WO2018124158A1 - プリプレグ、積層板、金属箔張積層板、プリント配線板、及び多層プリント配線板 - Google Patents
プリプレグ、積層板、金属箔張積層板、プリント配線板、及び多層プリント配線板 Download PDFInfo
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- WO2018124158A1 WO2018124158A1 PCT/JP2017/046840 JP2017046840W WO2018124158A1 WO 2018124158 A1 WO2018124158 A1 WO 2018124158A1 JP 2017046840 W JP2017046840 W JP 2017046840W WO 2018124158 A1 WO2018124158 A1 WO 2018124158A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- 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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- 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
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- 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
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- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- 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
- B32B2307/206—Insulating
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/24—Thermosetting resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/02—Polyglycidyl ethers of bis-phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a prepreg, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board.
- One of the measures is to reduce the thermal expansion of the insulating layer used for the printed wiring board. This is a technique for suppressing warpage by bringing the thermal expansion coefficient of a printed wiring board close to the thermal expansion coefficient of a semiconductor element, and is currently being actively worked on (see, for example, Patent Documents 1 to 3).
- methods for suppressing the warpage of the semiconductor plastic package include increasing the rigidity of the laminated board (higher rigidity) and increasing the glass transition temperature of the laminated board (high Tg). (For example, see Patent Documents 4 and 5).
- JP 2013-216684 A Japanese Patent No. 3173332 JP 2009-035728 A JP 2013-001807 A JP2011-177892A
- the present invention does not have a clear glass transition temperature (Tg) (so-called Tg-less), and can sufficiently reduce the warpage of a printed wiring board, particularly a multilayer coreless substrate (to achieve low warpage).
- Tg-less clear glass transition temperature
- An object of the present invention is to provide a prepreg, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board.
- the present inventors have heretofore been concerned about the warping behavior of a printed wiring board for a semiconductor plastic package.
- a resin composition capable of realizing a higher elastic modulus maintenance factor has been effective, it has been found that this is not always the case.
- the inventors of the present invention have achieved that the numerical values of the physical property parameters satisfy a predetermined condition range in the physical property parameters related to specific mechanical properties in the cured product obtained by thermosetting the prepreg. It has been found that the above problems can be solved. That is, the present inventors have found that the above problems can be solved by satisfying the specific condition ranges of the storage modulus during storage and the loss elastic modulus in a cured product obtained by thermosetting the prepreg, and have completed the present invention.
- thermosetting resin (200 ° C.) / E ′ (30 ° C.) ⁇ 0.90
- E ′ (260 ° C.) / E ′ (30 ° C.) ⁇ 0.85
- E ′ (330 ° C.) / E ′ (30 ° C.) ⁇ 0.80
- E ′′ max / E ′ (30 ° C.) ⁇ 3.0%
- E ′ represents the storage elastic modulus of the cured product at the temperature shown in parentheses
- E ′′ max is the maximum value of the loss elastic modulus of the cured product in the temperature range of 30 ° C.
- E ′′ min represents the minimum value of the loss elastic modulus of the cured product in the temperature range of 30 ° C. to 330 ° C.) Satisfy the numerical range of the physical property parameters for mechanical properties expressed by Prepreg.
- the substrate is a glass substrate;
- the glass substrate is composed of one or more glass fibers selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. is there, [3] prepreg
- At least one or more layers are laminated, the first insulating layer formed of the prepreg according to any one of [1] to [4], and at least one or more layers are laminated in one side direction of the first insulating layer.
- a plurality of insulating layers comprising the second insulating layer formed of the prepreg according to any one of [1] to [4];
- a plurality of conductor layers comprising a first conductor layer disposed between each of the plurality of insulating layers; and a second conductor layer disposed on a surface of the outermost layer of the plurality of insulating layers;
- a multilayer printed wiring board having:
- a printed wiring board in particular, a prepreg, a laminated board, a metal foil-clad laminated board, a printed wiring board, and a multilayer printed wiring capable of sufficiently reducing the warpage of a multilayer coreless substrate (achieving low warpage). Board can be provided.
- FIG. 9 is a process flow diagram showing an example of a procedure for manufacturing a panel of a multilayer coreless substrate (however, the method of manufacturing the multilayer coreless substrate is not limited to this, and the same applies to FIGS. 2 to 8 below). It is a process flow figure which shows an example of the procedure which produces the panel of a multilayer coreless board
- resin solid content means a component in the resin composition excluding the solvent and filler, unless otherwise specified, and “resin solid content 100 parts by mass” means resin The total of the components excluding the solvent and the filler in the composition is 100 parts by mass.
- the prepreg of this embodiment contains a base material and a resin composition described later impregnated or coated on the base material.
- the manufacturing method of a prepreg can be performed according to a conventional method, and is not specifically limited.
- the substrate is semi-cured (B stage) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes.
- the prepreg of this embodiment can be produced.
- a cured product obtained by thermally curing it at 230 ° C. for 100 minutes is a numerical range of physical property parameters relating to mechanical properties represented by the following formulas (1) to (5). And preferably satisfies the numerical range of the physical property parameters relating to mechanical properties represented by the following formulas (1A) to (5A).
- E ′ represents the storage elastic modulus of the cured product at the temperature indicated in parentheses
- E ′′ max is the maximum value of the loss elastic modulus of the cured product in the temperature range of 30 ° C. to 330 ° C
- E ′′ min indicates the minimum loss elastic modulus of the cured product in a temperature range of 30 ° C. to 330 ° C. (E ′′ indicates the loss elastic modulus of the cured product).
- the numerical value of the physical property parameter relating to the mechanical properties of the cured product obtained by thermally curing the prepreg at 230 ° C. for 100 minutes is not necessarily limited to the above formulas (1) to (5), preferably the formula (1A) to By being within the range of (5A), the glass transition temperature (Tg) can be sufficiently increased, and the amount of warpage of the laminate, metal foil-clad laminate, printed wiring board, especially the multilayer coreless substrate itself is sufficient. It becomes possible to reduce it.
- the numerical values of the physical property parameters relating to the mechanical properties of the cured product obtained by thermosetting the prepreg at 230 ° C. for 100 minutes are the above formulas (1) to (5), preferably the formulas (1A) to (5A).
- Tg-less clear glass transition temperature
- the warpage of the printed wiring board (particularly, the multilayer coreless substrate) is sufficiently reduced (low warpage is achieved). It becomes possible. That is, satisfying the formulas (4) and (5), preferably formulas (4A) and (5A) relating to the loss elastic modulus, is synonymous with the absence of a clear glass transition temperature (Tg) (Tg-less).
- the cured product satisfies the formulas (4) and (5), preferably only the formulas (4A) and (5A), and the formulas (1) to (3) preferably do not satisfy the formulas (1A) to (3A).
- the loss elastic modulus itself is small and difficult to stretch, when it is used as a printed wiring board, the difficulty of stretching is damaged and it is difficult to achieve low warpage.
- the cured product satisfies not only formulas (4) and (5), preferably formulas (4A) and (5A), but also formulas (1) to (5), preferably formulas (1A) to (5A). Some are difficult to stretch due to the Tg-less, and tend to achieve low warpage of the printed wiring board.
- the prepreg of the present embodiment preferably satisfies the mechanical characteristics represented by the following formula (6A), more preferably satisfies the mechanical characteristics represented by the following formula (6) and / or formula (6B). is there.
- E ′ (30 ° C.) ⁇ 30 GPa (6A) E ′ (30 ° C.) ⁇ 25 GPa (6) 1 GPa ⁇ E ′ (30 ° C.) (6B)
- E ' shows the storage elastic modulus of the said hardened
- the method for measuring the mechanical properties (storage elastic modulus E ′ and loss elastic modulus E ′′) of the cured prepreg is not particularly limited, and can be measured, for example, by the following method. That is, copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 ⁇ m) is arranged on both upper and lower surfaces of one prepreg, and laminated molding (thermosetting) at a pressure of 30 kgf / cm 2 and a temperature of 230 ° C. for 100 minutes. ) To obtain a copper foil-clad laminate having a predetermined insulating layer thickness.
- the obtained copper foil-clad laminate is cut into a size of 5.0 mm ⁇ 20 mm with a dicing saw, and then the copper foil on the surface is removed by etching to obtain a measurement sample.
- the content of the resin composition (including filler (H) described later) in the prepreg is preferably 30 to 90% by volume, more preferably 35 to 85% by volume, based on the total amount of the prepreg. More preferably, it is 40 to 80% by volume. When the content of the resin composition is within the above range, the moldability tends to be further improved.
- the substrate is not particularly limited, and known materials used for various printed wiring board materials can be appropriately selected and used depending on the intended use and performance.
- the substrate include a glass substrate, an inorganic substrate other than glass, an organic substrate, and the like.
- a glass substrate is particularly preferable from the viewpoint of high rigidity and heat dimensional stability.
- Specific examples of the fibers constituting these base materials are not particularly limited.
- glass base materials for example, from E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass.
- inorganic base materials other than glass inorganic fibers other than glass, such as quartz, are mentioned.
- polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technola (registered trademark), Teijin Techno Products Ltd.
- Wholly aromatic polyamides polyesters such as 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), Zexion (registered trademark, manufactured by KB Seiren);
- organic fibers such as phenylene benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.) and polyimide.
- These base materials may be used individually by 1 type, or may use 2 or more types together.
- a shape of a base material For example, a woven fabric, a nonwoven fabric, roving, a chopped strand mat, a surfacing mat, etc. are mentioned.
- the weaving method of the woven fabric is not particularly limited, and for example, plain weave, Nanako weave, twill weave and the like are known, and can be appropriately selected from these known ones depending on the intended use and performance. .
- the thing which spread-processed these, and the glass woven fabric surface-treated with the silane coupling agent etc. are used suitably.
