the molecular terminals hereinafter, It may be obtained by reacting a siloxane compound (sometimes called a siloxane compound (C)).
  • aromatic amine compound (A) having at least two primary amino groups in one molecule of the present invention examples include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1, 4-diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 4,4′-diamino-3 , 3'-diethyl-diphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, benzidine, 3,3'- Dimethyl-4,4′-diaminobiphenyl,
  • 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 and the like are more preferable.
  • 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 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 (B) 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 etc. are mentioned. Among these, for example, 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 (C) having at least two amino groups at the molecular ends of the present invention includes a structure represented by the following general formula (2). (Wherein 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) In the general formula (2), n is an integer of 1 to 100, more preferably an integer of 2 to 50.
  • a commercially available product may be used as the siloxane compound (C) having at least two amino groups at the molecular terminals.
  • 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 are particularly preferable from the viewpoint of excellent compatibility and high elastic modulus.
  • examples of the reaction for obtaining the siloxane compound include the following methods.
  • Reaction method a aromatic amine compound (A) having at least two primary amino groups in one molecule, aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule, molecular terminals
  • a siloxane compound (i) can be obtained by reacting a siloxane compound (C) having at least two amino groups.
  • Reaction method b First, an aromatic amine compound (A) having at least two primary amino groups in one molecule and an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule are reacted. To obtain an aromatic azomethine compound having at least one aldehyde group in one molecule. Next, the modified siloxane compound (ii) having an aromatic azomethine can be obtained by subjecting the compound and a siloxane compound (C) having at least two amino groups at the molecular ends to a dehydration condensation reaction in an organic solvent. .
  • Reaction method c First, by reacting an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule with a siloxane compound (C) having at least two amino groups at the molecular ends, 1 A modified siloxane compound having at least one aldehyde group and azomethine group (—N ⁇ CH—) in the molecule is obtained. Next, the modified siloxane compound (iii) having an aromatic azomethine can be obtained by reacting the compound with an aromatic amine compound (A) having at least two primary amino groups in one molecule.
  • the siloxane compound of the present invention can be obtained by using any of the above reaction methods a, b, and c.
  • the reaction method a is particularly easy to operate, and the modified siloxane compound of the present invention dissolves in a solvent. This is particularly effective when the performance is insufficient.
  • the reaction method b has a feature that the molecular weight of the aromatic azomethine in the molecule of the siloxane compound of the present invention can be easily controlled, and is particularly effective for increasing the elastic modulus of a resin composition containing the aromatic azomethine.
  • the reaction method c has a feature that the molecular weight of the siloxane in the molecule of the siloxane compound of the present invention can be easily controlled, and is effective for reducing the thermal expansion coefficient of the resin composition containing the same.
  • reaction method a an aromatic amine compound (A) having at least two primary amino groups in one molecule, an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule, and a molecule
  • the siloxane compound (i) of the present invention can be obtained by reacting the siloxane compound (C) having at least two amino groups at the terminals.
  • an aromatic amine compound (A) having at least two primary amino groups in one molecule an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule, and at least 2 at the molecular end
  • the amount of the siloxane compound (C) having one amino group is the number of primary amino groups of the aromatic amine compound (A) and the siloxane compound (C) [the amount of aromatic amine compound (A) used / aromatic amine compound ( A) primary amino group equivalent + amount of siloxane compound (C) used / primary amino group equivalent of siloxane compound (C)] is the number of aldehyde groups of aromatic aldehyde compound (B) [use of aromatic aldehyde compound (B) Amount / aldehyde group equivalent of aromatic aldehyde compound (B)] is preferably used in a range of 1.0 to 10.0 times.
  • thermosetting resin containing the modified siloxane compound (i) which has aromatic azomethine By setting it to 1.0 times or more, a decrease in solubility in a solvent tends to be suppressed. Moreover, it is in the tendency for the heat resistant fall of the thermosetting resin containing the modified siloxane compound (i) which has aromatic azomethine to be suppressed by setting it as 10.0 times or less.
  • organic solvent can be used for this reaction.
  • the organic solvent to be used is not particularly limited.
  • alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • Solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, sulfur atom containing solvents such as dimethyl sulfoxide, ⁇ - Examples thereof include ester solvents such as butyrolactone. These may be used alone or in combination of two or more. Among these, from the viewpoint of solubility, for example, propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, dimethylacetamide, and ⁇ -butyrolactone are preferable.
  • propylene glycol monomethyl ether and toluene are more preferable because they are highly volatile and hardly remain as residual solvents during the production of prepreg.
  • this reaction is a dehydration condensation reaction, water is produced as a by-product.
  • the amount of the organic solvent used is, for example, 25 to 2000 parts by mass per 100 parts by mass in terms of the solid content of the aromatic amine compound (A), aromatic aldehyde compound (B) and siloxane compound (C).
  • the amount is preferably 40 to 1000 parts by weight, more preferably 40 to 500 parts by weight. If the amount of the organic solvent used is 25 parts by mass or more, the lack of solubility tends to be suppressed. Moreover, if it is 2000 mass parts or less, reaction time will become suitable.
