CN114127205A - Resin sheet, metal foil-clad laminate, and printed wiring board - Google Patents

Resin sheet, metal foil-clad laminate, and printed wiring board Download PDF

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Publication number
CN114127205A
CN114127205A CN202080046749.3A CN202080046749A CN114127205A CN 114127205 A CN114127205 A CN 114127205A CN 202080046749 A CN202080046749 A CN 202080046749A CN 114127205 A CN114127205 A CN 114127205A
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Prior art keywords
resin composition
resin
compound
trade name
mass
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CN202080046749.3A
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CN114127205B (en
Inventor
川下和晃
加藤祯启
杉本宪明
小柏尊明
松山洋介
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of 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
    • 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
    • B32B27/08—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 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
    • 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
    • B32B15/09—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 polyesters
    • 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
    • B32B15/04—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
    • B32B15/098—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 condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/281—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 comprising polyimides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • B32B7/028—Heat-shrinkability
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B32B2307/102—Insulating
    • 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
    • B32B2307/202—Conductive
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • 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
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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  • Chemical Kinetics & Catalysis (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The resin sheet of the present invention comprises: a support; and a layer comprising a resin composition provided on the surface of the support, the resin composition satisfying the relationships represented by formulas (i), (ii), and (iii). 0.15. ltoreq. b/a. ltoreq.0.60. DEG. i (i), 0.015. ltoreq. c/a. ltoreq.0.07. DEG. ii), 3. ltoreq. a. ltoreq.10. DEG. iii (formulae (i), (ii) and (iii), a, b and c respectively represent storage moduli (unit: GPa) at 40 ℃, 170 ℃ and 230 ℃ of a cured product of the resin composition.

Description

Resin sheet, metal foil-clad laminate, and printed wiring board
Technical Field
The invention relates to a resin sheet, a metal foil-clad laminate, and a printed wiring board.
Background
In recent years, with the development of higher functionality and smaller size of semiconductor packages widely used in electronic devices, communication devices, personal computers, and the like, high integration and high-density mounting of each component thereof have been accelerated. Along with this, the characteristics required for the printed circuit board for the semiconductor package are also becoming more and more severe. Examples of the characteristics required for such printed wiring boards include low water absorption, moisture absorption and heat resistance, flame retardancy, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, heat resistance, chemical resistance, and high plating peel strength. In addition, in addition to these, suppression of warpage (realization of low warpage) of the printed circuit board has become an important technical problem, and various studies have been made.
For example, patent document 1 describes a resin sheet having a support and an adhesive layer, which is reduced in warpage in a high-temperature environment when applied to a printed wiring board.
Documents of the prior art
Patent document
Patent document 1, Japanese patent laid-open publication No. 2016-179564
Disclosure of Invention
Problems to be solved by the invention
However, in patent document 1, since the warpage is reduced by reducing the thermal expansion coefficient, the warpage of the printed circuit board cannot be sufficiently reduced. Therefore, further improvement is desired for reducing the warpage.
In contrast, the present inventors have intensively studied and found the following: in order to reduce the warpage of a printed circuit board, it is effective to reduce the elastic modulus of a cured product of a resin composition (hereinafter also referred to as "resin material") in a resin sheet having a layer containing the resin composition for use in a printed circuit board, so that the resin sheet exhibits a viscous behavior. For this reason, the present inventors have studied to use a resin material having a low elastic modulus and being easily plastically deformed (exhibiting a viscous behavior). However, when such a resin material is used, there is another problem that the handling property (workability) in the printed wiring board production process is insufficient due to low rigidity. In addition, since such a resin material tends to have a high water absorption rate and insufficient heat resistance and chemical resistance, there is a possibility that a further problem may occur from the viewpoint of product quality.
Accordingly, an object of the present invention is to provide a resin sheet, a metal foil-clad laminate, and a printed wiring board that can sufficiently reduce the warpage of the printed wiring board (realize low warpage) and can exhibit excellent rigidity and heat resistance.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems, and as a result, have found that: by using a resin sheet having a layer comprising the following resin composition, the warpage of a printed circuit board can be sufficiently reduced, and excellent rigidity and heat resistance can be exhibited; the present inventors have completed the present invention by finding that, in the form of a cured product obtained by curing a resin composition, physical property parameters defined by a storage modulus at a predetermined temperature satisfy a predetermined range.
Namely, the present invention is as follows.
[ 1] A resin sheet comprising: a support; and a layer comprising a resin composition provided on the surface of the support, the resin composition satisfying the relationships represented by the following formulae (i), (ii), and (iii),
0.15≤b/a≤0.60···(i)
0.015≤c/a≤0.07···(ii)
3≤a≤10···(iii)
in the formulae (i), (ii) and (iii), a, b and c represent storage moduli (unit: GPa) at 40 ℃, 170 ℃ and 230 ℃ respectively of a cured product of the resin composition.
The resin sheet according to [ 1], wherein the resin composition further satisfies the relationship represented by the following formula (iv),
175≤Tg≤215…(iv)
in the formula (iv), Tg represents a glass transition temperature (unit:. degree. C.) of a cured product of the resin composition.
[ 3] the resin sheet according to [ 1] or [ 2], wherein the resin composition further satisfies the relationship represented by the following formula (v),
0.015≤d/a≤0.08…(v)
in the formula (v), d represents the storage modulus (unit: GPa) at 260 ℃ of a cured product of the resin composition, and a is the same as described above.
The resin sheet according to any one of [ 1] to [ 3], wherein the resin composition contains an elastomer component.
The resin sheet according to any one of [ 1] to [ 4], wherein the resin composition contains at least 1 compound selected from the group consisting of a cyanate compound, a phenol compound, an epoxy compound and a maleimide compound.
The resin sheet according to [ 6 ] or [ 5], wherein the resin composition comprises: the cyanate ester compound and/or the phenol compound; and, the epoxy compound and/or the maleimide compound.
[ 7 ] the resin sheet according to [ 5] or [ 6 ], wherein the resin composition comprises: the phenol compound; and, the epoxy compound and/or the maleimide compound.
The resin sheet according to any one of [ 5] to [ 7 ], wherein the resin composition contains 2 or more kinds of the epoxy compounds, and the 2 or more kinds of epoxy compounds include a naphthalene-type epoxy resin and/or an aralkyl-type epoxy resin having a naphthalene skeleton.
The resin sheet according to any one of [ 1] to [ 8 ], wherein the resin composition contains a filler, and the content of the filler is 100 to 700 parts by mass based on 100 parts by mass of a resin solid content in the resin composition.
The resin sheet according to [ 9 ], wherein the filler contains an inorganic filler and/or an organic filler.
The resin sheet according to [ 10 ], wherein the inorganic filler contains at least 1 selected from the group consisting of silica, boehmite, and alumina.
The resin sheet according to any one of [ 1] to [ 11 ], wherein the support is a resin sheet or a metal foil.
[ 13 ] A metal-clad laminate comprising: a layer comprising a cured product of the resin composition according to any one of [ 1] to [ 11 ]; and a metal foil provided on one or both surfaces of the layer containing the cured product.
[ 14 ] A printed circuit board comprising: an insulating layer comprising a cured product of the resin composition according to any one of [ 1] to [ 11 ]; and a conductor layer disposed on a surface of the insulating layer.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a resin sheet, a metal foil-clad laminate, and a printed wiring board can be provided which can sufficiently reduce the warpage of the printed wiring board (realize low warpage) and can exhibit excellent rigidity and heat resistance.
Detailed Description
Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the spirit thereof.
The "resin solid content" described in the present specification means, unless otherwise specified, components other than additives (silane coupling agent, wetting dispersant, curing accelerator, and the like), solvent, and fillers (organic filler and inorganic filler) in the resin composition of the present embodiment; the resin solid content of 100 parts by mass means that the total of the components other than the additives (silane coupling agent, wetting dispersant, curing accelerator, etc.), solvent and filler (organic filler and inorganic filler) in the resin composition is 100 parts by mass.
[ resin sheet ]
The resin sheet of the present embodiment includes a support and a layer containing a resin composition provided on a surface of the support, and the resin composition satisfies the relationships expressed by the following formulas (i), (ii), and (iii). That is, the resin sheet of the present embodiment is, for example, a product obtained by applying the resin composition to one surface or both surfaces of a support.
0.15≤b/a≤0.60···(i)
0.015≤c/a≤0.07···(ii)
3≤a≤10···(iii)
In the formulae (i), (ii) and (iii), a, b and c represent storage moduli (unit: GPa) at 40 ℃, 170 ℃ and 230 ℃ respectively of a cured product obtained by curing the resin composition. Need toIn the present embodiment, the storage modulus of the cured product at 40 ℃, 170 ℃ and 230 ℃ is: using under a pressure of 30kgf/cm2And a value obtained by dynamic viscoelasticity measurement (DMA) according to JIS C6481 of a cured product obtained by curing the resin composition at 230 ℃ for 100 minutes. The specific measurement method is as described in examples.
In the present embodiment, by using a resin sheet having a layer containing the resin composition having the above-described characteristics, the warping of the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (for example, multilayer coreless substrate) can be sufficiently reduced, and excellent rigidity and heat resistance can be exhibited. The main reasons for this are considered as follows. The following description includes a review, but the review does not limit the present embodiment at all.
That is, in order to reduce the warpage of a printed circuit board, it is important to reduce the elastic modulus of a cured product of a resin composition (resin material) used for a printed circuit board so that the resin composition exhibits a viscous behavior. For this reason, it is conceivable to use a resin material that has a low elastic modulus and is easily plastically deformed (exhibits viscous behavior). However, when such a resin material is used, the rigidity is low, and therefore the handling property (workability) in the manufacturing process of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) is insufficient. In addition, such a resin material tends to have a high water absorption rate and insufficient heat resistance and chemical resistance, and therefore, there is a problem also from the viewpoint of product quality.
In contrast, in the resin sheet having a layer including the resin composition of the present embodiment, in the form of a cured product obtained by curing the resin composition (also referred to as "cured form of the resin composition"), the storage modulus at 40 ℃. In addition, in the cured form of the resin composition, the rigidity can be sufficiently maintained even when heated to 170 ℃ by mainly controlling the ratio of the storage modulus at 170 ℃ to the storage modulus at 40 ℃ within a predetermined range (satisfying the above formula (i)). As a result, by using the resin sheet of the present embodiment, for example, handling (workability) can be provided in a manufacturing process of a printed circuit board (for example, a thin substrate such as a multilayer coreless substrate). In addition, since the ratio of the storage modulus at 230 ℃ to the storage modulus at 40 ℃ is controlled within a predetermined range (satisfying the above formula (ii)), the adhesive behavior can be exhibited in a step including a heat treatment (for example, a press molding step, an annealing step, or the like). As a result, warping of the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (for example, a multilayer coreless substrate) can be reduced. In addition, since the storage modulus at 40 ℃ is mainly controlled to be within a predetermined range (satisfying the above formula (iii)), and the ratio of the storage modulus at 170 ℃ to the storage modulus at 40 ℃ is controlled to be within a predetermined range (satisfying the above formula (i)), excellent heat resistance can be provided to the metal-clad laminate, the printed circuit board, and the multilayer printed wiring body. As described later, by controlling the glass transition temperature of the cured product of the resin composition within a predetermined range (satisfying the following formula (iv)), more excellent heat resistance can be provided to the metal-clad laminate, the printed wiring board, and the multilayer printed wiring body. As described later, by controlling the storage modulus of the cured product of the resin composition at 260 ℃ within a predetermined range (satisfying the following formula (v)), more excellent heat resistance can be provided to the metal-clad laminate, the printed wiring board, and the multilayer printed wiring body.