- the thickness and mass of the base material are not particularly limited, but usually about 0.01 to 0.3 mm is preferably used.
- the base material is preferably a glass woven fabric having a thickness of 200 ⁇ m or less and a mass of 250 g / m 2 or less, and a glass woven fabric made of glass fibers of E glass, S glass, and T glass. More preferred.
- thermosetting resin e.g. a thermosetting resin and a filler
- a maleimide compound (A) e.g., a maleimide compound (A), an allyl group containing compound (B), and And an epoxy resin (C) comprising a bisphenol A type structural unit and a hydrocarbon-based structural unit, and relates to the mechanical properties represented by the above formulas (1) to (5), preferably represented by the formulas (1A) to (5A).
- a composition capable of realizing a numerical range of physical property parameters can be appropriately selected.
- Laminated boards, metal foil-clad laminated boards, printed wiring boards, especially multilayer coreless boards using prepregs containing such resin compositions and base materials, tend to be able to sufficiently reduce the amount of warping due to heating such as reflow It is in.
- the maleimide compound (A) is not particularly limited as long as it has one or more maleimide groups in the molecule.
- R 5 each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
- n1 represents an integer greater than or equal to 1 , Preferably it is an integer of 10 or less, More preferably, it is an integer of 7 or less.
- the content of the maleimide compound (A) is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and further preferably 25 to 50 parts by mass with respect to 100 parts by mass of the resin solid content. Yes, particularly preferably 35 to 50 parts by mass, and still more preferably 35 to 45 parts by mass.
- content of a maleimide compound (A) exists in the said range, it exists in the tendency for the thermal expansion coefficient of the hardened
- the allyl group-containing compound (B) is not particularly limited as long as it is a compound having one or more allyl groups in the molecule, but may further have a reactive functional group other than the allyl group.
- the reactive functional group other than the allyl group is not particularly limited, and examples thereof include a cyanate group (cyanate ester group), a hydroxyl group, an epoxy group, an amine group, an isocyanate group, a glycidyl group, and a phosphate group.
- At least one selected from the group consisting of a cyanate group (cyanate group), a hydroxyl group, and an epoxy group is preferable, and a cyanate group (cyanate group) is more preferable.
- a cyanate group (cyanate group) is more preferable.
- the allyl group-containing compound (B) one type may be used alone, or two or more types may be used in combination.
- the reactive functional groups other than the allyl group may be the same or different.
- the allyl group-containing compound (B) preferably contains an allyl group-containing compound whose reactive functional group is a cyanate group and an allyl group-containing compound whose reactive functional group is an epoxy group.
- the allyl group-containing compound (B) it is preferable to use an allyl group-containing compound having a reactive functional group other than an allyl group and / or an alkenyl-substituted nadiimide compound (E) described later.
- an allyl group-containing compound (B) By using such an allyl group-containing compound (B), the glass transition temperature (Tg), the thermal expansion coefficient, and the thermal conductivity tend to be improved.
- allyl group-containing compound (B) it is particularly preferable to use an allylphenol derivative (D) and / or an alkenyl-substituted nadiimide compound (E) described later.
- Tg glass transition temperature
- Tg thermal expansion coefficient
- T conductivity tend to be further improved.
- the content of the allyl group-containing compound (B) is preferably 1 to 90 parts by weight, more preferably 10 to 80 parts by weight, and still more preferably 20 to 75 parts by weight with respect to 100 parts by weight of the resin solid content. Part, particularly preferably 25 to 40 parts by weight.
- the content of the allyl group-containing compound (B) is within the above range, the flexibility, bending strength, bending elastic modulus, glass transition temperature (Tg), thermal expansion coefficient, thermal conductivity, and There exists a tendency for copper foil peel strength to improve more.
- the allylphenol derivative (D) is not particularly limited as long as it is a compound in which an allyl group and a phenolic hydroxyl group are directly bonded to an aromatic ring, and a derivative thereof.
- bisphenol in which an aromatic ring hydrogen atom is substituted with an allyl group A modified bisphenol compound in which the hydrogen atom of the aromatic ring is substituted with an allyl group, and the phenolic hydroxyl group is modified with a reactive functional group other than the hydroxyl group in the reactive functional group other than the above-mentioned allyl group
- Specific examples include compounds represented by the following formula (8), and more specifically, diallyl bisphenol A, a cyanate ester compound of diallyl bisphenol A, and diallyl bisphenol A type epoxy.
- each Ra independently represents a reactive substituent other than an allyl group.
- the compound represented by the formula (8) is not particularly limited, and examples thereof include a compound represented by the following formula (8a) and / or a compound represented by the following formula (8b).
- a compound represented by the following formula (8a) and / or a compound represented by the following formula (8b) By using such an allylphenol derivative (D), bending strength, bending elastic modulus, glass transition temperature (Tg), thermal expansion coefficient, thermal conductivity, and copper foil peel strength tend to be further improved.
- bisphenol A bisphenol A
- bisphenol AP bisphenol AF
- bisphenol B bisphenol BP
- bisphenol C bisphenol C
- bisphenol E bisphenol F
- bisphenol G bisphenol M
- bisphenol S bisphenol P Bisphenol PH
- bisphenol TMC bisphenol TMC
- bisphenol Z bisphenol Z.
- bisphenol A is preferred.
- the number of allyl groups in one molecule of the allylphenol derivative (D) is preferably 1 to 5, more preferably 2 to 4, and still more preferably 2.
- the bending strength, bending elastic modulus, copper foil peel strength, glass transition temperature (Tg) are further improved, and the thermal expansion coefficient is increased. It tends to be low and excellent in thermal conductivity.
- the number of reactive functional groups other than the allyl group in one molecule of the allylphenol derivative (D) is preferably 1 to 5, more preferably 2 to 4, and still more preferably 2.
- the bending strength, the bending elastic modulus, the copper foil peel strength, and the glass transition temperature (Tg) are further improved.
- the coefficient of thermal expansion is low and the thermal conductivity tends to be excellent.
- the preferable range of the content of the allylphenol derivative (D) conforms to the content of the allyl group-containing compound (B) described above.
- alkenyl-substituted nadiimide compound (E) is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadiimide groups in the molecule. Among these, the compound represented by the following formula (9) is preferable.
- each R 1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 2 represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, or a naphthylene. Or a group represented by the following formula (10) or (11).
- R 3 represents a methylene group, an isopropylidene group, or a substituent represented by CO, O, S, or SO 2 .
- each R 4 independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.
- the alkenyl-substituted nadiimide compound (E) is more preferably a compound represented by the following formula (12) and / or (13).
- alkenyl-substituted nadiimide compound (E) a commercially available product can be used.
- examples of commercially available products include, but are not limited to, for example, BANI-M (manufactured by Maruzen Petrochemical Co., Ltd., compound represented by the formula (12)), BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.) A compound represented by the formula (13)). These may be used alone or in combination of two or more.
- the content of the alkenyl-substituted nadiimide compound (E) is preferably 20 to 50 parts by mass, more preferably 20 to 35 parts by mass with respect to 100 parts by mass of the resin solid content. More preferably, the total content of the allylphenol derivative (D) and the alkenyl-substituted nadiimide compound (E) is preferably 20 to 50 parts by mass with respect to 100 parts by mass of the resin solid content, and more preferably Is 35 to 45 parts by mass.
- the content of the alkenyl-substituted nadiimide compound (E) is within the above range, the thermal expansion coefficient of the obtained cured product is further decreased, and the heat resistance tends to be further improved.
- Epoxy resin consisting of bisphenol A structural unit and hydrocarbon-based structural unit (C) The epoxy resin (C) composed of a bisphenol A structural unit and a hydrocarbon structural unit is a compound having one or more bisphenol A structural units and one or more hydrocarbon structural units in the molecule. There is no particular limitation. Among these, the compound represented by the following formula (14) is preferable.
- an epoxy resin (C) composed of such a bisphenol A structural unit and a hydrocarbon-based structural unit the storage elastic modulus E ′ during heating of the resulting cured product tends to be a value suitable for warpage suppression. is there.
- R 1 and R 2 each independently represent a hydrogen atom or a methyl group
- R 3 to R 6 each independently represent a hydrogen atom, a methyl group, or a chlorine atom.
- X represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, or a tri (propyleneoxy) propyl group.
- Group represents an alkylene group having 2 to 15 carbon atoms
- n represents a natural number.
- epoxy resin (C) comprising the above-described bisphenol A structural unit and hydrocarbon structural unit can be used.
- Commercially available products are not particularly limited.
- EPICLON EXA-4850-150 (a compound having a structure represented by the formula (14) manufactured by DIC Corporation), EPICLON EXA-4816 (DIC Corporation) And a compound in which X in formula (14) is an ethylene group). These may be used alone or in combination of two or more.
- the content of the epoxy resin (C) composed of a bisphenol A type structural unit and a hydrocarbon-based structural unit is preferably 5 to 25 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the resin solid content. Part, more preferably 10 to 20 parts by weight.
- the storage elastic modulus E ′ during heating of the obtained cured product is a value suitable for warpage suppression. It tends to be.
- the resin composition of this embodiment may further contain a cyanate ester compound (F).
- the cyanate ester compound (F) is not particularly limited as long as it is a cyanate ester compound other than the above-mentioned allylphenol derivative (D).
- each R 6 independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
- n 2 represents an integer of 1 or more. The upper limit value of n 2 is usually 10, and preferably 6.
- R 7 each independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferred.
- n 3 represents an integer of 1 or more. upper limit of n 3 is usually a 10, preferably a 7.
- the cyanate ester compound (F) is composed of a naphthol aralkyl-type cyanate ester represented by the formula (15), a novolak-type cyanate ester represented by the formula (16), and a biphenyl aralkyl-type cyanate ester. It is preferable to include at least one selected from the group, and at least one selected from the group consisting of a naphthol aralkyl-type cyanate ester represented by the formula (15) and a novolak-type cyanate ester represented by the formula (16) It is more preferable to contain.