  • reaction catalyst can be used if necessary.
  • the reaction catalyst used is not particularly limited.
  • 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 combination of two or more.
  • an acidic catalyst such as p-toluenesulfonic acid is preferred.
  • a siloxane compound (i) is obtained by charging the above raw materials, an organic solvent and, if necessary, a reaction catalyst into a reaction kettle and stirring for 0.1 to 10 hours while heating and keeping warm as necessary to cause a dehydration condensation reaction.
  • the reaction temperature is preferably 70 to 150 ° C., for example, and the reaction is desirably performed while removing water as a by-product, and the reaction temperature is more preferably 100 to 130.
  • the temperature is lower than 70 ° C., the reaction rate is slow, and when the temperature is 150 ° C. or lower, a high-boiling solvent is not required as a reaction solvent, and when producing a prepreg, it is difficult to leave a residual solvent and heat resistance is reduced. Can be suppressed.
  • reaction method b First, an aromatic amine compound (A) having at least two primary amino groups in one molecule and an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule. To obtain an aromatic azomethine compound having at least one aldehyde group in one molecule. Subsequently, the modified siloxane compound (ii) having an aromatic azomethine can be obtained by reacting the compound with a siloxane compound (C) having at least two amino groups at the molecular terminals.
  • the same organic solvent as used in reaction method a can be used as the organic solvent used in the reaction and, if necessary, the reaction catalyst.
  • an aromatic amine compound (A) having at least two primary amino groups per molecule and an aromatic aldehyde compound (B) having at least two aldehyde groups per molecule in an organic solvent By performing dehydration condensation reaction, an aromatic azomethine compound having at least one aldehyde group in one molecule is obtained.
  • the use amount of the aromatic amine compound (A) having at least two primary amino groups in one molecule and the aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule is, for example,
  • the number of primary amino groups of the aromatic amine compound (A) [the amount of the aromatic amine compound (A) used / the primary amino group equivalent of the aromatic amine compound (A)] is the number of aldehyde groups of the aromatic aldehyde compound (B) [
  • the amount used of the aromatic aldehyde compound (B) / the aldehyde group equivalent of the aromatic aldehyde compound (B)] is preferably 0.1 to 5.0 times.
  • the amount of the organic solvent used is preferably, for example, 25 to 2000 parts by mass with respect to 100 parts by mass of the total resin components of the aromatic amine compound (A) and aromatic aldehyde compound (B). More preferably, the content is set to ⁇ 1000 parts by mass, and particularly preferably 40 to 500 parts by mass. If the amount of the organic solvent used is 25 parts by mass or more, the lack of solubility tends to be suppressed. Moreover, if it is 2000 mass parts or less, reaction time will become suitable.
  • At least one aldehyde per molecule is prepared by charging the above raw materials, organic solvent, and if necessary, a reaction catalyst in a reaction kettle, and stirring and dehydrating condensation reaction for 0.1 to 10 hours while heating and holding as necessary.
  • An aromatic azomethine compound having a group is obtained.
  • the reaction temperature is, for example, preferably 70 to 150 ° C, more preferably 00 to 130 ° C. Moreover, it is preferable to react, removing the water which is a by-product. If 1 temperature is 70 degreeC or more, it exists in the tendency for reaction rate not to become too slow. If the reaction temperature is 150 ° C. or lower, a high-boiling solvent is not required for the reaction solvent, and when the prepreg is produced, it is difficult to leave a residual solvent, and a decrease in heat resistance can be suppressed.
  • a dehydration condensation reaction of the aromatic azomethine compound having at least one aldehyde group in one molecule obtained by the above reaction and the siloxane compound (C) having at least two amino groups at the molecular ends in an organic solvent By doing so, a modified siloxane compound (ii) having an aromatic azomethine can be obtained.
  • the amount of the aromatic azomethine compound and the siloxane compound (C) used is, for example, the number of primary amino groups of the siloxane compound (C) [the amount of siloxane compound (C) used / the primary amino group equivalent of the siloxane compound (C)].
  • the amount of the organic solvent used is, for example, from 25 to 100 parts by mass with respect to a total of 100 parts by mass of the resin component of the aromatic aromatic azomethine compound having at least one aldehyde group in one molecule and the siloxane compound (C).
  • the amount is preferably 2000 parts by mass, more preferably 40 to 1000 parts by mass, and particularly preferably 40 to 500 parts by mass. If the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility tends to be suppressed. Moreover, if it is 2000 mass parts or less, reaction time will become suitable.
  • a modified siloxane compound having an aromatic azomethine (ii) 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 keeping heat as necessary. ) Is obtained.
  • the reaction temperature is, for example, preferably 70 to 150 ° C, more preferably 100 to 130 ° C. Moreover, it is preferable to react, removing the water which is a by-product. When the reaction temperature is 70 ° C. or higher, the reaction rate tends not to be too slow. If reaction temperature is 150 degrees C or less, a high boiling point solvent is not required for a reaction solvent, and when manufacturing a prepreg, it will become difficult to leave a residual solvent and it can suppress a heat resistant fall.