The resin sheet of the present embodiment is preferably a product obtained by applying the resin composition in the layer containing the resin composition of the present embodiment to a support and then semi-curing (B-staging) the resin composition. In the present embodiment, the semi-cured state (B stage) means that the layer containing the resin composition is in a dry state, that is, a state in which the solvent is heated to a degree of non-tackiness by being volatilized, and also includes a state in which only the solvent is volatilized without being heated and not being cured, although the respective components contained in the layer containing the resin composition do not actively start to react (cure). In the present embodiment, the minimum melt viscosity in the semi-cured state (B stage) is usually 20000Pa · s or less. In the present embodiment, the minimum melt viscosity is measured by the following method. That is, the lowest melt viscosity was measured by a rheometer (ARES-G2 (trade name) manufactured by TA instruments) using 1G of the resin powder collected from the layer containing the resin composition as a sample. Wherein the lowest melt viscosity of the resin powder was measured using a disposable plate having a plate diameter of 25mm under conditions of a temperature range of 40 ℃ to 180 ℃, a temperature rise rate of 2 ℃/min, a frequency of 10.0 rad/sec, and a strain of 0.1%. The lower limit of the minimum melt viscosity is, for example, 10 pas or more.
The support and the layer containing the resin composition in the resin sheet of the present embodiment will be described.
(support body)
The support according to the present embodiment is not particularly limited, and known products that can be used as materials for various printed circuit boards, preferably a resin sheet or a metal foil, can be used. The resin sheet is different from the layer containing the resin composition layer according to the present embodiment. Examples of the resin sheet and the metal foil include resin sheets such as a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, and a Polyethylene (PE) film; and metal foils such as aluminum foil, copper foil, and gold foil. Among them, copper foil and PET film are preferable. As the copper foil, commercially available products can be used, and examples thereof include 3EC-VLP (trade name) manufactured by Mitsui Metal mining corporation, 3EC-M2S-VLP (trade name) manufactured by Mitsui Metal mining corporation, MT18Ex (trade name) manufactured by Mitsui Metal mining corporation, and JXUT-I (trade name) manufactured by JX Nigri metal.
[ characteristics of the resin composition ]
In the resin sheet having a layer including the resin composition of the present embodiment, in a state of a cured product obtained by curing the resin composition (hereinafter, also simply referred to as "cured product"), as described above, the physical property parameter defined by the storage modulus at a predetermined temperature satisfies the predetermined range.
0.15≤b/a≤0.60···(i)
0.015≤c/a≤0.07···(ii)
3≤a≤10···(iii)
In the formulae (i), (ii) and (iii), a, b and c represent storage moduli (unit: GPa) at 40 ℃, 170 ℃ and 230 ℃ of a cured product of the resin composition, respectively.
In the present embodiment, the cured product is a cured product that is obtained by thermally curing the resin composition at a heating temperature of 180 to 270 ℃ for a heating time of 30 to 210 minutes and that satisfies at least the above formulae (i), (ii), and (iii). The heating temperature is preferably 200 to 240 ℃, more preferably 225 to 235 ℃, and still more preferably 230 ℃. The heating time is preferably 60 minutes to 180 minutes, and more preferably 100 minutes. The pressure conditions for curing are not particularly limited as long as the effects of the present embodiment are not impaired, and generally, the preferred conditions for curing the resin composition can be used. The pressure condition is preferably 10kgf/cm2～50kgf/cm2More preferably 20kgf/cm2～40kgf/cm2More preferably 30kgf/cm2. The heating means for curing the resin composition is not particularly limited as long as the operation and effect of the present embodiment are not impaired, and a general heating means (for example, a dryer or the like) may be used.
The storage modulus of the cured product was measured by DMA method (Dynamic Mechanical Analysis method) in accordance with JIS C6481. The specific measurement method is as described in examples.
In the above formula (iii), it is considered that when a (storage modulus at 40 ℃) is 3GPa or more, sufficient rigidity can be ensured. From the same viewpoint, a is preferably 4GPa or more, and more preferably 4.5GPa or more. On the other hand, if a is 10GPa or less, warpage of the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (for example, a multilayer coreless substrate) can be reduced. From the same viewpoint, a is preferably 8GPa or less, and more preferably 7GPa or less.
In the above formula (i), it is considered that when b/a (the ratio of the storage modulus at 170 ℃ to the storage modulus at 40 ℃) is 0.15 or more, the rigidity can be sufficiently maintained even when the material is heated to 170 ℃. As a result, it is considered that by using the resin sheet having the layer containing the resin composition of the present embodiment, for example, excellent handling property (workability) in the manufacturing process of a printed circuit board (for example, a thin substrate such as a multilayer coreless substrate) can be achieved. From the same viewpoint, b/a is preferably 0.17 or more. On the other hand, b/a is preferably 0.60 or less.
In the above formula (ii), when c/a (the ratio of the storage modulus at 230 ℃ to the storage modulus at 40 ℃) is within the above range, it is considered that the viscous behavior can be exhibited in a step including a heat treatment (for example, a press molding step, an annealing step, and the like). As a result, it is considered that the warping of the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (for example, the multilayer coreless substrate) can be reduced. The lower limit of c/a is preferably 0.02 or more from the viewpoint of further improving the handling property (workability) in the manufacturing process of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate). The upper limit value of c/a is more preferably 0.06 or less from the viewpoint of further reducing warpage of the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (for example, a multilayer coreless substrate).
In the resin sheet having a layer containing the resin composition of the present embodiment, the glass transition temperature of a cured product obtained by curing the resin composition preferably satisfies the following formula (iv) in view of the improvement in heat resistance and the control of the formula (ii) within a desired range.
175≤Tg≤215…(iv)
The glass transition temperature is more preferably from 180 ℃ to 213 ℃.
The glass transition temperature of the cured product was measured by the DMA method in accordance with JIS C6481. The specific measurement method is as described in examples.
In the resin sheet having a layer containing the resin composition of the present embodiment, a cured product obtained by curing the resin composition preferably further satisfies the relationship represented by the following formula (v).
0.015≤d/a≤0.08…(v)
In the formula (v), d represents the storage modulus (unit: GPa) at 260 ℃ of a cured product of the resin composition, and a is the same as the above. In the present embodiment, the storage modulus at 260 ℃ of the cured product can be obtained by the same method as that of the above cured product, and can be measured by the DMA method according to JIS C6481. The specific measurement method is as described in examples.
When the cured product satisfies the relationship represented by the formula (v), the heat resistance of the cured product is further excellent. For example, it tends to exhibit sufficient heat resistance even when exposed to a high temperature of 300 ℃, and further, tends to be more excellent in handling property in a mounting process of mounting a semiconductor chip to a printed circuit board (e.g., a multilayer coreless substrate). From the same viewpoint, the lower limit value of d/a is more preferably 0.018 or more.
[ constituent Components of resin composition ]
(elastomer component)
The resin composition in the layer containing the resin composition according to the present embodiment may contain an elastomer component, but is not particularly limited. When the resin composition contains an elastomer component, the storage modulus of a cured product tends to decrease at a predetermined temperature. The elastomer component is not particularly limited, and examples thereof include acrylic rubber, silicone rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, polyisoprene rubber, urethane rubber, butyl rubber, and core shell rubber, other than the organic filler and other additives described later. These elastomer components can be used alone in 1 kind, or more than 2 kinds combined use.
The acrylic rubber is not particularly limited, and examples thereof include alkyl acrylates such as ethyl acrylate and butyl acrylate.
The silicone rubber is not particularly limited, and examples thereof include a copolymer containing dimethylsiloxane groups, methylvinyl groups, methylphenyl groups, and diphenylsiloxane groups, and polydimethylsiloxane composed of dimethylsiloxane groups only.
The core shell rubber is not particularly limited, and examples thereof include a methacrylate-styrene/butadiene rubber graft copolymer, an acrylonitrile-styrene/ethylene-propylene rubber graft copolymer, an acrylonitrile-styrene/acrylate ester graft copolymer, a methacrylate/acrylate ester rubber graft copolymer, and a methacrylate-acrylonitrile/acrylate ester rubber graft copolymer.
The content of the elastomer is not particularly limited, and is, for example, less than 30 parts by mass, preferably 25 parts by mass or less, more preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further more preferably 10 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. When the content is less than or equal to the above value, the heat resistance and water absorption of the obtained cured product tend to be further improved.
(short glass fiber having an average fiber length of 10 to 300 μm)
The resin composition in the layer containing the resin composition according to the present embodiment may contain short glass fibers having an average fiber length of 10 to 300 μm, but is not particularly limited. When the glass short fiber is contained in the resin composition, it tends to make it possible to obtain excellent adhesion to the copper foil, provide toughness to the layer comprising the resin composition, and have a low thermal expansion coefficient. In the present embodiment, the short glass fibers having an average fiber length of 10 to 300 μm are different from the inorganic filler described below. As such glass short fibers, SiO may be used2、Al2O3、CaO、MgO、B2O3、Na2O and K2O is a main component, and the average fiber length is 10 to 300. mu.m, but is not particularly limited.
The average fiber length of the short glass fibers is preferably 20 μm or more, and more preferably 30 μm or more, from the viewpoint of lowering the thermal expansion coefficient. In addition, from the viewpoint of improving the dispersibility of the short glass fibers, it is preferably 250 μm or less, more preferably 200 μm or less, and still more preferably 150 μm or less.
The average fiber diameter of the short glass fibers is not particularly limited, but is preferably 3 to 15 μm, more preferably 3 to 13 μm, and still more preferably 3.5 to 11 μm in view of making the thermal expansion coefficient lower.
The average fiber length and fiber diameter of the glass short fibers can be measured using an optical microscope, an electron microscope, or the like.
As specific examples of the glass short fibers, milled glass fibers (also called glass fiber powder), glass wool, and microfibers can be cited. As the glass short fibers, milled glass fibers are preferable because excellent adhesion to the copper foil can be obtained and the cost is low. These glass short fibers may be used in a mixture of 1 or 2 or more.