- a cyanate ester compound (F) By using such a cyanate ester compound (F), a cured product that is superior in flame retardancy, has higher curability, and has a lower thermal expansion coefficient tends to be obtained.
- the production method of these cyanate ester compounds (F) is not particularly limited, and a known method can be used as a synthesis method of the cyanate ester compounds.
- the known method is not particularly limited.
- a method of reacting a phenol resin and cyanogen halide in an inert organic solvent in the presence of a basic compound, a salt of the phenol resin and the basic compound, water examples thereof include a method of forming in a solution to be contained, and then causing the obtained salt and cyanogen halide to undergo a two-phase interface reaction.
- the phenol resin used as a raw material for these cyanate ester compounds (F) is not particularly limited, and examples thereof include naphthol aralkyl type phenol resins, novolak type phenol resins, and biphenyl aralkyl type phenol resins represented by the following formula (17). Can be mentioned.
- R 8 each independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable.
- n 4 represents an integer of 1 or more. The upper limit value of n 4 is usually 10 and preferably 6.
- the naphthol aralkyl type phenol resin represented by the formula (17) can be obtained by condensing a naphthol aralkyl resin and cyanic acid.
- the naphthol aralkyl type phenol resin is not particularly limited, and examples thereof include naphthols such as ⁇ -naphthol and ⁇ -naphthol, p-xylylene glycol, ⁇ , ⁇ '-dimethoxy-p-xylene, and 1,4- Examples thereof include those obtained by reaction with benzenes such as di (2-hydroxy-2-propyl) benzene.
- the naphthol aralkyl cyanate ester can be selected from those obtained by condensing the naphthol aralkyl resin obtained as described above and cyanic acid.
- the content of the cyanate ester compound (F) is preferably 0.5 to 45 parts by weight, more preferably 10 to 45 parts by weight, and more preferably 15 to 45 parts by weight with respect to 100 parts by weight of the resin solid content.
- the amount is 45 parts by mass, more preferably 20 to 35 parts by mass.
- the resin composition of this embodiment may further contain an epoxy compound (G) other than the epoxy resin (C) composed of the above-described bisphenol A-type structural unit and hydrocarbon-based structural unit.
- the epoxy compound (G) is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule other than the epoxy resin (C).
- bisphenol A type epoxy resin bisphenol E type Epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, 3 Functional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, glycidyl ester type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, aralkyl novolak type epoxy resin Resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, a polyol type epoxy resin, isocyanurate ring-containing epoxy resin, or these halides and the like.
- the epoxy compound (G) is other than the allyl group-containing compound (B) having an epoxy group.
- the content of the epoxy compound (G) is preferably 2.5 to 30 parts by mass, more preferably 5.0 to 27.5 parts by mass, further preferably 100 parts by mass of the resin solid content. 7.5 to 25 parts by mass.
- content of an epoxy compound (G) exists in the said range, it exists in the tendency for the softness
- the resin composition of this embodiment may further contain a filler (H).
- a filler H
- an inorganic filler and an organic filler are mentioned, It is preferable to contain the inorganic filler among both, and an organic filler is used with an inorganic filler. It is preferable.
- the inorganic filler examples include, but are not limited to, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, magnesium oxide, Metal oxides such as zirconium oxide; metal nitrides such as boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride; metal sulfates such as barium sulfate; aluminum hydroxide, aluminum hydroxide heat-treated products (heating aluminum hydroxide) Treated and reduced in part of crystal water), metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc compounds such as zinc borate and zinc stannate; alumina Clay, kaolin, talc, calcined clay, calcined kaolin,
- the organic filler is not particularly limited, and examples thereof include rubber powders such as styrene type powder, butadiene type powder, and acrylic type powder; core shell type rubber powder; silicone resin powder; silicone rubber powder; It is done.
- a filler (H) may be used individually by 1 type, or may use 2 or more types together.
- the inorganic filler may contain at least one selected from the group consisting of silica, alumina, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride.
- it contains at least one selected from the group consisting of silica, alumina, and boehmite.
- the content of the filler (H) (particularly inorganic filler) is preferably 100 to 700 parts by weight, more preferably 100 to 450 parts by weight, and still more preferably 100 parts by weight of the resin solid content. 120 to 250 parts by mass.
- the content of the filler (H) is within the above range, the resulting cured product tends to have higher rigidity and lower warpage.
- the resin composition of this embodiment may further contain a silane coupling agent and a wetting and dispersing agent.
- a silane coupling agent and a wetting and dispersing agent By including a silane coupling agent and a wetting and dispersing agent, the dispersibility of the filler (H), the resin component, the filler (H), and the adhesive strength of the substrate described later tend to be further improved.
- the silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances.
- ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ Aminosilane compounds such as aminopropyltrimethoxysilane; epoxysilane compounds such as ⁇ -glycidoxypropyltrimethoxysilane; acrylic silane compounds such as ⁇ -acryloxypropyltrimethoxysilane; N- ⁇ - (N— Cationic silane compounds such as vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride; phenylsilane compounds and the like.
- a silane coupling agent may be used individually by 1 type, or may use 2 or more types together.
- the wetting dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints.
- the resin composition of this embodiment may be an allyl group-containing compound (hereinafter also referred to as “other allyl group-containing compound”), phenol resin, oxetane resin, other than the above-described allyl group-containing compound (B).
- other allyl group-containing compound phenol resin, oxetane resin, other than the above-described allyl group-containing compound (B).
- You may further contain 1 type, or 2 or more types selected from the group which consists of a benzoxazine compound and the compound which has a polymerizable unsaturated group.
- the copper foil peel strength, bending strength, bending elastic modulus and the like of the obtained cured product tend to be further improved.
- allyl group-containing compounds examples include, but are not limited to, allyl chloride, allyl acetate, allyl ether, propylene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, diallyl maleate, and the like. Can be mentioned.
- the content of the other allyl group-containing compound is preferably 0 to 50 parts by mass, more preferably 10 to 45 parts by mass, and more preferably 15 to 45 parts by mass with respect to 100 parts by mass of the resin solid content. More preferably, it is 20 to 35 parts by mass.
- the content of the other allyl group-containing compound is within the above range, the bending strength, bending elastic modulus, heat resistance, and chemical resistance of the obtained cured product tend to be further improved.
- phenol resin generally known resins can be used as long as they are phenol resins having two or more hydroxy groups in one molecule, and the kind thereof is not particularly limited. Specific examples thereof include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type.
- the content of the phenol resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass with respect to 100 parts by mass of the resin solid content.
- the content of the phenol resin is within the above range, the obtained cured product tends to be more excellent in adhesiveness, flexibility, and the like.
- oxetane resin As the oxetane resin, generally known oxetane resins can be used, and the kind thereof is not particularly limited. Specific examples thereof include alkyloxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3 ′ -Di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name, manufactured by Toagosei), OXT-121 (produced by Toagosei) Product name). These oxetane resins can be used alone or in combination of two or more. By including such an o
- the content of the oxetane resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass with respect to 100 parts by mass of the resin solid content.
- the content of the oxetane resin is within the above range, the obtained cured product tends to be more excellent in adhesion and flexibility.
- benzoxazine compound As the benzoxazine compound, generally known compounds can be used as long as they have two or more dihydrobenzoxazine rings in one molecule, and the kind thereof is not particularly limited. Specific examples include bisphenol A type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical) bisphenol F type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical), bisphenol S type benzoxazine BS-BXZ (product manufactured by Konishi Chemical). Name). These benzoxazine compounds can be used alone or in combination. By including such a benzoxazine compound, the obtained cured product tends to be more excellent in flame retardancy, heat resistance, low water absorption, low dielectric constant, and the like.
- the content of the benzoxazine compound is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass with respect to 100 parts by mass of the resin solid content.
- the content of the benzoxazine compound is within the above range, the resulting cured product tends to be more excellent in heat resistance and the like.
- Compound having a polymerizable unsaturated group As the compound having a polymerizable unsaturated group, generally known compounds can be used, and the kind thereof is not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene and divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di ( Mono- or polyhydric alcohol (meth) such as (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Acrylates; Epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate and bisphenol F type
- the content of the compound having a polymerizable unsaturated group is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 3 to 100 parts by mass with respect to 100 parts by mass of the resin solid content. 80 parts by mass.
- the content of the polymerizable unsaturated group-containing compound is within the above range, the cured product obtained tends to be more excellent in heat resistance, toughness, and the like.
- the resin composition of this embodiment may further contain a curing accelerator.
- the curing accelerator is not particularly limited, and examples thereof include imidazoles such as triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-diperphthalate, and the like.
- Organic peroxides azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-dimethylpyridine, 2-N-ethylanilino Tertiary amines such as ethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenol, xylenol, cresol, resorcin, cateco Phenols such as lead; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; these organic metal salts Inorganic metal salts
- the resin composition of this embodiment may further contain a solvent.
- a solvent By including the solvent, the viscosity at the time of preparing the resin composition is lowered, the handling property is further improved, and the impregnation property to the base material described later tends to be further improved.
- the solvent is not particularly limited as long as it can dissolve a part or all of the resin component in the resin composition.
- ketones such as acetone, methyl ethyl ketone, and methyl cellosolve
- aromatics such as toluene and xylene Group hydrocarbons
- amides such as dimethylformamide
- a solvent may be used individually by 1 type, or may use 2 or more types together.
- the manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of mix
- known processes such as stirring, mixing, and kneading can be performed.
- the dispersibility of the filler (H) with respect to the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank provided with a stirrer having an appropriate stirring ability.