  • reaction method c First, an aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule and a siloxane compound (C) having at least two amino groups at the molecular ends are reacted. A modified siloxane compound having at least one aldehyde group and azomethine group (—N ⁇ CH—) in one molecule is obtained. Next, the modified siloxane compound (iii) having an aromatic azomethine can be obtained by reacting the compound with an aromatic amine compound (A) having at least two primary amino groups in one molecule.
  • the organic solvent used in the reaction and the reaction catalyst used as necessary can be the same as those used in the reaction methods a and b.
  • An aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule and a siloxane compound (C) having at least two amino groups at the molecular ends are subjected to a dehydration condensation reaction in an organic solvent.
  • a modified siloxane compound having at least one aldehyde group and azomethine group (—N ⁇ CH—) in the molecule is obtained.
  • the amount of the aromatic aldehyde compound (B) having at least two aldehyde groups in one molecule and the amount of the siloxane compound (C) having at least two amino groups at the molecular ends are, for example, siloxane compound ( C) number of primary amino groups [amount of siloxane compound (C) used / primary amino group equivalent of siloxane compound (C)] is the number of aldehyde groups of aromatic aldehyde compound (B) [amount of aromatic aldehyde compound (B) used] / Aldehyde group equivalent of aromatic aldehyde compound (B)] is preferably used in a range of 0.1 to 5.0 times.
  • the amount of the organic solvent used is preferably 25 to 2000 parts by mass with respect to 100 parts by mass of the total resin components of the aromatic aldehyde compound (B) and the siloxane compound (C), for example, 40 to 1000 parts.
  • the amount is more preferably part by mass, and particularly preferably 40 to 500 parts by mass. If the amount of the organic solvent used is 25 parts by mass or more, the solubility is not insufficient, and if it is 2000 parts by mass or less, the reaction time is appropriate.
  • At least one aldehyde per molecule is prepared by charging the above raw materials, organic solvent, and if necessary, a reaction catalyst in a reaction kettle, and stirring and dehydrating condensation reaction for 0.1 to 10 hours while heating and holding as necessary.
  • a modified siloxane compound having an azomethine group (—N ⁇ CH—) is obtained.
  • the reaction temperature is, for example, preferably 70 to 150 ° C, more preferably 100 to 130 ° C. Moreover, it is preferable to react, removing the water which is a by-product. When the reaction temperature is 70 ° C. or higher, the reaction rate tends not to be too slow. When the reaction temperature is 150 ° C. or lower, a high-boiling solvent is not required as the reaction solvent, and when the prepreg is produced, it is difficult to leave a residual solvent, and a decrease in heat resistance can be suppressed.
  • a modified siloxane compound (iii) having an aromatic azomethine can be obtained by subjecting the aromatic amine compound (A) to a dehydration condensation reaction in an organic solvent.
  • the usage amount of the modified siloxane compound and the aromatic amine compound (A) is, for example, the number of primary amino groups of the aromatic amine compound (A) [the usage amount of the aromatic amine compound (A) / the aromatic amine compound (A).
  • Primary amino group equivalent] is 1.0 to 10.0 times the number of aldehyde groups of the modified siloxane compound [amount of modified siloxane compound used / aldehyde group equivalent of the modified siloxane compound]. Is preferred. By setting it to 1.0 times or more, there is a tendency that a decrease in low thermal expansion of the thermosetting resin containing the modified siloxane compound (iii) having an aromatic azomethine is suppressed. Moreover, it exists in the tendency for the fall of the solubility to a solvent to be suppressed by setting it as 10.0 times or less.
  • the amount of the organic solvent used is, for example, the sum of the resin components of the modified siloxane compound having at least one aldehyde group and azomethine group (—N ⁇ CH—) in one molecule and the aromatic amine compound (A).
  • the amount is preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, and particularly preferably 40 to 500 parts by mass with respect to 100 parts by mass. If the amount of the organic solvent used is 25 parts by mass or more, the lack of solubility tends to be suppressed. Moreover, if it is 2000 mass parts or less, reaction time will become suitable.
  • a modified siloxane compound having an aromatic azomethine is prepared by charging the above raw materials, an organic solvent and, if necessary, a reaction catalyst into a reaction kettle and stirring and dehydrating and condensing for 0.1 to 10 hours while heating and holding as necessary. iii) is obtained.
  • the reaction temperature is, for example, preferably 70 to 150 ° C, more preferably 100 to 130 ° C. Moreover, it is preferable to react, removing the water which is a by-product. When the reaction temperature is 70 ° C. or higher, the reaction rate tends not to be too slow. If reaction temperature is 150 degrees C or less, it will become difficult to leave a residual solvent when manufacturing a prepreg, without requiring a high boiling point solvent as a reaction solvent, and a heat resistant fall can be suppressed.
  • the modified siloxane compound of the present invention obtained by the above reaction methods a, b and c can be confirmed by performing IR measurement.