The glass short fibers may be commercially available ones. The commercially available product of the glass staple fibers is not particularly limited, and examples thereof include "EFH 30-01 (trade name)", "EFH 50-01 (trade name)", "EFH 30-31 (trade name)", "EFH 75-01 (trade name)", "EFH 100-31 (trade name)", "EFH 150-01 (trade name)", "EFH 150-31 (trade name)", "EFK 80-31 (trade name)", "EFDE 50-01 (trade name)", "EFDE 50-31 (trade name)" and "EFDE 90-01 (trade name)" manufactured by central glass fiber co.
The content of the glass short fiber is not particularly limited, and is preferably 5 to 450 parts by mass, and more preferably 10 to 400 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoints of the thermal expansion coefficient, toughness and moldability.
(cyanate ester compound, phenol compound, epoxy compound and maleimide compound)
The resin composition in the layer including the resin composition according to the present embodiment preferably contains at least 1 compound selected from the group consisting of a cyanate compound, a phenol compound, an epoxy compound, and a maleimide compound, but is not particularly limited. When these compounds are contained in the resin composition, the glass transition temperature, chemical resistance and peel strength of the resulting cured product tend to be improved. These compounds may be used alone in 1 kind, or in combination of 2 or more kinds. Among them, the compound preferably contains a cyanate compound and/or a phenol compound, and an epoxy compound and/or a maleimide compound, from the viewpoint of further improving the glass transition temperature, chemical resistance and peel strength of the obtained cured product. From the same viewpoint, the compound more preferably contains a phenol compound, and an epoxy compound and/or a maleimide compound.
(cyanate ester compound)
In the present embodiment, "cyanate ester compound" refers to a compound having 2 or more cyanate groups (cyanate ester groups) in 1 molecule, and "compound" is a concept covering a resin. The cyanate ester compound is not particularly limited as long as it is a compound having 2 or more cyanate groups (cyanate ester groups) in 1 molecule, and examples thereof include an aromatic hydrocarbon compound having 2 or more cyanate groups in 1 molecule, a compound in which 2 aromatic rings having 2 or more cyanate groups are connected by a linking group, a novolak type cyanate ester compound, a bisphenol type cyanate ester compound, a diallylbisphenol type cyanate ester compound (for example, a diallylbisphenol a type cyanate ester compound, a diallylbisphenol E type cyanate ester compound, a diallylbisphenol F type cyanate ester compound, a diallylbisphenol S type cyanate ester compound, etc.), an aralkyl type cyanate ester compound, and prepolymers of these cyanate esters. These cyanate ester compounds may be used alone in 1 kind, or in combination of 2 or more kinds. Among them, in view of further improving the glass transition temperature, chemical resistance and peel strength of the obtained cured product, an aralkyl cyanate ester compound is preferable, and an α -naphthol aralkyl cyanate ester compound and a biphenyl aralkyl cyanate ester compound described later are more preferable.
As the aromatic hydrocarbon compound having 2 or more cyanate groups in 1 molecule, for example, there can be mentioned compounds represented by the formula (I): ar- (OCN)p(wherein Ar represents any one of a benzene ring, a naphthalene ring and a biphenyl ring, and p represents an integer of 2 or more). The compound represented by the formula (I) is not particularly limited, and examples thereof include 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1,3, 5-tricarbonylbenzene, 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1, 6-dicyanobenzene, 1, 8-dicyanobenzene, 2, 6-dicyanobenzene, 2, 7-dicyanobenzene, 1,3, 6-tricarbonylnaphthalene and 4, 4' -dicyanateBiphenylene radicals and the like.
The compound in which 2 aromatic rings having 2 or more cyanate groups are linked via a linking group is not particularly limited, and examples thereof include bis (4-cyanate ylphenyl) ether, bis (4-cyanate ylphenyl) sulfide, and bis (4-cyanate ylphenyl) sulfone.
Examples of the novolak type cyanate ester compound include compounds represented by the following formula (1).
Figure BDA0003433176350000121
In the above formula (1), R1aEach independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R1bEach independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. n represents an integer of 1 to 10, preferably an integer of 1 to 7.
The compound represented by the above formula (1) is not particularly limited, and examples thereof include bis (3, 5-dimethyl 4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, and 2, 2' -bis (4-cyanatophenyl) propane.
These cyanate ester compounds may be used alone in 1 kind, or in combination of 2 or more kinds. Among them, the cyanate ester compound is preferably a bisphenol type cyanate ester compound and/or an aralkyl type cyanate ester compound from the viewpoint of further excellent heat resistance and low water absorption of the obtained cured product.
(bisphenol type cyanate ester compound)
The bisphenol type cyanate ester compound is not particularly limited, and examples thereof include a bisphenol a type cyanate ester compound, a bisphenol E type cyanate ester compound, a bisphenol F type cyanate ester compound, and a bisphenol S type cyanate ester compound.
The bisphenol cyanate ester compound may be a commercially available product or a product prepared by a known method. Examples of commercially available products of the bisphenol cyanate ester compound include "CA 210 (trade name)" manufactured by mitsubishi gas chemical corporation.
(aralkyl type cyanate ester compound)
The aralkyl type cyanate ester compound is not particularly limited, and examples thereof include an α -naphthol aralkyl type cyanate ester compound and a biphenyl aralkyl type cyanate ester compound.
Examples of the α -naphthol aralkyl type cyanate ester compound include compounds represented by the following formula (1 a).
Figure BDA0003433176350000131
In the above formula (1a), R1cEach independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. n1 represents an integer of 1 to 10, preferably an integer of 1 to 6.
Examples of the biphenylaralkyl cyanate ester compound include compounds represented by the following formula (1 b).
Figure BDA0003433176350000141
In the above formula (1b), R1dEach independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R1eEach independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. n2 represents an integer of 1 to 10, preferably an integer of 1 to 6.
The aralkyl cyanate ester compound may be a commercially available product or a product synthesized by a known method. Examples of the method for synthesizing the aralkyl cyanate ester compound include the following methods: a method of reacting a phenol resin corresponding to the target product aralkyl type cyanate ester compound (hereinafter also referred to as "corresponding phenol resin") with a halogenated cyanide compound and a basic compound in an inert organic solvent; and a method in which a salt formed by reacting a corresponding phenol resin with an alkaline compound in an aqueous solution and a halogenated cyanide are subjected to a two-phase system interfacial reaction. In either method, an aralkyl type cyanate ester compound can be obtained by cyanating the hydrogen atom of the phenolic hydroxyl group of the corresponding phenol resin. In more detail, for example, the method described in the examples and the like can be used.
The content of the cyanate ester compound is not particularly limited, and is preferably 10 to 45 parts by mass with respect to 100 parts by mass of the resin solid content. When the content is within the above range, the storage modulus during heating tends to be a value advantageous for suppressing warpage, and warpage of the metal foil-clad laminate, the printed circuit board, and the multilayer printed circuit board (e.g., multilayer coreless substrate) tends to be further reduced. From the same viewpoint, the lower limit of the content is more preferably 15 parts by mass, more preferably 20 parts by mass, and still more preferably 30 parts by mass, and the upper limit of the content is more preferably 40 parts by mass, and more preferably 35 parts by mass.
The cyanate equivalent of the cyanate ester compound is preferably 100g/eq to 500g/eq, more preferably 400g/eq or less, and still more preferably 300g/eq or less. When the cyanate equivalent is within the above range, the rigidity of the obtained cured product is more excellent, and the glass transition temperature and the storage modulus during heating tend to be values advantageous for suppressing warpage.
(phenol Compound)
In the present embodiment, "phenol compound" means a compound having 2 or more phenolic hydroxyl groups in 1 molecule, and "compound" is a concept covering a resin. The phenol compound is not particularly limited as long as it is a compound having 2 or more phenolic hydroxyl groups in 1 molecule, and examples thereof include phenols having 2 or more phenolic hydroxyl groups in 1 molecule, bisphenols (for example, bisphenol a, bisphenol E, bisphenol F, bisphenol S, etc.), diallylbisphenols (for example, diallylbisphenol a, diallylbisphenol E, diallylbisphenol F, diallylbisphenol S, etc.), bisphenol-type phenol resins (for example, bisphenol a-type resins, bisphenol E-type resins, bisphenol F-type resins, bisphenol S-type resins, etc.), phenol novolac resins (for example, phenol novolac resins, naphthol novolac resins, cresol novolac resins, etc.), glycidyl ester-type phenol resins, naphthalene-type phenol resins, anthracene-type phenol resins, dicyclopentadiene-type phenol resins, biphenyl-type phenol resins, alicyclic phenol resins, phenol resins having 2 or more phenolic hydroxyl groups in 1 molecule, phenol resins, bisphenol E, bisphenol F, bisphenol S, etc, Polyhydric alcohol type phenolic resin, aralkyl type phenolic resin, phenol modified aromatic formaldehyde resin and the like. These phenol compounds may be used alone in 1 kind, or in combination of 2 or more kinds. Among them, the phenol compound is preferably an aralkyl type phenol resin and/or a phenol-modified aromatic hydrocarbon formaldehyde resin, and more preferably a biphenyl aralkyl type phenol resin and/or a phenol-modified xylene resin, from the viewpoint of further improving the heat resistance and low water absorption of the obtained cured product.
(aralkyl type phenol resin)
Examples of the aralkyl type phenol resin include compounds represented by the following formula (2 a).
Figure BDA0003433176350000151
In the above formula (2a), Ar1Each independently represents a benzene ring or a naphthalene ring. Ar (Ar)2Represents a benzene ring, a naphthalene ring or a biphenyl ring. R2aEach independently represents a hydrogen atom or a methyl group. m represents an integer of 1 to 50. Each ring may have a substituent other than a hydroxyl group (e.g., an alkyl group having 1 to 5 carbon atoms, a phenyl group, etc.).
The compound represented by the above formula (2a) is preferably Ar in the above formula (2a) from the viewpoint of more excellent heat resistance and low water absorption of the obtained cured product1Is naphthalene ring, Ar2A compound which is a benzene ring (also referred to as "naphthol aralkyl type phenol resin") and Ar in the above (2a)1Is benzene ring, Ar2A compound which is a biphenyl ring (also referred to as "biphenyl aralkyl type phenol resin").
The naphthol aralkyl type phenol resin is preferably a compound represented by the following formula (2 b).
Figure BDA0003433176350000161
In the above formula (2b), R2aAnd R in the above formula (2a)2aLikewise, hydrogen atoms are preferred. M is the same as M in the formula (2a), and is preferably an integer of 1 to 10, more preferably an integer of 1 to 6.
The biphenyl aralkyl type phenol resin is preferably a compound represented by the following formula (2 c).
Figure BDA0003433176350000162
In the above formula (2c), R2bEach independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, preferably a hydrogen atom. m1 represents an integer of 1 to 20, preferably an integer of 1 to 6.