- the above stirring, mixing, and kneading treatment can be appropriately performed using, for example, a known device such as a ball mill or a bead mill for mixing, or a revolving or rotating mixing device.
- an organic solvent can be used as necessary.
- the kind of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition. Specific examples thereof are as described above.
- the prepreg satisfying the numerical range of the physical property parameters related to the mechanical properties represented by the formulas (1) to (5), preferably the formulas (1A) to (5A) of the present embodiment is an insulating layer, a laminate, a metal foil-clad laminate It can be suitably used as a printed wiring board or a multilayer printed wiring board.
- a laminated board, a metal foil-clad laminated board, and a printed wiring board (including a multilayer printed wiring board) will be described.
- the laminated board of this embodiment has the prepreg of this embodiment laminated at least one or more.
- the metal foil-clad laminate of the present embodiment includes the laminate of the embodiment (that is, the prepreg of the embodiment laminated at least one sheet) and the metal foil disposed on one or both sides of the laminate. (Conductor layer).
- the laminate and the metal foil-clad laminate of the embodiment do not have a clear glass transition temperature (Tg-less) and tend to sufficiently reduce warpage (achieve low warpage).
- the conductor layer can be a metal foil such as copper or aluminum.
- the metal foil used here will not be specifically limited if it is used for printed wiring board material, Well-known copper foils, such as a rolled copper foil and an electrolytic copper foil, are preferable.
- the thickness of the conductor layer is not particularly limited, but is preferably 1 to 70 ⁇ m, more preferably 1.5 to 35 ⁇ m.
- the forming method and forming conditions of the laminated plate and the metal foil-clad laminated plate are not particularly limited, and general methods and conditions of a laminated plate for a printed wiring board and a multilayer plate can be applied.
- a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used at the time of shaping
- the temperature is generally 100 to 300 ° C.
- the pressure is 2 to 100 kgf / cm 2
- the heating time is generally 0.05 to 5 hours. It is.
- post-curing can be performed at a temperature of 150 to 300 ° C., if necessary.
- a temperature of 200 ° C. to 250 ° C. a pressure of 10 to 40 kgf / cm 2 , a heating time of 80 minutes to 130 minutes is preferable, and a temperature of 215 ° C. to More preferably, the temperature is 235 ° C., the pressure is 25 to 35 kgf / cm 2 , and the heating time is 90 to 120 minutes.
- a multilayer board can be formed by laminating and combining the above-described prepreg and a separately prepared wiring board for an inner layer.
- the printed wiring board of this embodiment is a printed wiring board having an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes the prepreg.
- the metal foil-clad laminate of this embodiment does not have a clear glass transition temperature (Tg-less) and tends to sufficiently reduce warpage (achieve low warpage). It can be used particularly effectively as a printed wiring board that requires such performance.
- the printed wiring board of the present embodiment can be manufactured by the following method, for example.
- the metal foil-clad laminate such as a copper-clad laminate
- An inner layer circuit is formed by etching the surface of the metal foil-clad laminate to produce an inner layer substrate.
- the inner layer circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, then the required number of the above-mentioned prepregs are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is further formed outside thereof.
- a multilayer laminate is produced in which an insulating layer made of a cured material of the base material and the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit.
- the method of lamination molding and the molding conditions thereof are the same as those of the above-described laminate or metal foil-clad laminate.
- desmear treatment is performed to remove smears, which are resin residues derived from the resin component contained in the cured product layer. .
- a plated metal film is formed on the wall surface of this hole to connect the inner layer circuit and the metal foil for the outer layer circuit, and the outer layer circuit is formed by etching the metal foil for the outer layer circuit to produce a printed wiring board. Is done.
- the above-described prepreg (the base material and the above-described resin composition attached thereto) constitutes the insulating layer.
- a printed wiring board may be produced by forming a conductor layer serving as a circuit on the prepreg. At this time, a method of electroless plating can be used for forming the conductor layer.
- the printed wiring board of the present embodiment includes a first insulating layer (1) formed of the above-described prepreg that is laminated at least one sheet, and the first insulating layer (1 ) And a plurality of insulating layers (1, 2) formed of the second insulating layer (2) formed of the above-mentioned prepreg laminated in at least one sheet in the one-side direction (the lower surface direction in the figure).
- a normal laminated board for example, it is performed to form a multilayer printed wiring board by laminating another prepreg on both sides of a prepreg that is one core substrate.
- the prepreg of the embodiment is a coreless type manufactured by stacking another prepreg that forms the second insulating layer (2) only in one direction of one prepreg that forms the first insulating layer (1). It was confirmed that the present invention is particularly effective for multilayer printed wiring boards (multilayer coreless substrates).
- the prepreg and the resin composition of the present embodiment can effectively reduce the amount of warping when used in a printed wiring board, and are not particularly limited. This is particularly effective for a coreless substrate. That is, a normal printed wiring board generally has a symmetrical structure on both sides, and thus tends to be warped. On the other hand, a multilayer coreless board tends to have a double-sided asymmetric structure, and thus is more likely to warp than a normal printed wiring board. There is a tendency. Therefore, by using the prepreg and the resin composition of the present embodiment, it is possible to particularly effectively reduce the amount of warping of the multilayer coreless substrate that has been prone to warping.
- FIG. 9 a configuration in which two second insulating layers (2) are stacked on one first insulating layer (1) (that is, a configuration in which a plurality of insulating layers are three layers) is provided.
- the number of the second insulating layer (2) may be one or two or more. Therefore, the first conductor layer (3) may be one layer or two or more layers.
- the prepreg satisfying the numerical range of the physical property parameters related to the mechanical properties (storage elastic modulus and loss elastic modulus) represented by the above formulas (1) to (5), preferably the formulas (1A) to (5A) is as described above.
- the printed wiring board of this embodiment having a configuration, particularly a multilayer coreless substrate there is no clear glass transition temperature (Tg-less), and warpage can be sufficiently reduced (low warpage can be achieved). It can be used particularly effectively as a printed wiring board and a multilayer coreless substrate.
- Example 1 Maleimide compound (A) (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd., maleimide equivalent 186 g / eq.) 45 parts by mass, allyl group-containing compound (B) and alkenyl-substituted nadiimide compound (E) (BANI-M, Maruzen Petrochemical Co., Ltd., allyl equivalent: 286 g / eq.) 34 parts by mass, epoxy resin (C) (EPICLON EXA-4850-150, made of bisphenol A structural unit and hydrocarbon structural unit, manufactured by DIC Corporation) , Epoxy equivalent: 450 g / eq.) 10 parts by mass, 1 part by mass of ⁇ -naphthol aralkyl-type cyanate ester compound (SN495VCN, cyanate equivalent: 261 g / eq.) Of Synthesis Example 1 which is a cyanate ester compound (F),
- This varnish was impregnated and applied to E glass woven fabric (manufactured by Arisawa Manufacturing Co., Ltd., IPC # 2116) and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 57 vol%.
- Example 2 The varnish obtained in Example 1 was impregnated and applied to an E glass woven fabric (manufactured by Unitika Ltd., IPC # 1030), heated and dried at 160 ° C. for 3 minutes, and a prepreg having a resin composition content of 73% by volume was obtained. Obtained.
- Example 3 From 43 parts by mass of maleimide compound (A) (BMI-2300), 32 parts by mass of allyl group-containing compound (B) and alkenyl-substituted nadiimide compound (E) (BANI-M), bisphenol A structural unit and hydrocarbon-based structural unit 10 parts by mass of epoxy resin (C) (EPICLON EXA-4816, manufactured by DIC Corporation, epoxy equivalent: 403 g / eq.), ⁇ -naphthol aralkyl type cyanic acid of Synthesis Example 1 which is a cyanate ester compound (F) 5 parts by mass of an ester compound (SN495VCN), 10 parts by mass of an epoxy compound (G) (NC-3000FH, Nippon Kayaku Co., Ltd., epoxy equivalent: 320 g / eq.), Slurry silica (SC) as a filler (H) -2050MB) 100 parts by mass, slurry silica (SC-5050MOB, Ad
- Example 4 The varnish obtained in Example 3 was impregnated and applied to an E glass woven fabric (IPC # 1030) and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 73 vol%.
- Comparative Example 2 The varnish obtained in Comparative Example 1 was impregnated and applied to E glass woven fabric (IPC # 1030) and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 73 vol%.
- Comparative Example 4 The varnish obtained in Comparative Example 3 was impregnated and applied to an E glass woven fabric (IPC # 1030) and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 73 vol%.
- Comparative Example 6 The varnish obtained in Comparative Example 5 was impregnated and applied to an E glass woven fabric (IPC # 1030) and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 73 vol%.
- a 20 mm ⁇ 200 mm strip-shaped plate is cut out from the obtained laminated plate, and the maximum value of the warpage at both ends in the longitudinal direction is measured with a metal rule with the surface of the prepreg laminated on the second sheet facing up.
- the average value was defined as the “warp amount” by the bimetal method.
- carrier copper foil surfaces of an ultrathin copper foil with carrier (b1) (MT18Ex, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 5 ⁇ m) are provided on both sides of the prepreg to be the support (a).
- the prepreg (c1) obtained in Examples 1 to 4 and Comparative Examples 1 to 6 was further arranged on the copper foil (d) (3EC-VLP, Mitsui Mining & Mining).
- a copper foil-clad laminate shown in FIG. 2 was obtained by performing laminate molding at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes.
- the copper foil (d) of the obtained copper foil-clad laminate shown in FIG. 2 was etched into a predetermined wiring pattern as shown in FIG. 3, for example, to form a conductor layer (d ′).
- the prepregs (c2) obtained in Examples 1 to 4 and Comparative Examples 1 to 6 are placed on the laminate shown in FIG. 3 on which the conductor layer (d ′) is formed.