  • the weight average molecular weight (Mw) is, for example, preferably 1000 to 300000, and particularly preferably 6000 to 150,000.
  • weight average molecular weight (Mw) is not less than the lower limit, low curing shrinkage and low thermal expansion are improved, and if it is not more than the upper limit, compatibility and elastic modulus are improved.
  • the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and converted by a calibration curve produced using standard polystyrene. For example, it can be performed under the following conditions.
  • 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 ( JASCO Corporation 870-UV) and HPLC pump (JASCO Corporation 880-PU) are used.
  • TSKgel SuperHZ2000, 2300 manufactured by Tosoh Corporation can be used as the column used, and measurement can be performed by using a measurement temperature of 40 ° C., a flow rate of 0.5 ml / min, and a solvent 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 (3).
  • 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, carboxyl group or 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.
  • the thermosetting resin composition of the present invention comprises the modified siloxane compound of the present invention and a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule.
  • maleimide compounds (D) having at least two N-substituted maleimide groups in one molecule include bis (4-maleimidophenyl) methane, polyphenyl Methanemaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene Examples thereof include bismaleimide, m-phenylene bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, and the like. These maleimide compounds may be used alone
  • bis (4-maleimidophenyl) methane bis (4-maleimidophenyl) sulfone, 2,2-bis (4- (4-maleimidophenoxy), which has high reactivity and can have higher heat resistance.
  • bis (4-maleimidophenyl) methane and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are more preferable and inexpensive.
  • Bis (4-maleimidophenyl) methane is particularly preferred.
  • the amount (blending amount) of the siloxane compound of the present invention 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 maleimide compound (D) used is, for example, preferably 30 to 99 parts by weight, and 40 to 95 parts by weight per 100 parts by weight of the total resin components. More preferable in terms
  • thermosetting resin composition of the present invention comprises the siloxane compound of the present invention and a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule.
  • D maleimide compound
  • a modified imide resin by reacting the siloxane compound of the present invention and the maleimide compound (D) while heating and keeping in an organic solvent.
  • the reaction temperature when reacting the modified siloxane compound and maleimide compound (D) in an organic solvent is preferably, for example, 70 to 150 ° C., more preferably 100 to 130 ° C.
  • the reaction time is, for example, preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
  • the amount of maleimide compound (D) and the siloxane compound of the present invention used is, for example, the number of maleimide groups of maleimide compound (D) [the amount of maleimide compound (D) used / maleimide group equivalent of maleimide compound (D) Is preferably in the range of 2.0 to 10.0 times the number of primary amino groups of the siloxane compound of the present invention [the amount of the siloxane compound of the present invention used / the primary amino group equivalent of the siloxane compound of the present invention]. .
  • 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 maleimide compound (D) used in the pre-reaction is preferably 50 to 3000 parts by weight, for example, 100 to 1500 parts per 100 parts by weight of the resin component of the siloxane compound of the present invention while maintaining the above relationship. Part by mass is more preferable. When the amount is 50 parts by mass or more, a decrease in heat resistance tends to be suppressed. Moreover, 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 may 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 preferably, for example, 25 to 2000 parts by mass, preferably 40 to 1000 parts by mass with respect to 100 parts by mass of the total of the resin components of the siloxane compound and maleimide compound (D) of the present invention. More preferred is 40 to 500 parts by mass. If the amount of the organic solvent used is 25 parts by mass or more, the solubility is not insufficient, and if it is 2000 parts by mass or less, the reaction time is appropriate.
  • reaction catalyst can be optionally used for this pre-reaction.
  • the reaction catalyst is not particularly limited.
  • amines such as triethylamine, pyridine, and tributylamine
  • imidazoles such as methylimidazole and phenylimidazole
  • phosphorus-based catalysts such as triphenylphosphine
  • lithium amide sodium amide
  • potassium amide examples include alkali metal amides. These may 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. Low thermal expansion and high elastic modulus can be obtained by setting the blended amount of the modified imide resin having aromatic azomethine to 50 parts by mass or more.
  • thermosetting resin composition comprising the siloxane compound of the present invention and a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule, and an aromatic obtained by pre-reacting the above compound
  • the modified imide resin having azomethine alone has good thermosetting reactivity, but if necessary, a curing agent and a radical initiator may 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.
  • the radical initiator is not particularly limited, and examples thereof include acyl peroxides, hydroperoxides, ketone peroxides, organic peroxides having a t-butyl group, and peroxides having a cumyl group.
  • Organic peroxides 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 (E) having an acidic substituent represented by the following general formula (3).
  • each R 5 independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent
  • each R 6 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 (E) 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 and the like can be mentioned.
  • m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5- Dihydroxyaniline is preferred, and m-aminophenol and p-aminophenol are more preferred from the viewpoint of heat resistance.
  • the amount of the amine compound (E) having an acidic substituent is, for example, preferably 0.5 to 30 parts by mass, and preferably 1 to 20 parts by mass per 100 parts by mass of the total resin components. More preferable in terms of expansibility
  • thermosetting resin composition of the present invention comprises the modified siloxane compound of the present invention, a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule, and an amine compound (E) having an acidic substituent.