The aralkyl type phenol resin may be a commercially available one or one synthesized by a known method. Examples of commercially available aralkyl type phenol resins include "SN-495 (trade name)" (belonging to naphthol aralkyl type phenol resins represented by the formula (2 b)) manufactured by Nissan iron chemical Co., Ltd, "KAYAHARD (registered trademark) GPH-65 (trade name)", "KAYAHARD (registered trademark) GPH-78 (trade name)", and "KAYAHARD (registered trademark) GPH-103 (trade name)" (belonging to biphenyl aralkyl type phenol resins represented by the formula (2 c)).
(phenol-modified aromatic Formaldehyde resin)
In the present specification, the term "phenol-modified aromatic hydrocarbon-formaldehyde resin" refers to a resin obtained by heating an aromatic hydrocarbon-formaldehyde resin and a phenol in the presence of an acidic catalyst (for example, p-toluenesulfonic acid, oxalic acid, etc.) to cause a condensation reaction (modified condensation reaction).
The aromatic hydrocarbon formaldehyde resin is not particularly limited, and examples thereof include compounds obtained by condensation reaction of an aromatic hydrocarbon compound (for example, toluene, ethylbenzene, xylene, mesitylene, pseudocumene, monocyclic aromatic hydrocarbon compound having 10 or more carbon atoms, polycyclic aromatic hydrocarbon compound such as methylnaphthalene, and the like) with formaldehyde. Among them, xylene formaldehyde resins obtained by condensation reaction of xylene and formaldehyde are preferable.
The phenol is not particularly limited, and examples thereof include phenol, cresol, bisphenol propane, bisphenol methane, resorcinol, catechol, hydroquinone, p-tert-butylphenol, bisphenol sulfone, bisphenol ether, and p-phenol. These phenols may be used alone in 1 kind, or in combination of 2 or more kinds.
The phenol-modified aromatic hydrocarbon-formaldehyde resin is preferably a phenol-modified xylene-formaldehyde resin obtained by heating a xylene-formaldehyde resin and the phenol in the presence of the acidic catalyst to cause a condensation reaction, and more preferably a phenol-modified xylene-formaldehyde resin.
The phenol-modified aromatic hydrocarbon formaldehyde resin may be a commercially available product or a product prepared by a known method. Examples of commercially available products of the phenol-modified aromatic hydrocarbon formaldehyde resin include XISTAR (registered trademark) series "HP-120 (trade name)", "HP-100 (trade name)", "HP-210 (trade name)", "HP-70 (trade name)", "NP-100 (trade name)", "GP-212 (trade name)", "P-100 (trade name)", "GP-200 (trade name)", and "HP-30 (trade name)", manufactured by FUDOW corporation. Examples of known methods include the method described in Japanese patent laid-open publication No. 2015-174874.
The content of the phenol compound is not particularly limited, and is preferably 10 to 60 parts by mass per 100 parts by mass of the resin solid content. When the content is within the above range, the storage modulus during heating tends to be a value advantageous for suppressing warpage, and warpage of the metal foil-clad laminate, the printed circuit board, and the multilayer printed circuit board (e.g., multilayer coreless substrate) tends to be further reduced. From the same viewpoint, the lower limit of the content is more preferably 20 parts by mass, still more preferably 30 parts by mass, and the upper limit of the content is more preferably 55 parts by mass, still more preferably 50 parts by mass, and still more preferably 40 parts by mass.
The phenolic equivalent (hydroxyl equivalent of phenolic hydroxyl group) of the phenolic compound is preferably 500g/eq or less, more preferably 400g/eq or less, still more preferably 350g/eq or less, and particularly preferably 300g/eq or less. When the phenol equivalent is within the above range, the rigidity of the resulting cured product is more excellent, and the glass transition temperature and the storage modulus during heating tend to be values advantageous for suppressing warpage. The lower limit is not particularly limited, and may be 100g/eq or more.
(epoxy compound)
In the present embodiment, "epoxy compound" refers to a compound having 2 or more epoxy groups in 1 molecule, and "compound" is a concept covering a resin. The epoxy compound is not particularly limited as long as it has 1 epoxy group in a molecule of 2 or more, and examples thereof include bisphenol type epoxy resins (e.g., bisphenol a type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin), diallyl bisphenol type epoxy resins (e.g., diallyl bisphenol a type epoxy resin, diallyl bisphenol E type epoxy resin, diallyl bisphenol F type epoxy resin, and diallyl bisphenol S type epoxy resin), phenol novolac type epoxy resins (e.g., phenol novolac type epoxy resin, bisphenol a novolac type epoxy resin, and cresol novolac type epoxy resin), aralkyl type epoxy resins, biphenyl type epoxy resins having a biphenyl skeleton, naphthalene type epoxy resins having a naphthalene skeleton, anthracene type epoxy resins having an anthracene skeleton, epoxy resins having a diallyl bisphenol a novolac skeleton, and the like), phenol novolac type epoxy resins, and the like, Glycidyl ester type epoxy resin, polyol type epoxy resin, isocyanurate ring-containing epoxy resin, dicyclopentadiene type epoxy resin, epoxy resin comprising a bisphenol A type structural unit and a hydrocarbon type structural unit, and halogenated compounds thereof. These epoxy compounds may be used alone in 1 kind, or in combination of 2 or more kinds. Among them, from the viewpoint of more excellent heat resistance and low water absorption of the resulting cured product, 1 or more selected from the group consisting of aralkyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, and epoxy resins composed of bisphenol a type structural units and hydrocarbon type structural units are preferable. In the present embodiment, from the viewpoint of the storage modulus during heating being a value more advantageous for suppressing warpage, 2 or more epoxy compounds are preferably contained, and 2 or more epoxy compounds preferably contain a naphthalene-type epoxy resin and/or an aralkyl-type epoxy resin having a naphthalene skeleton, and more preferably contain a naphthalene-type epoxy resin and an aralkyl-type epoxy resin. The aralkyl type epoxy resin is more preferably a biphenyl aralkyl type epoxy resin.
(aralkyl type epoxy resin)
As aralkyl type
Examples of the epoxy resin include compounds represented by the following formula (3 a).
Figure BDA0003433176350000191
In the above formula (3a), Ar3Each independently represents a benzene ring or a naphthalene ring. Ar (Ar)4Represents a benzene ring, a naphthalene ring or a biphenyl ring. R3aEach independently represents a hydrogen atom or a methyl group. k represents an integer of 1 to 50. Each ring may have a substituent other than a glycidyloxy group (for example, an alkyl group having 1 to 5 carbon atoms or a phenyl group).
The compound represented by the above formula (3a) is preferably Ar in the above formula (3a) from the viewpoint of more excellent heat resistance and low water absorption of the obtained cured product3Is naphthalene ring, Ar4A compound which is a benzene ring (also referred to as "naphthylaralkyl type epoxy resin") and Ar3Is benzene ring, Ar4The compound which is a biphenyl ring (also referred to as "biphenyl aralkyl type epoxy resin"), more preferably a biphenyl aralkyl type epoxy resin.
The aralkyl type epoxy resin may be a commercially available one or a preparation prepared by a known method. Examples of commercially available products of the naphthylaralkyl type epoxy resin include "Epotohto (registered trademark) ESN-155 (trade name)", "Epotohto (registered trademark) ESN-355 (trade name)", "Epotohto (registered trademark) ESN-375 (trade name)", "Epotohto (registered trademark) ESN-475V (trade name)", "Epotohto (registered trademark) ESN-485 (trade name)" and "Epotohto (registered trademark) ESN-175 (trade name)", manufactured by Nippon Tekko chemical Co., Ltd., "NC-7000 (trade name)", "NC-7300 (trade name)" and "NC-7300L (trade name)", manufactured by Nippon Kabushiki Kaisha, "HP-5000 (trade name)", "HP-9900 (trade name)", "HP-9540 (trade name)" and "HP-9500 (trade name)" manufactured by DIC corporation, and the like. Examples of the biphenylene group as a commercially available product of the alkyl-type epoxy resin include "NC-3000 (trade name)", "NC-3000L (trade name)", and "NC-3000 FH (trade name)" manufactured by Nippon Kagaku corporation.
The biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (3b) from the viewpoint of more excellent heat resistance and low water absorption of the obtained cured product.
Figure BDA0003433176350000201
In the formula (3b), ka represents an integer of 1 or more, preferably an integer of 1 to 20, and more preferably an integer of 1 to 6.
Further, the aralkyl type epoxy resin is preferably a compound represented by the following formula (3 c).
Figure BDA0003433176350000202
In the formula (3c), ky represents an integer of 1 to 10. Me represents a methyl group.
(naphthalene type epoxy resin)
The naphthalene type epoxy resin is not particularly limited, and examples thereof include, among epoxy resins other than the above-mentioned naphthalene aralkyl type epoxy resin, a naphthalene skeleton-containing polyfunctional epoxy resin having a naphthalene skeleton represented by the following formula (3d) and an epoxy resin having a naphthalene skeleton (for example, an epoxy resin represented by the following formula (3 e)). Specific examples of the naphthalene type epoxy resin include, for example, a naphthalene ether type epoxy resin, and the naphthalene ether type epoxy resin is preferable from the viewpoint of further excellent heat resistance and low water absorption of the resulting cured product.
Figure BDA0003433176350000211
In the above formula (3d), Ar31Each independently represents a benzene ring or a naphthalene ring. Ar (Ar)41Represents a benzene ring, a naphthalene ring or a biphenyl ring. R31aEach independently represents a hydrogen atom or a methyl group. p represents an integer of 0 to 2, preferably 0 or 1. kz represents an integer of 1 to 50. Each ring may have a substituent other than glycidyloxy (e.g.C1-C5 alkyl, alkoxy, or phenyl), Ar31And Ar41At least one of (a) is a naphthalene ring.
Examples of the compound represented by the formula (3d) include compounds represented by the following formula (3 f).
Figure BDA0003433176350000212
In the formula (3f), kz is synonymous with kz in the formula (3 d).
The naphthalene skeleton-containing polyfunctional epoxy resin may be a commercially available one, or a preparation prepared by a known method may be used. Examples of commercially available products of the naphthalene skeleton-containing polyfunctional epoxy resin include "HP-9540 (trade name)" and "HP-9500 (trade name)" manufactured by DIC corporation.
Figure BDA0003433176350000213
The epoxy resin represented by the above formula (3e) may be a commercially available one or a preparation prepared by a known method. Examples of commercially available products include "HP-4710 (trade name)" manufactured by DIC.
(Naphthalene ether type epoxy resin)
Examples of the naphthalene ether type epoxy resin include compounds represented by the following formula (3 g).
Figure BDA0003433176350000221
In the above formula (3g), R3bEach independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aralkyl group, a naphthyl group or a naphthyl group containing a glycidyloxy group. k1 represents an integer of 1 to 10.
In the compound represented by the formula (3g), the number of glycidyloxy groups containing an epoxy group in the molecule is preferably 2 to 6, more preferably 2 to 4.