- an ultrathin copper foil with carrier (b2) (MT18Ex, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 5 ⁇ m) is further placed thereon, and laminated molding is performed at a pressure of 30 kgf / cm 2 and a temperature of 230 ° C. for 120 minutes.
- a copper foil clad laminate shown in FIG. 5 was obtained.
- the carrier copper foil and the ultrathin copper foil of the carrier-attached ultrathin copper foil (b1) placed on the support (a) (cured support prepreg) are peeled off.
- the two laminated plates were peeled from the support (a), and the carrier copper foil was further peeled from the ultrathin copper foil with carrier (b2) on the upper portion of each laminated plate.
- processing by a laser processing machine was performed on the upper and lower ultrathin copper foils of each obtained laminate, and a predetermined via (v) was formed by chemical copper plating as shown in FIG. Then, for example, as shown in FIG.
- a conductor layer was formed by etching into a predetermined wiring pattern to obtain a panel (size: 500 mm ⁇ 400 mm) of a multilayer coreless substrate. Then, the amount of warpage at a total of eight locations of the four corners and the center of the four sides of the obtained panel was measured with a metal ruler, and the average value was defined as the “warpage amount” of the panel of the multilayer coreless substrate.
- Copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 ⁇ m) was placed on both the upper and lower surfaces of one prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 6, and the pressure was 30 kgf / cm 2. Then, lamination molding was performed at a temperature of 220 ° C. for 120 minutes to obtain a copper foil-clad laminate. Next, the obtained copper foil-clad laminate was drilled at nine points uniformly in a grid pattern with a drill, and then the copper foil was removed.
- the distance between the holes in the laminate from which the copper foil was removed was measured (distance A).
- the laminate was subjected to a reflow treatment at a maximum temperature of 260 ° C. using a salamander reflow apparatus. Thereafter, the distance between the holes in the laminate was measured again (distance b).
- the measured distance A and distance B were substituted into the following formula (I) to determine the dimensional change rate of the substrate in the reflow process, and the value was used as the substrate shrinkage rate before and after the reflow process. ((Distance A)-(Distance B)) / Distance A x 100 ...
- Formula (I) ((Distance A)-(Distance B)) / Distance A x 100 ...
- the prepreg of this embodiment has industrial applicability as a material for a laminated board, a metal foil-clad laminated board, a printed wiring board, or a multilayer printed wiring board.
- This application is based on Japanese Patent Application No. 2016-255270 filed on Dec. 28, 2016, and the description is incorporated herein.
Abstract
Description
〔1〕
熱硬化性樹脂と、
充填材と、
基材と、
を含有するプリプレグであって、
該プリプレグを230℃及び100分の条件で熱硬化させて得られる硬化物が、下記式(1)~(5);
E’(200℃)/E’(30℃)≦0.90 …(1)
E’(260℃)/E’(30℃)≦0.85 …(2)
E’(330℃)/E’(30℃)≦0.80 …(3)
E’’max/E’(30℃)≦3.0% …(4)
E’’min/E’(30℃)≧0.5% …(5)
(各式中、E’は、括弧内に示す温度における前記硬化物の貯蔵弾性率を示し、E’’maxは、30℃から330℃の温度範囲における前記硬化物の損失弾性率の最大値を示し、E’’minは、30℃から330℃の温度範囲における前記硬化物の損失弾性率の最小値を示す。)
で表される機械特性に関する物性パラメータの数値範囲を満たす、
プリプレグ。
下記式(6A);
E’(30℃)≦30GPa …(6A)
(式中、E’は、括弧内に示す温度における前記硬化物の貯蔵弾性率を示す。)
で表される機械特性を更に満たす、
〔1〕に記載のプリプレグ。
前記基材が、ガラス基材である、
〔1〕又は〔2〕に記載のプリプレグ。
前記ガラス基材が、Eガラス、Dガラス、Sガラス、Tガラス、Qガラス、Lガラス、NEガラス、及びHMEガラスからなる群より選択される1種以上のガラスの繊維で構成されたものである、
〔3〕に記載のプリプレグ
少なくとも1枚以上積層された〔1〕~〔4〕のいずれかに記載のプリプレグを有する、
積層板。
少なくとも1枚以上積層された〔1〕~〔4〕のいずれかに記載のプリプレグと、
該プリプレグの片面又は両面に配された金属箔と、
を有する金属箔張積層板。
〔1〕~〔4〕のいずれかに記載のプリプレグで形成された絶縁層と、
該絶縁層の表面に形成された導体層と、
を有するプリント配線板。
少なくとも1枚以上積層された〔1〕~〔4〕のいずれかに記載のプリプレグで形成された第1の絶縁層、及び、前記第1の絶縁層の片面方向に少なくとも1枚以上積層された〔1〕~〔4〕のいずれかに記載のプリプレグで形成された第2の絶縁層からなる複数の絶縁層と、
前記複数の絶縁層の各々の間に配された第1の導体層、及び、前記複数の絶縁層の最外層の表面に配された第2の導体層からなる複数の導体層と、
を有する多層プリント配線板。
本実施形態のプリプレグは、基材と、該基材に含浸又は塗布された後述する樹脂組成物と、を含有する。プリプレグの製造方法は、常法にしたがって行うことができ、特に限定されない。例えば、本実施形態における樹脂組成物を基材に含浸又は塗布させた後、100~200℃の乾燥機中で1~30分加熱する等して半硬化(Bステ-ジ化)させることで、本実施形態のプリプレグを作製することができる。
E’(260℃)/E’(30℃)≦0.85 …(2)
E’(330℃)/E’(30℃)≦0.80 …(3)
E’’max/E’(30℃)≦3.0% …(4)
E’’min/E’(30℃)≧0.5% …(5)
0.40≦E’(200℃)/E’(30℃)≦0.90 …(1A)
0.40≦E’(260℃)/E’(30℃)≦0.85 …(2A)
0.40≦E’(330℃)/E’(30℃)≦0.80 …(3A)
0.5%≦E’’max/E’(30℃)≦3.0% …(4A)
3.0%≧E’’min/E’(30℃)≧0.5% …(5A)
E’(30℃)≦25GPa …(6)
1GPa≦E’(30℃) …(6B)
ここで、式中、E’は、括弧内に示す温度における前記硬化物の貯蔵弾性率を示す。すなわち、本実施形態のプリプレグは、そのE’(30℃)が30GPa以下であると好ましく、25GPa以下であるとより好ましい。また、そのE’(30℃)の下限値は、特に限定されるものではないが、1GPa以上であることが好ましい。