  • the above compound may 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.
  • a modified imide resin having an acidic substituent is synthesized by reacting the siloxane compound of the present invention, a maleimide compound (D), and an amine compound (E) having an acidic substituent while being heated and kept in an organic solvent. It is preferable to do.
  • the reaction temperature when the siloxane compound of the present invention, maleimide compound (D), and amine compound (E) having an acidic substituent are reacted in an organic solvent is preferably 70 to 150 ° C., for example, and preferably 100 to 130. More preferably, it is ° C.
  • the reaction time is, for example, preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
  • the amount of the maleimide compound (D), the siloxane compound of the present invention and the amine compound (E) having an acidic substituent is, for example, the number of maleimide groups of the maleimide compound (D) [use of the maleimide compound (D).
  • Amount / maleimide group equivalent of maleimide compound (D)] is the number of primary amino groups of the amine compound (E) having an acidic substituent and the siloxane compound of the present invention [the amount of the siloxane compound of the present invention used / of the siloxane compound of the present invention] Primary amino group equivalent + Amount of amine compound (E) having acidic substituent / Primary amino group equivalent of amine compound (E) having acidic substituent] Is preferred.
  • Gelation and a decrease in heat resistance tend to be suppressed.
  • it can suppress that the solubility to an organic solvent and heat resistance fall by making it 10.0 times or less.
  • the amount of the maleimide compound (D) used in the pre-reaction is preferably 50 to 3000 parts by weight, for example, 100 to 1500 parts per 100 parts by weight of the resin component of the siloxane compound of the present invention while maintaining the above relationship. Part by mass is more preferable. By setting it to 50 parts by mass or more, a decrease in heat resistance can be suppressed. Moreover, low thermal expansibility can be kept favorable by setting it as 3000 mass parts or less.
  • the amount of the amine compound (E) having an acidic substituent in the pre-reaction is, for example, preferably 1 to 1000 parts by weight, and preferably 5 to 500 parts by weight with respect to 100 parts by weight of the resin component of the siloxane compound of the present invention. More preferred. By setting it as 1 mass part or more, a heat resistant fall can be suppressed, and low thermal expansion can be kept favorable by setting it as 1000 mass parts or less.
  • the organic solvent used in this pre-reaction is not particularly limited, but, for example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • Ketone solvents examples include a solvent containing a sulfur atom-containing solvent such as dimethyl sulfoxide. These 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 resin component of the siloxane compound, maleimide compound (D), and amine compound (E) having an acidic substituent of the present invention. It is preferably 40 to 1000 parts by mass, more preferably 40 to 500 parts by mass. If the amount of the organic solvent used is 25 parts by mass or more, the lack of solubility tends to be suppressed. Moreover, if it is 2000 mass parts or less, reaction time will become suitable.
  • reaction catalyst can be arbitrarily used for this pre-reaction.
  • the reaction catalyst is not particularly limited.
  • amines such as triethylamine, pyridine, and tributylamine
  • imidazoles such as methylimidazole and phenylimidazole
  • phosphorus-based catalysts such as triphenylphosphine
  • lithium amide sodium amide
  • potassium amide examples include alkali metal amides. These may 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 100 parts by mass.
  • a heat comprising the modified siloxane compound having an aromatic azomethine of the present invention, a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule, and an amine compound (E) having an acidic substituent.
  • the curable resin composition and the modified imide resin having an aromatic substituent and an aromatic azomethine obtained by pre-reacting the above compound have good thermosetting reactivity alone, 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.
  • 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 (F).
  • thermoplastic elastomer (F) examples include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, silicone elastomers and derivatives thereof. These 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.
  • those having a reactive functional group at the molecular terminal 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 in terms of heat resistance and insulation reliability, and styrene elastomers and olefins are preferable in terms of dielectric properties. Elastomers are particularly preferred.
  • the reactive functional group possessed in the molecular terminal or molecular chain of these elastomers 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. From the viewpoint of insulation reliability, an epoxy group, a hydroxyl group, and an amino group are particularly preferable.
  • the amount of the thermoplastic elastomer (F) component used is, for example, preferably from 0.1 to 50 parts by weight, preferably from 2 to 30 parts by weight, based on 100 parts by weight of the total resin components. It is more preferable because it has good compatibility and can effectively exhibit low curing shrinkage, low thermal expansion and excellent dielectric properties of the cured product.
  • thermosetting resin composition of the present invention can contain at least one thermosetting resin (G) selected from an epoxy resin and a cyanate resin.
  • the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak 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 ether compounds of polycyclic aromatics such as anthracene Beauty These and phosphorus-containing epoxy resin obtained by introducing a phosphorus compound is mentioned. These may be used alone or in admixture of two or more. Among these, for example, biphenyl aralkyl type epoxy resins and naphthalene type epoxy resins are preferable from the viewpoint of heat resistance and flame retardancy.
  • cyanate resin examples include novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, and bisphenol type cyanate resin such as tetramethylbisphenol F type cyanate resin, and prepolymers in which these are partially triazine. Is mentioned. 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.