In the above formula (3g), k1 represents an integer of 0 to 10, and k1 preferably represents an integer of 0 to 6, more preferably 0 to 4, and even more preferably 2 to 3, from the viewpoint of more effectively and reliably producing the operational effect of the present embodiment.
In the above formula (3g), R is preferably used from the viewpoint of more effectively and reliably producing the operation and effect of the present embodiment3bEach independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aralkyl group, or a naphthyl group.
When the naphthyl ether epoxy resin contains the compound represented by the above formula (3g), the naphthyl ether epoxy resin may contain a plurality of compounds having the same k1, or may contain a plurality of compounds having different k 1. When the naphthyl ether epoxy resin contains a plurality of compounds having different k1, the naphthyl ether epoxy resin preferably contains a compound having k1 of an integer of 0 to 4 in the formula (3g), and more preferably contains a compound having k1 of an integer of 2 to 3.
Examples of the compound represented by the formula (3g) include a compound represented by the following formula (3 h).
Figure BDA0003433176350000222
The epoxy resin represented by the above formula (3h) may be a commercially available one or a preparation prepared by a known method. Examples of commercially available products include "HP-4032 (trade name)" manufactured by DIC.
The naphthalene ether type epoxy resin may be a commercially available one or a prepared one prepared by a known method. Examples of commercially available products of the naphthalene ether type epoxy resin include "HP-4032 (trade name)", "HP-6000 (trade name)", "EXA-7300 (trade name)", "EXA-7310 (trade name)", "EXA-7311L (trade name)" and "EXA 7311-G3 (trade name)" manufactured by DIC corporation.
(dicyclopentadiene type epoxy resin)
Examples of the dicyclopentadiene type epoxy resin include compounds represented by the following formula (3 i).
Figure BDA0003433176350000231
In the above formula (3i), R3cEach independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. k2 represents an integer of 0 to 10.
In the above formula (3i), k2 represents an integer of 0 to 10, and is preferably an integer of 0 to 6, more preferably an integer of 0 to 2, and still more preferably 0 to 1, from the viewpoint of more effectively and reliably producing the operational effect of the present embodiment.
When the dicyclopentadiene type epoxy resin contains the compound represented by the above formula (3i), the resin may contain a plurality of compounds having the same k2 or a plurality of compounds having different k 2. When the dicyclopentadiene type epoxy resin contains a plurality of compounds having different k2, it is preferable to contain a compound in which k2 is an integer of 0 to 2 in the formula (3 i).
The dicyclopentadiene type epoxy resin may be a commercially available one or a prepared one prepared by a known method. Commercially available dicyclopentadiene type epoxy resins include "EPICRON (registered trademark) HP-7200L (trade name)", "EPICRON (registered trademark) HP-7200H (trade name)", and "EPICRON (registered trademark) HP-7000HH (trade name)" manufactured by Dainippon ink chemical industries, Ltd.
(epoxy resin comprising bisphenol A structural units and hydrocarbon structural units)
An epoxy resin (also referred to as a "specific epoxy resin") composed of a bisphenol a structural unit and a hydrocarbon structural unit has 1 or more bisphenol a structural units and 1 or more hydrocarbon structural units in a molecule. Examples of the specific epoxy resin include compounds represented by the following formula (3 j).
Figure BDA0003433176350000241
In the above formula (3j), R1xAnd R2xEach independently represents a hydrogen atom or a methyl group. R3x～R6xEach independently represents a hydrogen atom, a methyl group, a chlorine atom or a bromine atom. X represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, or an alkylene group having 2 to 15 carbon atoms. k3 represents an integer.
In the above formula (3j), k3 represents an integer, and is preferably an integer of 1 to 10, more preferably an integer of 1 to 6, even more preferably an integer of 1 to 2, and particularly preferably 1, from the viewpoint of more effectively and reliably producing the operational effect of the present embodiment.
In the formula (3j), X is preferably an ethylene group from the viewpoint of more effectively and reliably producing the operation and effect of the present embodiment.
The specific epoxy resin may be a commercially available one or a preparation prepared by a known method. Examples of commercially available products of the specific epoxy resin include "EPICLON (registered trademark) EXA-4850-" and "EPICLON (registered trademark) EXA-4816 (trade name)" manufactured by DIC corporation.
The content of the epoxy compound is not particularly limited, and is preferably 10 to 80 parts by mass with respect to 100 parts by mass of the resin solid content. When the content is within the above range, the storage modulus during heating tends to be a value advantageous for suppressing warpage, and warpage of the metal foil-clad laminate, the printed circuit board, and the multilayer printed circuit board (e.g., multilayer coreless substrate) tends to be further reduced. When the content is within the above range, the rigidity, heat resistance and low water absorption of the resulting cured product tend to be further improved. From the same viewpoint, the lower limit of the content is more preferably 20 parts by mass, more preferably 25 parts by mass, still more preferably 30 parts by mass, and particularly preferably 45 parts by mass, and the upper limit of the content is more preferably 75 parts by mass, more preferably 64 parts by mass, still more preferably 70 parts by mass, and particularly preferably 55 parts by mass.
The epoxy equivalent of the epoxy compound is preferably 500g/eq or less, more preferably 400g/eq or less, and still more preferably 350g/eq or less. When the epoxy equivalent is within the above range, the rigidity of the resulting cured product is more excellent, and the glass transition temperature and the storage modulus during heating tend to be values advantageous for suppressing warpage. The lower limit is not particularly limited, but is preferably 100g/eq or more.
When the resin composition contains a phenol compound and/or a cyanate ester compound and an epoxy compound, the ratio of the amount of phenol groups (contained parts by mass/phenol equivalent) and/or the amount of cyanate ester groups (contained parts by mass/cyanate ester equivalent) in the resin composition to the amount of epoxy groups (contained parts by mass/epoxy equivalent) in the resin composition is preferably 0.5 to 1.5. When the resin composition contains both a phenol compound and a cyanate ester compound, the ratio is a ratio of the total amount of the phenol group and the cyanate ester group to the amount of the epoxy group. When the ratio is within the above range, the storage modulus upon heating tends to be a value advantageous for suppressing warpage. From the same viewpoint, the lower limit of the ratio is preferably 0.5, more preferably 0.6, more preferably 0.7, and still more preferably 0.9. The upper limit value of the ratio is preferably 1.5, more preferably 1.4, more preferably 1.3, and further more preferably 1.2. When there are a plurality of phenol compounds, the amount of the phenol group means the total amount of the phenol groups of the respective phenol compounds; when there are a plurality of cyanate ester compounds, the above cyanate ester group amount means the sum of the cyanate ester group amounts of the respective cyanate ester compounds; when there are a plurality of epoxy compounds, the epoxy group amount refers to the sum of the epoxy group amounts of the respective epoxy compounds.
(Maleimide Compound)
In the present embodiment, "maleimide compound" refers to a compound having 1 or more maleimide groups in 1 molecule, and "compound" is a concept covering a resin. The maleimide compound is not particularly limited as long as it is a compound having 1 or more maleimide groups in 1 molecule, and examples thereof include maleimide compounds such as a monomaleimide compound having 1 maleimide group in 1 molecule (e.g., N-phenylmaleimide, N-hydroxyphenylmaleimide and the like), polymaleimide compounds having 2 or more maleimide groups in 1 molecule (e.g., bis (4-maleimidophenyl) methane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane and polyphenylmethane compounds), And prepolymers of these maleimide compounds and amine compounds. These maleimide compounds may be used alone in 1 kind, or in combination of 2 or more kinds. Among them, the maleimide compound is preferably a polymaleimide compound from the viewpoint of further improving the heat resistance and glass transition temperature of the obtained cured product.
Examples of the polymaleimide compound include compounds having a plurality of maleimide groups linked to a benzene ring (e.g., phenylenebismaleimides such as m-phenylenebismaleimide, and 4-methyl-1, 3-phenylenebismaleimide), compounds having maleimide groups linked to both ends of a straight or branched alkyl chain (e.g., 1, 6-bismaleimide- (2,2, 4-trimethyl) hexane), bisphenol a diphenyl ether bismaleimide, and compounds represented by the following formula (4 a).
Figure BDA0003433176350000261
In the above formula (4a), R4aAnd R5aEach independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom. R4bEach independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. s represents an integer of 1 or more. The upper limit of s is not particularly limited, but is preferably an integer of 10 or less, and more preferably an integer of 7 or less.
Examples of the compound represented by the formula (4a) include bis (4-maleimidophenyl) methane, 2, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane and bis (3-ethyl-5-methyl-4-maleimidophenyl) methane. When the maleimide compound contains the maleimide compound represented by the above formula (4a), the thermal expansion coefficient of the obtained cured product tends to be further lowered, and the heat resistance and the glass transition temperature (Tg) tend to be further increased. The maleimide compound may be used alone in 1 kind, or in combination of 2 or more kinds.
As the maleimide compound, commercially available compounds or preparations prepared by known methods can be used. As the maleimide compound, commercially available products such as "BMI-70 (trade name)", "BMI-80 (trade name)", BMI-2300 (trade name) ", BMI-1000P (trade name)", "BMI-3000 (trade name)", "BMI-4000 (trade name)", "BMI-5100 (trade name)", and "BMI-7000 (trade name)" manufactured by KI Kabushiki Kaisha can be mentioned.
The content of the maleimide compound is not particularly limited, and is preferably 1 to 45 parts by mass per 100 parts by mass of the resin solid content. When the content is within the above range, the resulting cured product tends to have a lower water absorption and more excellent properties, and the warpage of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) can be further reduced. From the same viewpoint, the lower limit of the content is more preferably 4 parts by mass, more preferably 10 parts by mass, and still more preferably 15 parts by mass, and the upper limit of the content is more preferably 40 parts by mass, more preferably 30 parts by mass, still more preferably 25 parts by mass, and particularly preferably 20 parts by mass.
(other resins)
The resin composition in the layer containing the resin composition according to the present embodiment may contain other resins, and is not particularly limited. Examples of the other resin include an alkenyl-substituted nadiimide compound, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. These resins may be used alone in 1 kind, or in combination of 2 or more kinds.
(alkenyl substituted nadimide Compound)
In the present specification, the "alkenyl-substituted nadimide compound" refers to a compound having 1 or more alkenyl-substituted nadimide groups in the molecule. Examples of the alkenyl-substituted nadimide compound include compounds represented by the following formula (5 a).
Figure BDA0003433176350000271
In the above formula (5a), R6aEach independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R6bRepresents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by the following formula (5b) or (5 c).
Figure BDA0003433176350000281
In the above formula (5b), R6cRepresenting methylene, isopropylidene, or from CO, O, S or SO2Divalent substituents as indicated.
Figure BDA0003433176350000282
In the above formula (5c), R6dEach independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.
Further, examples of the alkenyl-substituted nadimide compound include compounds represented by the following formulae (6) and/or (7).