上記プリプレグに用いられる本実施形態の樹脂組成物は、熱硬化性樹脂及び充填材を含むものであれば、特に限定されず、例えば、マレイミド化合物(A)と、アリル基含有化合物(B)と、ビスフェノールA型構造単位と炭化水素系構造単位からなるエポキシ樹脂(C)とを含有し、上記式(1)~(5)好ましくは式(1A)~(5A)で表される機械特性に関する物性パラメータの数値範囲を実現することができる組成を適宜選択することができる。そのような樹脂組成物と基材とを含有するプリプレグを用いた、積層板、金属箔張り積層板、プリント配線板、特に多層コアレス基板が、リフロー等の加熱による反り量を十分に低減できる傾向にある。
マレイミド化合物(A)としては、分子中に1個以上のマレイミド基を有する化合物であれば特に限定されないが、例えば、N-フェニルマレイミド、N-ヒドロキシフェニルマレイミド、ビス(4-マレイミドフェニル)メタン、2,2-ビス{4-(4-マレイミドフェノキシ)-フェニル}プロパン、ビス(3,5-ジメチル-4-マレイミドフェニル)メタン、ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン、ビス(3,5-ジエチル-4-マレイミドフェニル)メタン、下記式(7)で表されるマレイミド化合物、これらマレイミド化合物のプレポリマー、若しくはマレイミド化合物とアミン化合物のプレポリマーが挙げられる。このなかでも、ビス(4-マレイミドフェニル)メタン、2,2-ビス{4-(4-マレイミドフェノキシ)-フェニル}プロパン、ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン、及び下記式(7)で表されるマレイミド化合物からなる群より選択される少なくとも1種が好ましく、特に下記式(7)で表されるマレイミド化合物が好ましい。このようなマレイミド化合物(A)を含むことにより、得られる硬化物の熱膨張率がより低下し、耐熱性、ガラス転移温度(Tg)がより向上する傾向にある。
アリル基含有化合物(B)は、分子中に1個以上のアリル基を有する化合物であれば特に限定されないが、アリル基以外の反応性官能基を更に有していてもよい。アリル基以外の反応性官能基としては、特に限定されないが、例えば、シアネート基(シアン酸エステル基)、ヒドロキシル基、エポキシ基、アミン基、イソシアネート基、グリシジル基、及びリン酸基が挙げられる。このなかでも、シアネート基(シアン酸エステル基)、ヒドロキシル基、及びエポキシ基からなる群より選択される少なくとも1つが好ましく、シアネート基(シアン酸エステル基)がより好ましい。ヒドロキシル基、シアネート基(シアン酸エステル基)、エポキシ基を有することにより、高い曲げ強度及び曲げ弾性率、低い誘電率、高いガラス転移温度(高Tg)を有し、熱膨張係数が低く、熱伝導率がより向上する傾向にある。
アリルフェノール誘導体(D)としては、芳香環にアリル基とフェノール性水酸基が直接結合した化合物及びその誘導体であれば、特に限定されないが、例えば、芳香環の水素原子がアリル基で置換されたビスフェノール、芳香環の水素原子がアリル基で置換され、フェノール性水酸基が、上述したアリル基以外の反応性官能基中、ヒドロキシル基以外の反応性官能基で変性された変性ビスフェノール化合物が挙げられ、より具体的には、下記式(8)で表される化合物が挙げられ、更に具体的にはジアリルビスフェノールA、ジアリルビスフェノールAのシアン酸エステル化合物、ジアリルビスフェノールA型エポキシが挙げられる。
アルケニル置換ナジイミド化合物(E)は、分子中に1個以上のアルケニル置換ナジイミド基を有する化合物であれば特に限定されない。このなかでも、下記式(9)で表される化合物が好ましい。このようなアルケニル置換ナジイミド化合物(E)を用いることにより、得られる硬化物の熱膨張率がより低下し、耐熱性がより向上する傾向にある。
ビスフェノールA型構造単位と炭化水素系構造単位からなるエポキシ樹脂(C)は、分子中に、1個以上のビスフェノールA型構造単位と、1個以上の炭化水素系構造単位を有する化合物であれば特に限定されない。このなかでも、下記式(14)で表される化合物が好ましい。このようなビスフェノールA型構造単位と炭化水素系構造単位からなるエポキシ樹脂(C)を用いることにより、得られる硬化物の加熱時の貯蔵弾性率E’が反り抑制に好適な値となる傾向にある。
本実施形態の樹脂組成物は、シアン酸エステル化合物(F)を更に含有してもよい。シアン酸エステル化合物(F)としては、上述したアリルフェノール誘導体(D)以外のシアン酸エステル化合物であれば特に限定されないが、例えば、下記式(15)で示されるナフトールアラルキル型シアン酸エステル、下記式(16)で示されるノボラック型シアン酸エステル、ビフェニルアラルキル型シアン酸エステル、ビス(3,5-ジメチル4-シアナトフェニル)メタン、ビス(4-シアナトフェニル)メタン、1,3-ジシアナトベンゼン、1,4-ジシアナトベンゼン、1,3,5-トリシアナトベンゼン、1,3-ジシアナトナフタレン、1,4-ジシアナトナフタレン、1,6-ジシアナトナフタレン、1,8-ジシアナトナフタレン、2,6-ジシアナトナフタレン、2、7-ジシアナトナフタレン、1,3,6-トリシアナトナフタレン、4、4’-ジシアナトビフェニル、ビス(4-シアナトフェニル)エーテル、ビス(4-シアナトフェニル)チオエーテル、ビス(4-シアナトフェニル)スルホン、及び2、2’-ビス(4-シアナトフェニル)プロパン;これらシアン酸エステルのプレポリマー等が挙げられる。これらのシアン酸エステル化合物(F)は、1種単独で、又は2種以上を組み合わせて使用してもよい。
本実施形態の樹脂組成物は、上述したビスフェノールA型構造単位と炭化水素系構造単位からなるエポキシ樹脂(C)以外のエポキシ化合物(G)を更に含有してもよい。かかるエポキシ化合物(G)としては、前記エポキシ樹脂(C)以外の、1分子中に2つ以上のエポキシ基を有する化合物であれば特に限定されないが、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールE型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、アントラセン型エポキシ樹脂、3官能フェノール型エポキシ樹脂、4官能フェノール型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、アラルキルノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ポリオール型エポキシ樹脂、イソシアヌレート環含有エポキシ樹脂、或いはこれらのハロゲン化物が挙げられる。なお、アリル基含有化合物(B)がエポキシ基を有する場合、エポキシ化合物(G)は、エポキシ基を有するアリル基含有化合物(B)以外のものである。
本実施形態の樹脂組成物は、充填材(H)を更に含有してもよい。充填材(H)としては、特に限定されないが、例えば、無機充填材及び有機充填材が挙げられ、両者のうち無機充填材を含有していることが好ましく、有機充填材は無機充填材とともに用いること好適である。無機充填材としては、特に限定されないが、例えば、天然シリカ、溶融シリカ、合成シリカ、アモルファスシリカ、アエロジル、中空シリカ等のシリカ類;ホワイトカーボン等のケイ素化合物;チタンホワイト、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム等の金属酸化物;窒化ホウ素、凝集窒化ホウ素、窒化ケイ素、窒化アルミニウム等の金属窒化物;硫酸バリウム等の金属硫酸化物;水酸化アルミニウム、水酸化アルミニウム加熱処理品(水酸化アルミニウムを加熱処理し、結晶水の一部を減じたもの)、ベーマイト、水酸化マグネシウム等の金属水和物;酸化モリブデン、モリブデン酸亜鉛等のモリブデン化合物;ホウ酸亜鉛、錫酸亜鉛等の亜鉛化合物;アルミナ、クレー、カオリン、タルク、焼成クレー、焼成カオリン、焼成タルク、マイカ、E-ガラス、A-ガラス、NE-ガラス、C-ガラス、L-ガラス、D-ガラス、S-ガラス、M-ガラスG20、ガラス短繊維(Eガラス、Tガラス、Dガラス、Sガラス、Qガラス等のガラス微粉末類を含む。)、中空ガラス、球状ガラス等が挙げられる。また、有機充填材としては、特に限定されないが、例えば、スチレン型パウダー、ブタジエン型パウダー、アクリル型パウダー等のゴムパウダー;コアシェル型ゴムパウダー;シリコーンレジンパウダー;シリコーンゴムパウダー;シリコーン複合パウダー等が挙げられる。充填材(H)は、1種を単独で用いても、2種以上を併用してもよい。
本実施形態の樹脂組成物は、シランカップリング剤や湿潤分散剤を更に含有してもよい。シランカップリング剤や湿潤分散剤を含むことにより、上記充填材(H)の分散性、樹脂成分、充填材(H)、及び後述する基材の接着強度がより向上する傾向にある。
本実施形態の樹脂組成物は、必要に応じて、上述したアリル基含有化合物(B)以外の、アリル基含有化合物(以下「その他のアリル基含有化合物」ともいう)、フェノール樹脂、オキセタン樹脂、ベンゾオキサジン化合物、及び重合可能な不飽和基を有する化合物からなる群より選択される1種又は2種以上を更に含有してもよい。このようなその他の樹脂等を含むことにより、得られる硬化物の銅箔ピール強度、曲げ強度、及び曲げ弾性率等がより向上する傾向にある。
その他のアリル基含有化合物としては、特に限定されないが、例えば、アリルクロライド、酢酸アリル、アリルエーテル、プロピレン、トリアリルシアヌレート、トリアリルイソシアヌレート、フタル酸ジアリル、イソフタル酸ジアリル、マレイン酸ジアリル等が挙げられる。
フェノール樹脂としては、1分子中に2個以上のヒドロキシ基を有するフェノール樹脂であれば、一般に公知のものを使用でき、その種類は特に限定されない。その具体例としては、ビスフェノールA型フェノール樹脂、ビスフェノールE型フェノール樹脂、ビスフェノールF型フェノール樹脂、ビスフェノールS型フェノール樹脂、フェノールノボラック樹脂、ビスフェノールAノボラック型フェノール樹脂、グリシジルエステル型フェノール樹脂、アラルキルノボラック型フェノール樹脂、ビフェニルアラルキル型フェノール樹脂、クレゾールノボラック型フェノール樹脂、多官能フェノール樹脂、ナフトール樹脂、ナフトールノボラック樹脂、多官能ナフトール樹脂、アントラセン型フェノール樹脂、ナフタレン骨格変性ノボラック型フェノール樹脂、フェノールアラルキル型フェノール樹脂、ナフトールアラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、ビフェニル型フェノール樹脂、脂環式フェノール樹脂、ポリオール型フェノール樹脂、リン含有フェノール樹脂、水酸基含有シリコーン樹脂類等が挙げられるが、特に制限されるものではない。これらのフェノール樹脂は、1種を単独で又は2種以上を組み合わせて用いることができる。このようなフェノール樹脂を含むことにより、得られる硬化物の接着性や可撓性等により優れる傾向にある。