  • thermosetting resins (G) can be used for these thermosetting resins (G) 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
  • acid 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 the thermosetting resin (G) used is preferably, for example, 1 to 50 parts by mass per 100 parts by mass of the total resin components, and 3 to 30 parts by mass from the viewpoint of heat resistance and chemical resistance. It is more preferable that
  • the thermosetting resin composition of the present invention can contain an inorganic filler (H).
  • inorganic fillers include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, and barium sulfate.
  • Aluminum borate, potassium titanate, glass powder such as E glass, T glass, 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 or the like.
  • 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 diameter of the fused spherical silica 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 inorganic filler is, for example, preferably 20 to 500 parts by mass and more preferably 50 to 350 parts by mass with respect to 100 parts by mass of the total resin components.
  • the content of the inorganic filler is, for example, preferably 20 to 500 parts by mass and more preferably 50 to 350 parts by mass with respect to 100 parts by mass of the total resin components.
  • the moldability and low thermal expansion of the resin composition can be kept good.
  • the inorganic filler is blended in the resin composition, for example, the inorganic filler is pretreated with a silane or titanate coupling agent, a surface treatment agent such as a silicone oligomer, or an integral blend treatment. It is also preferable.
  • the thermosetting resin composition of the present invention can contain a curing accelerator (I).
  • the curing accelerator include zinc metal naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III) and the like, imidazoles and Examples thereof include organic phosphorus compounds such as phosphines and phosphonium salts, secondary amines, tertiary amines, and quaternary ammonium salts. These 1 type can be used individually or in mixture of 2 or more types. Among these, for example, zinc naphthenate, imidazole derivatives, and phosphonium salts are preferable from the viewpoint of the promoting effect and the storage stability.
  • the content of the curing accelerator is, for example, preferably 0.01 to 3.0 parts by mass, more preferably 0.05 to 1.5 parts by mass with respect to 100 parts by mass of the total resin components. .
  • the content of the curing accelerator is, for example, preferably 0.01 to 3.0 parts by mass, more preferably 0.05 to 1.5 parts by mass with respect to 100 parts by mass of the total resin components.
  • 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 can be used individually by 1 type or in mixture of 2 or more types.
  • 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 siloxane compound of the present invention is used for a prepreg, it is preferable to finally make a varnish in which each component is dissolved or dispersed in an organic solvent.
  • 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 resin component in the finally obtained varnish is, for example, preferably 40 to 90% by mass, more preferably 50 to 80% by mass of the entire varnish.
  • the “resin component” means a siloxane compound, a modified imide resin (modified imide having an acidic substituent derived from the acidic substituent of the amine compound (D) represented by the general formula (3) described above) 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 is, for example, such 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 be usually obtained by heating and drying 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.
  • a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. Is done. 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, polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and the like.
  • PET polyethylene terephthalate
  • polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and the like.
  • the film include metal foil such as release paper, copper foil, and aluminum foil.
  • the thickness of the support is, for example, preferably 10 to 150 ⁇ m, more preferably 25 to 50 ⁇ m.
  • a protective film according to the support can be further laminated on the surface of the resin composition layer where the support is not provided.
  • 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, while pressing and heating the film with resin Crimp to circuit board.
  • 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.
  • the laminating method may be a batch method or a continuous method using a roll.
  • 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.
  • the support is not peeled off after the insulating resin layer is formed, it is peeled off here.
  • holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, 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 resin layer by dry plating or wet plating.
  • dry plating 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 and forming a metal foil such as copper or aluminum on one or both sides thereof.
  • a laminate plate for an electrical insulating material and a multilayer plate method can be applied.
  • a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. are used, and Molding can be performed at 250 ° C., pressure of 0.2 to 10 MPa, and 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 a through hole or blind via hole by drilling or laser processing, and formation of an 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.
  • 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.
  • Flexural modulus A copper-clad laminate was immersed in a copper etching solution to produce a 25 mm ⁇ 50 mm evaluation board from which the copper foil was removed, using a 5-ton tensilon manufactured by Orientec Co., Ltd., and a crosshead speed of 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 Siloxane Compound (i-1) Into a reaction vessel with 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, 3,3′-dimethyl- 4,4′-diaminobiphenyl: 0.27 g, terephthalaldehyde: 0.33 g, X-22-161B: 199.4 g, propylene glycol monomethyl ether: 300.0 g were added and reacted at 115 ° C. for 4 hours. The mixture was heated to 0 ° C. and dehydrated by atmospheric concentration to obtain a modified siloxane compound (i-1) -containing solution (Mw: 30000, resin component: 90% by mass) having aromatic azomethine.
  • Mw modified siloxane compound
  • resin component 90% by mass
  • Production Example 2 Production of Siloxane Compound (i-2) 4,4′-Diaminobenze was placed in a reaction vessel with 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.
  • Anilide: 0.27 g, terephthalaldehyde: 0.31 g, X-22-161B: 199.4 g, propylene glycol monomethyl ether: 300.0 g were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C.