Figure BDA0003433176350000283
The alkenyl-substituted nadiimide compound may be a commercially available compound or a product prepared by a known method. The commercially available product of the alkenyl-substituted nadimide compound is not particularly limited, and examples thereof include "BANI-M (trade name)" and "BANI-X (trade name)" manufactured by Wanshan petrochemical Co.
These alkenyl-substituted nadimide compounds may be used alone in 1 kind, or in combination of 2 or more kinds.
(Oxetane resin)
Examples of the oxetane resin include oxetane, 2-methyloxetane, 2-dimethyloxetane, 3-methyloxetane, alkyl oxetane such as 3, 3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3' -bis (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3-bis (chloromethyl) oxetane, biphenyl-type oxetane and "OXT-101 (trade name)" and "OXT-121 (trade name)" manufactured by Toyao Kabushiki Kaisha.
These oxetane resins may be used alone in 1 kind, or in combination of 2 or more kinds.
(benzoxazine compound)
The "benzoxazine compound" as used herein refers to a compound having 2 or more dihydrobenzoxazine rings in 1 molecule. Examples of the benzoxazine compound include "bisphenol F-type benzoxazine BF-BXZ (trade name)" and "bisphenol S-type benzoxazine BS-BXZ (trade name)" manufactured by Michelia chemical Co., Ltd.
These オ benzoxazine compounds may be used alone in 1 kind, or in combination of 2 or more kinds.
(Compound having polymerizable unsaturated group)
Examples of the compound having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene and divinylbiphenyl; (meth) acrylates of monohydric or polyhydric alcohols such as methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate; epoxy (meth) acrylates such as bisphenol a type epoxy (meth) acrylate and bisphenol F type epoxy (meth) acrylate; benzocyclobutene resins, and the like.
These compounds having a polymerizable unsaturated group may be used alone in 1 kind, or in combination of 2 or more kinds.
These other resins are not particularly limited, but are preferably 1 to 30 parts by mass, respectively, based on 100 parts by mass of the solid resin component.
(Filler)
The resin composition in the layer containing the resin composition according to the present embodiment preferably contains a filler, but is not particularly limited. Examples of the filler include an inorganic filler and/or an organic filler.
The inorganic filler is not particularly limited, and examples thereof include silica, silicon compounds (e.g., white carbon), metal oxides (e.g., alumina, titanium white, zinc oxide, magnesium oxide, and zirconium oxide), metal nitrides (e.g., boron nitride, solidified boron nitride, silicon nitride, and aluminum nitride), metal sulfates (e.g., barium sulfate), metal hydroxides (e.g., aluminum hydroxide and aluminum hydroxide heat-treated products (e.g., products obtained by heat-treating aluminum hydroxide to reduce partial crystal water), boehmite, and magnesium hydroxide), molybdenum compounds (e.g., molybdenum oxide, and zinc molybdate), zinc compounds (e.g., zinc borate, and zinc stannate), clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, and the like, L-glass, D-glass, S-glass, M-glass G20, glass short fibers (including glass particles such as E-glass, T-glass, D-glass, S-glass, and Q-glass), hollow glass, spherical glass, and the like. These inorganic fillers may be used alone in 1 kind, or in combination of 2 or more kinds. Among them, the filler is preferably at least 1 selected from the group consisting of silica, metal hydroxide and metal oxide, more preferably at least 1 selected from the group consisting of silica, boehmite and alumina, and even more preferably silica, from the viewpoint of further improving the rigidity of the obtained cured product and further reducing the warpage of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate).
Examples of the silica include natural silica, fused silica, synthetic silica, amorphous silica, fumed silica, and hollow silica. Among these, spherical fused silica is preferable from the viewpoint of further improving the rigidity of the obtained cured product and further reducing the warpage of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate). Examples of commercially available spherical fused silica include SC2050-MB (trade name), SC5050-MOB (trade name), SC2500-SQ (trade name), SC4500-SQ (trade name), SC5050-MOB (trade name), SO-C2 (trade name), SO-C1 (trade name), and SFP-130MC (trade name) manufactured by electrochemical industries, Inc.
The organic filler is not particularly limited, and examples thereof include rubber powders such as styrene powders, butadiene powders and acrylic powders; core-shell rubber powder; silicone-based powders, and the like. These organic fillers may be used alone in 1 kind, or in combination of 2 or more kinds. Among these, silicone-based powders are preferable from the viewpoint of further improving the rigidity of the resulting cured product and further reducing the warpage of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate).
Examples of the silicone powder include a silicone resin powder, a silicone rubber powder, and a silicone composite powder. These silicone powders may be used alone in 1 kind, or in combination of 2 or more kinds. Among these, the silicone composite powder is preferable from the viewpoint of further improving the rigidity of the obtained cured product and further reducing the warpage of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate). Examples of the silicone composite powder include KMP-600 (trade name), KMP-601 (trade name), KMP-602 (trade name), KMP-605 (trade name), and X-52-7030 (trade name), which are manufactured by Nissan chemical Co., Ltd.
The content of the silicone powder is not particularly limited, and is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the resin solid content. When the content is within the above range, the rigidity of the resulting cured product tends to be further improved, and the warpage of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) can be further reduced. From the same viewpoint, the lower limit of the content is more preferably 10 parts by mass, still more preferably 15 parts by mass, and the upper limit of the content is more preferably 50 parts by mass, still more preferably 40 parts by mass, and still more preferably 30 parts by mass.
The filler of the present embodiment preferably includes an inorganic filler and an organic filler. This tends to result in a cured product having more excellent rigidity, and can further reduce warpage of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate).
The content of the inorganic filler is not particularly limited, and is preferably 90 to 700 parts by mass with respect to 100 parts by mass of the resin solid content. When the content is within the above range, the rigidity of the resulting cured product tends to be further improved, the warpage of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) can be further reduced, and the above formulae (i), (ii) and (iii) can be controlled to be within desired ranges. From the same viewpoint, the lower limit of the content is more preferably 120 parts by mass, and still more preferably 140 parts by mass; the upper limit of the content is more preferably 600 parts by mass, still more preferably 500 parts by mass, and still more preferably 250 parts by mass.
When the resin composition contains an organic filler, the content of the organic filler is not particularly limited, and is preferably 1 to 50 parts by mass per 100 parts by mass of the resin solid content. When the content is within the above range, the rigidity of the resulting cured product tends to be further improved, and the warpage of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) can be further reduced. From the same viewpoint, the lower limit of the content is more preferably 5 parts by mass, and still more preferably 10 parts by mass; the upper limit of the content is more preferably 40 parts by mass, still more preferably 30 parts by mass, and still more preferably 25 parts by mass.
The total content of the filler is not particularly limited, and is preferably 100 to 700 parts by mass with respect to 100 parts by mass of the resin solid content. When the content is within the above range, the rigidity of the resulting cured product tends to be further improved, and the warpage of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) can be further reduced. From the same viewpoint, the lower limit of the content is more preferably 130 parts by mass, and still more preferably 150 parts by mass; the upper limit of the content is more preferably 600 parts by mass, still more preferably 500 parts by mass, and still more preferably 250 parts by mass.
(silane coupling agent)
The resin composition in the layer containing the resin composition according to the present embodiment preferably contains a silane coupling agent, but is not particularly limited. In the present embodiment, when the silane coupling agent is contained, the dispersibility of the filler tends to be further improved, and the adhesion strength between the component of the resin composition in the layer containing the resin composition according to the present embodiment and the substrate described later can be further improved.
The silane coupling agent is not particularly limited, and examples thereof include silane coupling agents conventionally used for surface treatment of inorganic materials, such as aminosilane compounds (e.g., γ -aminopropyltriethoxysilane and N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane), epoxy silane compounds (e.g., γ -glycidoxypropyltrimethoxysilane), acrylate silane compounds (e.g., γ -acryloxypropyltrimethoxysilane), cationic silane compounds (e.g., N- β - (N-vinylbenzylaminoethyl) - γ -aminopropyltrimethoxysilane hydrochloride), and phenyl silane compounds. These silane coupling agents may be used alone in 1 kind, or in combination of 2 or more kinds. Among them, the silane coupling agent is preferably an epoxy silane compound. Examples of the epoxy silane compound include "KBM-403 (trade name)", "KBM-303 (trade name)", "KBM-402 (trade name)" and "KBE-403 (trade name)" manufactured by shin-Etsu chemical Co., Ltd.
The content of the silane coupling agent is not particularly limited, and is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin solid content.
(wetting and dispersing agent)
The resin composition in the layer containing the resin composition according to the present embodiment preferably contains a wetting dispersant, but is not particularly limited. In the present embodiment, when the wetting dispersant is contained, the dispersibility of the filler tends to be further improved, the rigidity of the obtained cured product is further improved, and the warpage of the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (for example, a multilayer coreless substrate) can be further reduced.
As the wetting dispersant, a known dispersant (dispersion stabilizer) that can be used for dispersing the filler may be used, and examples thereof include DISPERBYK (registered trademark) -110 (trade name), 111 (trade name), 118 (trade name), 180 (trade name), 161 (trade name), W996 (trade name), W9010 (trade name), and W903 (trade name) manufactured by japan large chemical corporation. These wetting and dispersing agents may be used alone in 1 kind, or in combination of 2 or more kinds.
The content of the wetting dispersant is not particularly limited, but is preferably 1 to 5 parts by mass with respect to 100 parts by mass of the resin solid content. When the content is within the above range, the dispersibility of the filler tends to be further improved, the rigidity of the obtained cured product is further improved, and the warpage of the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (for example, multilayer coreless substrate) can be further reduced. From the same viewpoint, the lower limit of the content is more preferably 1.5 parts by mass, and still more preferably 2 parts by mass.
(curing accelerators)
The resin composition in the layer containing the resin composition according to the present embodiment preferably contains a curing accelerator, but is not particularly limited. The curing accelerator is not particularly limited, and examples thereof include imidazoles (e.g., triphenylimidazole), organic peroxides (e.g., benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl perphthalate, etc.), azo compounds (e.g., azodinitrile), tertiary amines (e.g., N-dimethylbenzylamine, N-dimethylaniline, N-dimethyltoluidine, N-lutidine, 2-N-ethylanilinoethanol, tri-N-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine, etc.), phenols (e.g., phenol, xylenol, cresol, resorcinol, catechol, etc.), organic metal salts (e.g., lead naphthenate, and the like, Lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate, and the like), products of these organic metal salts dissolved in hydroxyl group-containing compounds such as phenol, bisphenol, and the like, inorganic metal salts (e.g., tin chloride, zinc chloride, aluminum chloride, and the like), organic tin compounds (e.g., dioctyltin oxide, other alkyltin, and alkyltin oxide, and the like). These curing accelerators may be used alone in 1 kind, or in combination of 2 or more kinds. Among them, the curing accelerator is preferably 2,4, 5-triphenylimidazole from the viewpoint of accelerating the curing reaction and further improving the glass transition temperature (Tg) of the resulting cured product.