オキセタン樹脂としては、一般に公知のものを使用でき、その種類は特に限定されない。その具体例としては、オキセタン、2-メチルオキセタン、2,2-ジメチルオキセタン、3-メチルオキセタン、3,3-ジメチルオキセタン等のアルキルオキセタン、3-メチル-3-メトキシメチルオキセタン、3,3’-ジ(トリフルオロメチル)パーフルオキセタン、2-クロロメチルオキセタン、3,3-ビス(クロロメチル)オキセタン、ビフェニル型オキセタン、OXT-101(東亞合成製商品名)、OXT-121(東亞合成製商品名)等が挙げられる。これらのオキセタン樹脂は、1種又は2種以上を組み合わせて用いることができる。このようなオキセタン樹脂を含むことにより、得られる硬化物の接着性や可撓性等により優れる傾向にある。
ベンゾオキサジン化合物としては、1分子中に2個以上のジヒドロベンゾオキサジン環を有する化合物であれば、一般に公知のものを用いることができ、その種類は特に限定されない。その具体例としては、ビスフェノールA型ベンゾオキサジンBA-BXZ(小西化学製商品名)ビスフェノールF型ベンゾオキサジンBF-BXZ(小西化学製商品名)、ビスフェノールS型ベンゾオキサジンBS-BXZ(小西化学製商品名)等が挙げられる。これらのベンゾオキサジン化合物は、1種又は2種以上混合して用いることができる。このようなベンゾオキサジン化合物を含むことにより、得られる硬化物の難燃性、耐熱性、低吸水性、低誘電等により優れる傾向にある。
重合可能な不飽和基を有する化合物としては、一般に公知のものを使用でき、その種類は特に限定されない。その具体例としては、エチレン、プロピレン、スチレン、ジビニルベンゼン、ジビニルビフェニル等のビニル化合物;メチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等の1価又は多価アルコールの(メタ)アクリレート類;ビスフェノールA型エポキシ(メタ)アクリレート、ビスフェノールF型エポキシ(メタ)アクリレート等のエポキシ(メタ)アクリレート類;ベンゾシクロブテン樹脂;(ビス)マレイミド樹脂等が挙げられる。これらの不飽和基を有する化合物は、1種又は2種以上混合して用いることができる。このような重合可能な不飽和基を有する化合物を含むことにより、得られる硬化物の耐熱性や靱性等により優れる傾向にある。
本実施形態の樹脂組成物は、硬化促進剤を更に含有してもよい。硬化促進剤としては、特に限定されないが、例えば、トリフェニルイミダゾール等のイミダゾール類;過酸化ベンゾイル、ラウロイルパーオキサイド、アセチルパーオキサイド、パラクロロベンゾイルパーオキサイド、ジ-tert-ブチル-ジ-パーフタレート等の有機過酸化物;アゾビスニトリル等のアゾ化合物;N,N-ジメチルベンジルアミン、N,N-ジメチルアニリン、N,N-ジメチルトルイジン、N,N-ジメチルピリジン、2-N-エチルアニリノエタノール、トリ-n-ブチルアミン、ピリジン、キノリン、N-メチルモルホリン、トリエタノールアミン、トリエチレンジアミン、テトラメチルブタンジアミン、N-メチルピペリジン等の第3級アミン類;フェノール、キシレノール、クレゾール、レゾルシン、カテコール等のフェノール類;ナフテン酸鉛、ステアリン酸鉛、ナフテン酸亜鉛、オクチル酸亜鉛、オレイン酸錫、ジブチル錫マレート、ナフテン酸マンガン、ナフテン酸コバルト、アセチルアセトン鉄等の有機金属塩;これら有機金属塩をフェノール、ビスフェノール等の水酸基含有化合物に溶解してなるもの;塩化錫、塩化亜鉛、塩化アルミニウム等の無機金属塩;ジオクチル錫オキサイド、その他のアルキル錫、アルキル錫オキサイド等の有機錫化合物等が挙げられる。これらのなかでも、トリフェニルイミダゾールが硬化反応を促進し、ガラス転移温度(Tg)、熱膨張率が優れる傾向にあるため、特に好ましい。
本実施形態の樹脂組成物は、溶剤を更に含有してもよい。溶剤を含むことにより、樹脂組成物の調製時における粘度が下がり、ハンドリング性がより向上するとともに後述する基材への含浸性がより向上する傾向にある。
本実施形態の樹脂組成物の製造方法は、特に限定されないが、例えば、各成分を順次溶剤に配合し、十分に攪拌する方法が挙げられる。この際、各成分を均一に溶解或いは分散させるため、攪拌、混合、混練処理等の公知の処理を行うことができる。具体的には、適切な攪拌能力を有する攪拌機を付設した攪拌槽を用いて攪拌分散処理を行うことで、樹脂組成物に対する充填材(H)の分散性を向上させることができる。上記の攪拌、混合、混練処理は、例えば、ボールミル、ビーズミル等の混合を目的とした装置、又は、公転又は自転型の混合装置等の公知の装置を用いて適宜行うことができる。
本実施形態の式(1)~(5)好ましくは式(1A)~(5A)で表される機械特性に関する物性パラメータの数値範囲を満たすプリプレグは、絶縁層、積層板、金属箔張積層板、プリント配線板、又は多層プリント配線板として好適に用いることができる。以下、積層板、金属箔張積層板、及びプリント配線板(多層プリント配線板を含む。)について説明する。
本実施形態の積層板は、少なくとも1枚以上積層された本実施形態の上記プリプレグを有するものである。また、本実施形態の金属箔張積層板は、本実施形態の積層板(すなわち少なくとも1枚以上積層された本実施形態の上記プリプレグ)と、その積層板の片面又は両面に配された金属箔(導体層)とを有するものである。上述した式(1)~(5)好ましくは式(1A)~(5A)で表される機械特性(貯蔵弾性率及び損失弾性率)に関する物性パラメータの数値範囲を満たすプリプレグを用いることにより、本実施形態の積層板及び金属箔張積層板は、明確なガラス転移温度が存在せず(Tgレス)、かつ、反りを十分に低減(低反りを達成)できる傾向にある。
本実施形態のプリント配線板は、絶縁層と、該絶縁層の表面に形成された導体層とを有するプリント配線板であって、絶縁層が、上記プリプレグを含む。例えば、上述した本実施形態の金属箔張積層板に、所定の配線パターンを形成することにより、プリント配線板として好適に用いることができる。上述したように、本実施形態の金属箔張積層板は、明確なガラス転移温度が存在せず(Tgレス)、かつ、反りを十分に低減(低反りを達成)できる傾向にあるので、そのような性能が要求されるプリント配線板として、殊に有効に用いることができる。
反応器内で、α-ナフトールアラルキル樹脂(SN495V、OH基当量:236g/eq.、新日鐵化学(株)製:ナフトールアラルキルの繰り返し単位数nは1~5のものが含まれる。)0.47モル(OH基換算)を、クロロホルム500mlに溶解させ、この溶液にトリエチルアミン0.7モルを添加した。温度を-10℃に保ちながら反応器内に0.93モルの塩化シアンのクロロホルム溶液300gを1.5時間かけて滴下し、滴下終了後、30分撹拌した。その後さらに、0.1モルのトリエチルアミンとクロロホルム30gの混合溶液を反応器内に滴下し、30分撹拌して反応を完結させた。副生したトリエチルアミンの塩酸塩を反応液から濾別した後、得られた濾液を0.1N塩酸500mlで洗浄した後、水500mlでの洗浄を4回繰り返した。これを硫酸ナトリウムにより乾燥した後、75℃でエバポレートし、さらに90℃で減圧脱気することにより、褐色固形の上記式(15)で表されるα-ナフトールアラルキル型シアン酸エステル化合物(式中のR6はすべて水素原子である。)を得た。得られたα-ナフトールアラルキル型シアン酸エステル化合物を赤外吸収スペクトルにより分析したところ、2264cm-1付近にシアン酸エステル基の吸収が確認された。
マレイミド化合物(A)(BMI-2300、大和化成工業(株)製、マレイミド当量186g/eq.)45質量部、アリル基含有化合物(B)かつアルケニル置換ナジイミド化合物(E)(BANI-M、丸善石油化学(株)製、アリル当量:286g/eq.)34質量部、ビスフェノールA型構造単位と炭化水素系構造単位からなるエポキシ樹脂(C)(EPICLON EXA-4850-150、DIC(株)製、エポキシ当量:450g/eq.)10質量部、シアン酸エステル化合物(F)である合成例1のα-ナフトールアラルキル型シアン酸エステル化合物(SN495VCN、シアネート当量:261g/eq.)1質量部、エポキシ化合物(G)(NC-3000FH、日本化薬(株)製、エポキシ当量:320g/eq.)10質量部、充填材(H)であるスラリーシリカ(SC-2050MB、アドマテックス(株)製)120質量部及び同シリコーン複合パウダー(KMP-600、信越化学工業(株)製)20質量部、シランカップリング剤(Z-6040、東レ・ダウコーニング(株)製)5質量部、湿潤分散剤(DISPERBYK-161、ビッグケミー・ジャパン(株)製)1質量部、並びに、硬化促進剤であるトリフェニルイミダゾール(和光純薬工業(株)製)0.5質量部及び同オクチル酸亜鉛(日本化学産業(株)製)0.1質量部を混合し、メチルエチルケトンで希釈することでワニスを得た。このワニスをEガラス織布((株)有沢製作所製、IPC#2116)に含浸塗工し、160℃で3分間加熱乾燥して、樹脂組成物含有量57体積%のプリプレグを得た。
実施例1で得たワニスをEガラス織布(ユニチカ(株)製、IPC#1030)に含浸塗工し、160℃で3分間加熱乾燥して、樹脂組成物含有量73体積%のプリプレグを得た。
マレイミド化合物(A)(BMI-2300)43質量部、アリル基含有化合物(B)かつアルケニル置換ナジイミド化合物(E)(BANI-M)32質量部、ビスフェノールA型構造単位と炭化水素系構造単位からなるエポキシ樹脂(C)(EPICLON EXA-4816、DIC(株)製、エポキシ当量:403g/eq.)10質量部、シアン酸エステル化合物(F)である合成例1のα-ナフトールアラルキル型シアン酸エステル化合物(SN495VCN)5質量部、エポキシ化合物(G)(NC-3000FH、日本化薬(株)製、エポキシ当量:320g/eq.)10質量部、充填材(H)であるスラリーシリカ(SC-2050MB)100質量部、同スラリーシリカ(SC-5050MOB、アドマテックス(株)製)100質量部、及び同シリコーン複合パウダー(KMP-600)20質量部、シランカップリング剤(Z-6040)5質量部、湿潤分散剤(DISPERBYK-111、ビッグケミー・ジャパン(株)製)2質量部及び同(DISPERBYK-161)1質量部、並びに、硬化促進剤であるトリフェニルイミダゾール0.5質量部及び同オクチル酸亜鉛0.1質量部を混合し、メチルエチルケトンで希釈することでワニスを得た。このワニスをEガラス織布(IPC#2116)に含浸塗工し、160℃で3分間加熱乾燥して、樹脂組成物含有量57体積%のプリプレグを得た。