  • Production Example 5 Production of Siloxane Compound (i-5) 3,3′-Diethyl-into a reaction vessel having a thermometer, a stirrer, a moisture meter with a reflux condenser and a heat-coolable volume of 2 liters.
  • 4,4′-diaminodiphenylmethane: 0.18 g, terephthalaldehyde: 0.19 g, KF-8012: 199.6 g, propylene glycol monomethyl ether: 300.0 g were added, reacted at 115 ° C. for 4 hours, and then to 130 ° C.
  • the temperature was raised and dehydration was performed by concentration under atmospheric pressure to obtain a modified siloxane compound (i-5) -containing solution (Mw: 50000, resin component: 90% by mass) having an aromatic azomethine.
  • X-22-161B 325.5 g and propylene glycol monomethyl ether: 513.3 g were added to the above reaction solution, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and dehydrated by normal pressure concentration.
  • a modified siloxane compound (ii-1) -containing solution having an aromatic azomethine (Mw: 30000, resin component: 90% by mass) was obtained.
  • Production Example 7 Production of siloxane compound (ii-2) 2,5-dimethyl-1 was placed in a 2 liter reaction vessel having a thermometer, a stirrer, and a water quantifier with a reflux condenser and capable of heating and cooling.
  • 4-diaminobenzene 8.7 g
  • terephthalaldehyde 21.3
  • propylene glycol monomethyl ether 45.0 g
  • reacted at 115 ° C. for 4 hours heated to 130 ° C. and dehydrated by normal pressure concentration
  • An aromatic azomethine compound-containing solution (resin component: 60% by mass) was obtained.
  • X-22-161B 413.8 g and propylene glycol monomethyl ether: 645.7 g are added to the above reaction solution, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and dehydrated by normal pressure concentration.
  • a modified siloxane compound (ii-2) -containing solution having an aromatic azomethine (Mw: 25000 resin component: 90% by mass) was obtained.
  • Production Example 8 Production of Siloxane Compound (ii-3) 4,4′-Diaminobenz was placed in 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.
  • Anilide: 12.1 g, terephthalaldehyde: 17.9 g, propylene glycol monomethyl ether: 45.0 g were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and dehydrated by atmospheric concentration, and aromatic azomethine A compound-containing solution (resin component: 60% by mass) was obtained.
  • X-22-161B 342.1 g and propylene glycol monomethyl ether: 538.1 g were added to the reaction solution, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and dehydrated by concentration at normal pressure.
  • a modified siloxane compound (ii-3) -containing solution having an aromatic azomethine (Mw: 31000, resin component: 90% by mass) was obtained.
  • X-22-161B 341.6 g and propylene glycol monomethyl ether: 537.3 g were added to the above reaction solution, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and dehydrated by concentration at normal pressure.
  • a modified siloxane compound (ii-4) -containing solution having aromatic azomethine Mw: 31000, resin component: 90% by mass
  • X-22-161B 352.1 g and propylene glycol monomethyl ether: 553.1 g were added to the reaction solution, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and dehydrated by concentration at normal pressure.
  • a modified siloxane compound (ii-5) -containing solution having aromatic azomethine (Mw: 30000, resin component: 90% by mass) was obtained.
  • Production Example 12 Production of siloxane compound (iii-2) In a reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser and a heat-coolable volume of 2 liters, terephthalaldehyde: 3.0 g, X-22-161B: 27.0 g and propylene glycol monomethyl ether: 45.0 g were added and reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and dehydrated by concentration under normal pressure to remove aldehyde groups and azomethine groups. A modified siloxane compound-containing solution (60% by mass) was obtained.
  • Production Example 17 Production of Modified Imide Resin (j-2) Having Aromatic Azomethine Into 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, Modified siloxane compound (i-2) -containing solution having a group azomethine (resin component: 90% by mass): 62.5 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane: 243.8 g, propylene 443.8 g of glycol monomethyl ether was added, reacted at 115 ° C. for 4 hours, heated to 130 ° C. and concentrated at normal pressure, and a modified imide resin (j-2) -containing solution containing aromatic azomethine (resin component: 60% by mass) was obtained.
  • Production Example 25 Production of Modified Imide Resin (k-4) Having Acid Substituent and Aromatic Azomethine Reaction of 2 liters capable of heating and cooling with thermometer, stirrer, moisture meter with reflux condenser
  • a modified imide resin (k-4) -containing solution having azomethine (resin component: 60% by mass) was obtained.
  • 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.
  • the varnish was impregnated with 0.1 mm thick E glass cloth and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin 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 9 show the measurement and evaluation results of the obtained resin plates and copper-clad laminates.
  • Aromatic amine compound (A) KAYAHARD AA: 3,3′-diethyl-4,4′-diaminodiphenylmethane [manufactured by Nippon Kayaku Co., Ltd., trade name] ⁇ 4,4'-Diaminobenzanilide (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.) ⁇ 4-Aminophenyl-4'-aminobenzoate (Changzhou Yoko Pharmaceutical Co., Ltd., trade name)
  • Siloxane compound (C) X-22-161B Amino-modified siloxane at both ends (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Amine compound having acidic substituent (E) ⁇ P-Aminophenol (trade name, manufactured by Kanto Chemical Co., Inc.)