The content of the curing accelerator is not particularly limited, and is preferably 0.1 to 5 parts by mass per 100 parts by mass of the resin solid content.
(other additives)
The resin composition in the layer containing the resin composition according to the present embodiment may contain various polymer compounds such as thermosetting resins, thermoplastic resins and oligomers thereof, and elastomers, which are not described above, within a range that does not impair the characteristics of the present embodiment; the additives and the like which are not listed before are not particularly limited. These are not particularly limited as long as they are conventionally used. The additives are not particularly limited, and examples thereof include an ultraviolet absorber, an antioxidant, a photopolymerization initiator, brightener, a photosensitizer, a dye, a pigment, a thickener, a flow control agent, a lubricant, an antifoaming agent, a dispersant, a leveling agent, a brightener, a polymerization inhibitor, and the like. These other additives may be used alone in 1 kind, or 2 or more kinds may be appropriately mixed and used.
The content of the other additives is not particularly limited, and is usually 0.1 to 10 parts by mass per 100 parts by mass of the resin solid content.
(solvent)
The resin composition in the layer containing the resin composition according to the present embodiment may contain a solvent, but is not particularly limited. When the resin composition of the present embodiment contains a solvent, the viscosity at the time of production of the resin composition tends to be lowered, the handling property (workability) tends to be further improved, and the impregnation property with respect to the base material tends to be further improved.
The solvent is not particularly limited as long as it can dissolve a part or all of the resin in the resin composition, and examples thereof include ketones (acetone, methyl ethyl ketone, methyl cellosolve, etc.), aromatic hydrocarbons (toluene, xylene, etc., for example), amides (dimethyl formaldehyde, etc., for example), propylene glycol monomethyl ether and acetate thereof. These solvents may be used alone in 1 kind, or in combination of 2 or more kinds.
(method for producing resin composition)
Examples of the method for producing the resin composition in the layer containing the resin composition according to the present embodiment include the following methods: the components are mixed with a solvent at once or in portions and stirred, and the mixture is obtained in the form of a varnish in which the components are dissolved or dispersed in the solvent. In this case, known processes such as stirring, mixing, and kneading may be employed in order to uniformly dissolve or disperse the respective components. The solvent is as described above. The specific manufacturing method can refer to the examples.
(method for producing resin sheet)
The method for producing a resin sheet according to the present embodiment is preferably a method for conventionally producing a composite of a layer containing a B-stage resin composition and a support. Specifically, for example, the following methods can be mentioned: the resin composition according to the present embodiment is prepared in the form of a varnish, and the varnish is applied to a support such as a copper foil by a known method such as a bar coater, and then semi-cured by heating in a drier at 100 to 200 ℃ for 1 to 60 minutes, to produce a resin sheet. The specific manufacturing method can refer to the examples. The thickness of the layer containing the resin composition is not particularly limited, but is preferably in the range of 1.0 μm to 300 μm.
[ use ]
As described above, the resin sheet of the present embodiment can sufficiently reduce warpage of the metal foil-clad laminate, the printed circuit board, and the multilayer printed circuit board (for example, a multilayer coreless substrate), and can exhibit excellent rigidity and heat resistance. Therefore, the resin sheet of the present embodiment can be used for, for example, a metal foil-clad laminate, a printed circuit board, and a multilayer printed circuit board. The resin composition of the present embodiment can also be advantageously used as an insulating layer or a laminate of a printed wiring board and the like.
[ laminated sheet ]
In the present embodiment, the resin sheet of the present embodiment can be used for a laminated plate. The laminate is a laminate having 1 or more layers containing a cured product of the resin composition in the resin sheet of the present embodiment, and when a plurality of layers are provided, the layers containing the cured product are in a laminated form or a laminated form with a conductive layer such as a metal foil interposed therebetween. By using the resin sheet of the present embodiment, the laminated board has sufficiently reduced warpage and excellent rigidity and heat resistance.
[ Metal-clad laminate ]
The metal foil-clad laminate of the present embodiment is a metal foil provided on one or both sides of a layer containing a cured product of the resin composition in the resin sheet of the present embodiment. The metal foil-clad laminate of the present embodiment has 1 or more layers containing a cured product of the resin composition in the resin sheet of the present embodiment. When the number of layers containing a cured product is 1, the metal foil-clad laminate has a form in which a metal foil is provided on one or both surfaces of the layer containing a cured product. When the number of layers containing a cured product is large, the metal foil-clad laminate has a form in which a metal foil is provided on one or both surfaces of the laminated layers containing a cured product. By using the resin sheet of the present embodiment, the metal foil-clad laminate of the present embodiment has sufficiently reduced warpage and excellent rigidity and heat resistance.
As the metal foil (conductor layer), metal foils used for various printed circuit board materials may be mentioned, and examples thereof include metal foils such as copper and aluminum, and as the metal foil of copper, copper foils such as rolled copper foil and electrolytic copper foil may be mentioned. The thickness of the conductor layer is, for example, 1 to 70 μm, preferably 1.5 to 35 μm.
The method of molding the laminate and the metal foil-clad laminate and the molding conditions thereof are not particularly limited, and the method and conditions of the conventional laminate and multilayer board for printed wiring boards can be applied. For example, laminated plates or metal-cladThe foil laminate can be formed by a multistage press, a multistage vacuum press, a continuous forming machine, an autoclave forming machine, or the like. In the molding (lamination molding) of the laminate or the metal foil-clad laminate, the temperature is generally 100 to 300 ℃ and the pressure is generally 2kgf/cm2～100kgf/cm2And a heating time ranging from 0.05 hour to 5 hours. If necessary, the post-curing may be carried out at a temperature of 150 to 300 ℃. For example, when a multistage press is used, the temperature is preferably 200 to 250 ℃ and the pressure is preferably 10kgf/cm from the viewpoint of sufficiently accelerating the curing of the resin composition in the resin sheet2～40kgf/cm2And a heating time of 80 to 130 minutes, more preferably 215 to 235 ℃ and a pressure of 25kgf/cm2～35kgf/cm2And the heating time is 90 to 120 minutes. In the resin sheet of the present embodiment, a layer containing a cured product of the resin composition and a separately produced wiring board for an inner layer are combined and then laminated and molded to form a multilayer board.
[ printed Circuit Board ]
The printed wiring board of the present embodiment includes an insulating layer formed from a cured product of the resin composition and a conductor layer formed on a surface of the insulating layer in the resin sheet of the present embodiment. The printed wiring board of the present embodiment can be formed by, for example, etching the metal foil of the metal foil-clad laminate of the present embodiment into a predetermined wiring pattern to form a conductor layer. By using the resin sheet of the present embodiment, the printed circuit board of the present embodiment has sufficiently reduced warpage and excellent rigidity and heat resistance.
The printed circuit board of the present embodiment can be manufactured by, for example, the following method. First, the metal foil-clad laminate of the present embodiment is prepared. The metal foil of the metal foil-clad laminate is etched into a predetermined wiring pattern to produce an inner layer substrate having a conductor layer (inner layer circuit). Next, on the surface of the conductor layer (built-in circuit) of the inner layer substrate, a predetermined number of layers containing the resin composition in the prepreg or resin sheet and the outer layer circuit metal foil are laminated in this order, and integrated molding (lamination molding) is performed by heating and pressing to obtain a laminate. The method of lamination molding and the molding conditions thereof are the same as those of the above-described laminate and metal foil-clad laminate. Next, a through hole or a via hole is formed in the laminate, and a plated metal film for electrically connecting the conductor layer (internal circuit) and the metal foil for the external circuit is formed on the wall surface of the hole thus formed. Next, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern, and an outer layer substrate having a conductor layer (outer layer circuit) is fabricated. Thus, a printed circuit board is manufactured.
Here, the prepreg refers to a product including a substrate and a resin composition impregnated or coated on the substrate. The prepreg can be obtained by a known method, specifically, a prepreg obtained by impregnating or coating a base material with a resin composition, and then semi-curing (B-staging) the impregnated or coated resin composition by heat drying at 100 to 200 ℃. The resin composition is not particularly limited, and examples thereof include known resin compositions that can be used as materials for various printed wiring boards. The substrate is not particularly limited, and examples thereof include known substrates that can be used as materials for various printed wiring boards.
In addition, in the case where a metal foil-clad laminate is not used, a conductor layer serving as a circuit may be formed on a layer containing the resin composition in the resin sheet to produce a printed wiring board. At this time, the conductor layer may be formed using an electroless plating method.
[ multilayer printed Circuit Board (multilayer Coreless substrate) ]
In this embodiment, the resin sheet of this embodiment can be used for a multilayer printed circuit board. The multilayer printed wiring board is not particularly limited, and examples thereof include the following: the multilayer printed wiring board includes a first insulating layer, a plurality of insulating layers each including 1 or a plurality of second insulating layers laminated on one surface side of the first insulating layer, a first conductor layer disposed between each of the plurality of insulating layers, and a plurality of conductor layers each including a second conductor layer provided on an outermost surface of the plurality of insulating layers, and the first insulating layer and the second insulating layer are each an insulating layer formed of a cured product of a resin composition in the resin sheet of the present embodiment.
As the multilayer printed wiring board, for example, a so-called coreless multilayer printed wiring board (multilayer coreless substrate) in which a second insulating layer is laminated only in one-side direction of a first insulating layer can be cited. In the present embodiment, the insulating layer formed of the cured product of the resin composition in the resin sheet of the present embodiment is used, whereby the multilayer printed circuit board has sufficiently reduced warpage and excellent rigidity and heat resistance. Therefore, in the present embodiment, the multilayer coreless substrate can sufficiently reduce the warpage (realize low warpage), and therefore, can be effectively used as a multilayer coreless substrate for a semiconductor package.
Examples
The present invention will be further illustrated by the following examples and comparative examples, but the present invention is not limited to these examples.
[ Synthesis example 1]
An α -naphthol aralkyl type cyanate ester compound (SN495VCN) was synthesized by the following procedure and used.
0.47 mol (in terms of OH group) of an α -naphthol aralkyl resin (SN495V, OH group equivalent: 236g/eq., manufactured by Nippon iron chemical Co., Ltd.; product containing 1 to 5 of naphthol aralkyl repeating unit number n) was dissolved in 500ml of chloroform, and 0.7 mol (solution 1) of triethylamine was added to the solution. While the temperature was maintained at-10 ℃, 300g of a chloroform solution containing 0.93 mol of cyanogen chloride was added dropwise to the solution 1 over 1.5 hours, and after completion of the dropwise addition, the mixture was stirred for 30 minutes. Then, a mixed solution of 0.1 mol of triethylamine and 30g of chloroform was added dropwise to the reactor, and the reaction was completed by stirring for 30 minutes. After the hydrochloride of triethylamine as a by-product was filtered off from the reaction solution, the obtained filtrate was washed with 500mL of 0.1N hydrochloric acid, and then washing with 500mL of water was repeated 4 times. Drying the mixture with sodium sulfate, drying the dried mixture under reduced pressure at 75 ℃ and further degassing the dried mixture under reduced pressure at 90 ℃ to obtain a brown solid of the α -naphthol aralkyl type cyanate ester compound represented by the above formula (1a) (R in the formula)1cAll are hydrogen atoms, and the number of repeating units n1 is 1 to 5). Red for the obtained alpha-naphthol aralkyl cyanate ester compoundThe external absorption spectrum was analyzed at 2264cm-1Nearby, the absorption of cyanate ester groups was confirmed.