実施例3で得たワニスをEガラス織布(IPC#1030)に含浸塗工し、160℃で3分間加熱乾燥して、樹脂組成物含有量73体積%のプリプレグを得た。
マレイミド化合物(A)(BMI-2300)51質量部、アリル基含有化合物(B)かつアルケニル置換ナジイミド化合物(E)(BANI-M)38質量部、シアン酸エステル化合物(F)である合成例1のα-ナフトールアラルキル型シアン酸エステル化合物(SN495VCN)1質量部、エポキシ化合物(G)(NC-3000FH)10質量部、充填材(H)であるスラリーシリカ(SC-2050MB)120質量部、及び同シリコーン複合パウダー(KMP-600)20質量部、シランカップリング剤(Z-6040)5質量部、湿潤分散剤(DISPERBYK-161)1質量部、並びに、硬化促進剤であるトリフェニルイミダゾール0.5質量部及び同オクチル酸亜鉛0.1質量部を混合し、メチルエチルケトンで希釈することでワニスを得た。このワニスをEガラス織布(IPC#2116)に含浸塗工し、160℃で3分間加熱乾燥して、樹脂組成物含有量57体積%のプリプレグを得た。
比較例1で得たワニスをEガラス織布(IPC#1030)に含浸塗工し、160℃で3分間加熱乾燥して、樹脂組成物含有量73体積%のプリプレグを得た。
マレイミド化合物(A)(BMI-2300)49質量部、アリル基含有化合物(B)かつアルケニル置換ナジイミド化合物(E)(BANI-M)36質量部、シアン酸エステル化合物(F)である合成例1のα-ナフトールアラルキル型シアン酸エステル化合物(SN495VCN)5質量部、エポキシ化合物(G)(NC-3000FH)10質量部、充填材(H)であるスラリーシリカ(SC-2050MB)100質量部、同スラリーシリカ(SC-5050MOB)100質量部、及び同シリコーン複合パウダー(KMP-600)20質量部、シランカップリング剤(Z-6040)5質量部、湿潤分散剤(DISPERBYK-111)2質量部及び同(DISPERBYK-161)1質量部、並びに、硬化促進剤であるトリフェニルイミダゾール0.5質量部及び同オクチル酸亜鉛0.1質量部を混合し、メチルエチルケトンで希釈することでワニスを得た。このワニスをEガラス織布(IPC#2116)に含浸塗工し、160℃で3分間加熱乾燥して、樹脂組成物含有量57体積%のプリプレグを得た。
比較例3で得たワニスをEガラス織布(IPC#1030)に含浸塗工し、160℃で3分間加熱乾燥して、樹脂組成物含有量73体積%のプリプレグを得た。
マレイミド化合物(BMI-70、ケイ・アイ化成(株)製、マレイミド当量:221g/eq.)15質量部、シアン酸エステル化合物(F)である合成例1のα-ナフトールアラルキル型シアン酸エステル化合物(SN495VCN)35質量部、エポキシ化合物(G)(NC-3000FH)50質量部、充填材(H)であるスラリーシリカ(SC-2050MB)100質量部、同スラリーシリカ(SC-5050MOB)100質量部及び同シリコーン複合パウダー(KMP-600)20質量部、シランカップリング剤(Z-6040)5質量部、湿潤分散剤(DISPERBYK-111)2質量部及び同(DISPERBYK-161)1質量部、並びに、硬化促進剤であるトリフェニルイミダゾール0.5質量部及び同オクチル酸亜鉛0.1質量部を混合し、メチルエチルケトンで希釈することでワニスを得た。このワニスをEガラス織布(IPC#2116)に含浸塗工し、160℃で3分間加熱乾燥して、樹脂組成物含有量57体積%のプリプレグを得た。
比較例5で得たワニスをEガラス織布(IPC#1030)に含浸塗工し、160℃で3分間加熱乾燥して、樹脂組成物含有量73体積%のプリプレグを得た。
実施例1~4及び比較例1~6で得られたプリプレグを用い、以下の各項目に示す手順により物性測定評価用のサンプルを作製し、機械特性(貯蔵弾性率、及び損失弾性率)、式(1)~(5)及び式(1A)~(5A)における機械特性に関する物性パラメータ、ガラス転移温度(Tg)、反り量(2種類)、並びにリフロー工程前後基板収縮率を測定評価した。実施例の結果をまとめて表1に示し、比較例の結果をまとめて表2に示す。
実施例1~4及び比較例1~6で得られたプリプレグ1枚の上下両面に、銅箔(3EC-VLP、三井金属鉱業(株)製、厚み12μm)を配置し、圧力30kgf/cm2、温度230℃で100分間の積層成形(熱硬化)を行い、所定の絶縁層厚さの銅箔張積層板を得た。得られた銅箔張積層板をダイシングソーでサイズ5.0mm×20mmに切断後、表面の銅箔をエッチングにより除去し、測定用サンプルを得た。この測定用サンプルを用い、JIS C6481に準拠して動的粘弾性分析装置(TAインスツルメント製)でDMA法により、機械特性(貯蔵弾性率E’及び損失弾性率E’’)を測定した(n=3の平均値)。
実施例1~4及び比較例1~6で得られたプリプレグ1枚の上下両面に、銅箔(3EC-VLP、三井金属鉱業(株)製、厚み12μm)を配置し、圧力30kgf/cm2、温度230℃で100分間の積層成形(熱硬化)を行い、所定の絶縁層厚さの銅箔張積層板を得た。得られた銅箔張積層板をダイシングソーでサイズ12.7mm×2.5mmに切断後、表面の銅箔をエッチングにより除去し、測定用サンプルを得た。この測定用サンプルを用い、JIS C6481に準拠して動的粘弾性分析装置(TAインスツルメント製)でDMA法により、ガラス転移温度(Tg)を測定した(n=3の平均値)。
まず、実施例1~4及び比較例1~6で得られたプリプレグ1枚の上下両面に、銅箔(3EC-VLP、三井金属鉱業(株)製、厚み12μm)を配置し、圧力30kgf/cm2、温度220℃で120分間の積層成形(熱硬化)を行い、銅箔張積層板を得た。次に、得られた銅箔張積層板から上記銅箔を除去した。次いで、銅箔を除去した積層板の片面に、実施例1~4及び比較例1~6で得られたプリプレグ1枚を更に配置し、その上下両面に、上記銅箔(3EC-VLP、三井金属鉱業(株)製、厚み12μm)を配置し、圧力30kgf/cm2、温度220℃で120分間の積層成形(熱硬化)を行い、再び銅箔張積層板を得た。さらに、得られた銅箔張積層板から上記銅箔を除去し、積層板を得た。そして、得られた積層板から20mm×200mmの短冊状板を切りだし、2枚目に積層したプリプレグの面を上にして、長尺方向両端の反り量の最大値を金尺にて測定し、その平均値をバイメタル法による「反り量」とした。
まず、図1に示す如く、支持体(a)となるプリプレグの両面に、キャリア付極薄銅箔(b1)(MT18Ex、三井金属鉱業(株)製、厚み5μm)のキャリア銅箔面をプリプレグ側に向けて配置し、その上に実施例1~4及び比較例1~6で得られたプリプレグ(c1)を更に配置し、その上に銅箔(d)(3EC-VLP、三井金属鉱業(株)製、厚み12μm)を更に配置し、圧力30kgf/cm2、温度220℃で120分間の積層成形を行って図2に示す銅箔張積層板を得た。
実施例1~4及び比較例1~6で得られたプリプレグ1枚の上下両面に、銅箔(3EC-VLP、三井金属鉱業(株)製、厚み12μm)を配置し、圧力30kgf/cm2、温度220℃で120分間の積層成形を行って、銅箔張積層板を得た。次に、得られた銅箔張積層板にドリルにて格子状均等に9点の穴あけ加工を実施した後、上記銅箔を除去した。
((距離イ)-(距離ロ))/距離イ×100 …式(I)
Claims (8)
- 熱硬化性樹脂と、
充填材と、
基材と、
を含有するプリプレグであって、
該プリプレグを230℃及び100分の条件で熱硬化させて得られる硬化物が、下記式(1)~(5);
E’(200℃)/E’(30℃)≦0.90 …(1)
E’(260℃)/E’(30℃)≦0.85 …(2)
E’(330℃)/E’(30℃)≦0.80 …(3)
E’’max/E’(30℃)≦3.0% …(4)
E’’min/E’(30℃)≧0.5% …(5)
(各式中、E’は、括弧内に示す温度における前記硬化物の貯蔵弾性率を示し、E’’maxは、30℃から330℃の温度範囲における前記硬化物の損失弾性率の最大値を示し、E’’minは、30℃から330℃の温度範囲における前記硬化物の損失弾性率の最小値を示す。)
で表される機械特性に関する物性パラメータの数値範囲を満たす、
プリプレグ。 - 下記式(6A);
E’(30℃)≦30GPa …(6A)
(式中、E’は、括弧内に示す温度における前記硬化物の貯蔵弾性率を示す。)
で表される機械特性を更に満たす、
請求項1に記載のプリプレグ。 - 前記基材が、ガラス基材である、
請求項1又は2に記載のプリプレグ。 - 前記ガラス基材が、Eガラス、Dガラス、Sガラス、Tガラス、Qガラス、Lガラス、NEガラス、及びHMEガラスからなる群より選択される1種以上のガラスの繊維で構成されたものである、
請求項3に記載のプリプレグ。 - 少なくとも1枚以上積層された請求項1~4のいずれか1項に記載のプリプレグを有する、
積層板。 - 少なくとも1枚以上積層された請求項1~4のいずれか1項に記載のプリプレグと、
該プリプレグの片面又は両面に配された金属箔と、
を有する金属箔張積層板。 - 請求項1~4のいずれか1項に記載のプリプレグで形成された絶縁層と、
該絶縁層の表面に形成された導体層と、
を有するプリント配線板。 - 少なくとも1枚以上積層された請求項1~4のいずれか1項に記載のプリプレグで形成された第1の絶縁層、及び、前記第1の絶縁層の片面方向に少なくとも1枚以上積層された請求項1~4のいずれか1項に記載のプリプレグで形成された第2の絶縁層からなる複数の絶縁層と、
前記複数の絶縁層の各々の間に配された第1の導体層、及び、前記複数の絶縁層の最外層の表面に配された第2の導体層からなる複数の導体層と、
を有する多層プリント配線板。
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