  • Tuftec H1043 Hydrogenated styrene-butadiene copolymer resin (trade name, manufactured by Asahi Kasei Chemicals Corporation)
  • Epofriend CT-310 Epoxy-modified styrene-butadiene copolymer resin (trade name, manufactured by Daicel Corporation)
  • Thermosetting resin (G) 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.)
  • G-8809L Isocyanate mask imidazole
  • TPP-MK Tetraphenylphosphonium tetra-p-tolylborate [made by Hokuko Chemical Co., Ltd., trade name]
  • solutions containing siloxane compounds (i-1) to (iii-5) in Tables 1 to 4 solutions containing modified imide resins (j-1) to (j-6) having aromatic azomethine, and acidic substituents
  • the blending amount (part by mass) of the solution containing the modified imide resins (k-1) to (k-6) having an 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 the thermosetting resin composition containing the siloxane compound of the present invention, a film with a resin obtained by coating on a support, and the prepreg are laminated.
  • the laminated board produced by this method has low cure shrinkage, low thermal expansion, copper foil adhesion, high elastic modulus, excellent dielectric properties, and highly integrated multilayer printed wiring boards for semiconductor packages and electronic devices. As useful.

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Abstract

L'invention concerne un composé siloxane contenant les structures indiquées dans la formule (1) et la formule (2). (Dans la formule (1), R1 et R2 représentent chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle comportant de 1 à 3 atomes de carbone, un groupe alkyle halogéné, un groupe thiol, un groupe acétyle, un groupe hydroxyle, un groupe acide sulfonique, un groupe sulfoalcoxyle comportant de 1 à 3 atomes de carbone, ou un groupe alcoxyle comportant de 1 à 3 atomes de carbone, et x et y représentent chacun un nombre entier de 0 à 4. A représente une liaison simple, un groupe azométhine, un groupe ester, un groupe amide, un groupe azoxy, un groupe azo, un groupe éthylène ou un groupe acétylène.) (Dans la formule (2), R3 et R4 représentent chacun un groupe alkyle, un groupe phényle ou un groupe phényle substitué, et n est un nombre entier de 1 à 100.)
PCT/JP2013/082072 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 WO2014084318A1 (fr)

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JP2014549897A JP6747655B2 (ja) 2012-11-28 2013-11-28 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
KR1020157013901A KR102166235B1 (ko) 2012-11-28 2013-11-28 실록산 화합물, 변성 이미드 수지, 열경화성 수지 조성물, 프리프레그, 수지 부착 필름, 적층판, 다층 프린트 배선판 및 반도체 패키지
CN201380061809.9A CN104812805B (zh) 2012-11-28 2013-11-28 硅氧烷化合物、改性酰亚胺树脂、热固性树脂组合物、预浸渍坯、带有树脂的膜、层叠板、多层印刷布线板及半导体封装件

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PCT/JP2013/082054 WO2014084310A1 (fr) 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

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JP2014129520A (ja) * 2012-11-28 2014-07-10 Hitachi Chemical Co Ltd アミノ変性シロキサン化合物、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
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
JPWO2014084310A1 (ja) * 2012-11-28 2017-01-05 日立化成株式会社 アミノ変性シロキサン化合物、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
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
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
JP2016190966A (ja) * 2015-03-31 2016-11-10 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、積層板及びプリント配線板及び半導体パッケージ
JP2017114964A (ja) * 2015-12-22 2017-06-29 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、多層プリント配線板及び半導体パッケージ
JP2018016793A (ja) * 2016-07-25 2018-02-01 晉一化工股▲ふん▼有限公司Ｃｈｉｎ Ｙｅｅ Ｃｈｅｍｉｃａｌ Ｉｎｄｕｓｔｒｉｅｓ Ｃｏ．， Ｌｔｄ． 熱硬化性樹脂及びその組成物、用途
JP2018070761A (ja) * 2016-10-28 2018-05-10 株式会社日本触媒 硬化性樹脂組成物、それを用いた封止材及び半導体装置
JP2021080457A (ja) * 2021-01-13 2021-05-27 昭和電工マテリアルズ株式会社 熱硬化性樹脂組成物、プリプレグ、積層板、プリント配線板及び半導体パッケージ
JP7124898B2 (ja) 2021-01-13 2022-08-24 昭和電工マテリアルズ株式会社 熱硬化性樹脂組成物、プリプレグ、積層板、プリント配線板及び半導体パッケージ
DE102022202324A1 (de) 2022-03-08 2023-09-14 Siemens Aktiengesellschaft Prepreg, Teilleiterisolation und elektrische rotierende Maschine mit Teilleiterisolation

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CN104812805A (zh) 2015-07-29
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CN106973490A (zh) 2017-07-21
JPWO2014084318A1 (ja) 2017-01-05
KR102166235B1 (ko) 2020-10-15
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