[ example 1]
A biphenyl aralkyl type phenol resin (KAYAHARD (registered trademark) GPH-103 (trade name, manufactured by Nippon Kabushiki Kaisha) having a hydroxyl group equivalent of 231g/eq, as represented by the above formula (2c), wherein R is represented by2bAll hydrogen atoms) 36 parts by mass, biphenyl aralkyl type epoxy resin (NC-3000FH (trade name), epoxy equivalent: 320g/eq, manufactured by japan chemicals corporation; represented by the above formula (3 b)) 39 parts by mass, an aralkyl type epoxy resin (HP-9900 (trade name), epoxy equivalent: 274g/eq, manufactured by DIC corporation; as shown in the above formula (3c), 7 parts by mass of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70 (trade name), manufactured by KI Kasei chemical Co., Ltd.), 18 parts by mass of slurry silica 1(SC2050-MB (trade name), average particle diameter 0.7 μm, manufactured by Admatox K.K.) 100 parts by mass, slurry silica 2(SC5050-MOB (trade name), average particle diameter 1.5 μm, manufactured by Admatox Co., Ltd.) 100 parts by mass, silicone composite powder (KMP-600 (trade name), manufactured by Nissan chemical Co., Ltd.), 20 parts by mass of wetting dispersant 1(DISPERBYK (registered trade name) -161 (trade name), manufactured by Nippon Kagaku K.K.) 1 part by mass, wetting dispersant 2(DISPERBYK (registered trade name) -111 (trade name), manufactured by japan large chemical co., ltd.) 2 parts by mass, 1 part by mass of a silane coupling agent (KBM-403 (trade name), manufactured by shin-Etsu chemical Co., Ltd.), and 0.5 part by mass of 2,4, 5-triphenylimidazole (manufactured by tokyo chemical Co., Ltd.) were mixed (mixed), and then diluted with methyl ethyl ketone to obtain a varnish (resin composition). The varnish (resin composition) was diluted with methyl ethyl ketone, applied to the matte side of a copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metal mining Co., Ltd.) having a thickness of 350mm X250 mm X12 μ M by a bar coater, and heat-dried at 130 ℃ for 5 minutes, thereby obtaining a copper foil with a B-staged (minimum melt viscosity: about 1500Pa · s) layer comprising a resin composition, wherein the layer comprising a resin composition had a thickness of 20 μ M.
[ example 2]
Except that biphenyl aryl is of the typeThe amount of the epoxy resin (NC-3000-FH (trade name)) was changed from 39 parts by mass to 19 parts by mass, and a naphthalene ether type epoxy resin (HP-6000 (trade name), epoxy equivalent: 250g/eq., manufactured by DIC Co., Ltd., wherein R in the formula (3g) is represented3bAll hydrogen atoms, the number of repeating units k1 was 2) and 20 parts by mass, a resin composition having a B-stage structure (minimum melt viscosity: about 1000Pa · s), wherein the layer comprising the resin composition has a thickness of 20 μm.
[ example 3]
20 parts by mass of a biphenyl aralkyl type phenol resin (KAYAHARD (registered trademark) GPH-103 (trade name)), 15 parts by mass of a phenol-modified xylene resin (XISTAR (registered trademark) GP-100 (trade name), FUDOW Kabushiki Kaisha phenol equivalent: 194g/eq.), 34 parts by mass of a biphenyl aralkyl type epoxy resin (NC-3000-FH (trade name)), 5 parts by mass of a naphthalene aralkyl type epoxy resin (HP-9900 (trade name)), a dicyclopentadiene type epoxy resin (EPICRON (registered trademark) HP-7200L (trade name), an epoxy equivalent: 249g/eq., manufactured by DIC Kabushiki Kaisha, R in the formula (3i) is represented by the above formula3cAll of which are hydrogen atoms) 7 parts by mass, a polymethylenemaleimide compound (BMI-2300 (trade name), manufactured by Daihe Kabushiki Kaisha) 19 parts by mass, a slurry silica 1(SC2050-MB (trade name), average particle diameter 0.7 μm)100 parts by mass, a slurry silica 2(SC5050-MOB (trade name), average particle diameter 1.5 μm)100 parts by mass, a silicone composite powder (KMP-600 (trade name)) 20 parts by mass, a wetting dispersant 1(DISPERBYK (registered trademark) -161 (trade name)) 1 part by mass, a wetting dispersant 2(DISPERBYK (registered trademark) -111 (trade name)) 2 parts by mass, a silane coupling agent (KBM-403 (trade name)) 1 part by mass, and 2,4, 5-triphenylimidazole 0.5 parts by mass, which are mixed and then diluted with methyl ethyl ketone, a varnish (resin composition) was obtained. The varnish (resin composition) was diluted with methyl ethyl ketone, applied to the matte side of a copper foil (3EC-M2S-VLP (trade name, manufactured by Mitsui Metal mining Co., Ltd.) having a thickness of 350 mm. times.250 mm. times.12 μ M by a bar coater, and heat-dried at 130 ℃ for 5 minutes, thereby obtaining a film having a B-staged (minimum melt viscosity: about 1000 Pa. s) layer comprising the resin compositionA copper foil, wherein the layer comprising the resin composition has a thickness of 20 μm.
[ example 4]
34 parts by mass of an α -naphthol aralkyl type cyanate ester compound (cyanate equivalent: 261g/eq), 15 parts by mass of a biphenylaralkyl type epoxy resin (NC-3000-FH (trade name)), 5 parts by mass of a naphthalene ether type epoxy resin (HP-6000 (trade name)), 26 parts by mass of a dicyclopentadiene type epoxy resin (EPICRON (registered trademark) HP-7200L (trade name)), 15 parts by mass of an epoxy resin composed of a bisphenol A type structural unit and a hydrocarbon type structural unit (EPICLON (registered trademark) EXA-4816 (trade name), manufactured by DIC corporation, and 5 parts by mass of a bis (3-ethyl-5-methyl-maleimidophenyl) methane (BMI-70 (trade name)) synthesized by the method described in Synthesis example 1, and, 100 parts by mass of slurry silica 1(SC2050-MB (trade name), average particle diameter 0.7 μm), 100 parts by mass of slurry silica 2(SC5050-MOB (trade name), average particle diameter 1.5 μm), 20 parts by mass of silicone composite powder (KMP-600 (trade name)), 1 part by mass of wetting dispersant 1(DISPERBYK (registered trademark) -161 (trade name)), 2 parts by mass of wetting dispersant 2(DISPERBYK (registered trademark) -111 (trade name)), 1 part by mass of silane coupling agent (KBM-403 (trade name)), and 0.5 part by mass of 2,4, 5-triphenylimidazole were mixed and then diluted with methyl ethyl ketone to obtain a varnish (resin composition). The varnish (resin composition) was diluted with methyl ethyl ketone, applied to the matte side of a copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metal mining Co., Ltd.) having a thickness of 350mm X250 mm X12 μ M by a bar coater, and heat-dried at 130 ℃ for 5 minutes, thereby obtaining a copper foil with a B-staged (minimum melt viscosity: about 1500Pa · s) layer comprising a resin composition, wherein the layer comprising a resin composition had a thickness of 20 μ M.
Comparative example 1
40 parts by mass of an α -naphthol aralkyl type cyanate ester compound (cyanate equivalent: 261g/eq) synthesized by the method described in Synthesis example 1, 20 parts by mass of a polyphenylmethylenemaleimide compound (BMI-2300 (trade name)), 40 parts by mass of a naphthalene ether type epoxy resin (HP-6000 (trade name)), 100 parts by mass of slurry silica 1(SC2050-MB (trade name), average particle diameter 0.7 μm), 100 parts by mass of slurry silica 2(SC5050-MOB (trade name), average particle diameter 1.5 μm), 20 parts by mass of a silicone composite powder (KMP-600 (trade name)), 1 part by mass of a dispersant 1(DISPERBYK (registered trademark) -161 (trade name)), 2 parts by mass of a dispersant 2(DISPERBYK (registered trademark) -111 (trade name)), 1 part by mass of a silane coupling agent (KBM-403 (trade name)), 1 part by mass of a silane coupling agent, 0.5 parts by mass of 2,4, 5-triphenylimidazole was mixed, and then diluted with methyl ethyl ketone to obtain a varnish (resin composition). The varnish (resin composition) was diluted with methyl ethyl ketone, applied to the matte side of a copper foil (3EC-M2S-VLP (trade name), manufactured by mitsui metal mining co., ltd.) having a thickness of 350mm × 250mm × 12 μ M with a bar coater, and heat-dried at 130 ℃ for 5 minutes, thereby obtaining a copper foil with a B-stage layer comprising a resin composition, wherein the layer comprising a resin composition had a thickness of 20 μ M.
Comparative example 2
20 parts by mass of a biphenylaralkyl type phenol compound (KAYAHARD (registered trademark) GPH-103 (trade name)), 15 parts by mass of a phenol-modified xylene compound (XISTAR (registered trademark) GP-100 (trade name)), 30 parts by mass of a biphenylaralkyl type epoxy resin (NC-3000-FH (trade name)), 20 parts by mass of a dicyclopentadiene type epoxy resin (EPICRON (registered trademark) HP-7200L (trade name)), 15 parts by mass of bis (3-ethyl-5-methyl-maleimidophenyl) methane (BMI-70 (trade name)), 100 parts by mass of slurry silica 1(SC2050-MB (trade name)), 100 parts by mass of an average particle diameter of 0.7 μm), 100 parts by mass of slurry silica 2(SC5050-MOB (trade name), 1.5 μm), 20 parts by mass of a silicone composite powder (KMP-600 (trade name)), and, 1 part by mass of wetting dispersant 1(DISPERBYK (registered trademark) -161 (trade name)), 2 parts by mass of wetting dispersant 2(DISPERBYK (registered trademark) -111 (trade name)), 1 part by mass of silane coupling agent (KBM-403 (trade name)), and 0.5 part by mass of 2,4, 5-triphenylimidazole were mixed, and then diluted with methyl ethyl ketone to obtain a varnish (resin composition). The varnish (resin composition) was diluted with methyl ethyl ketone, applied to the matte side of a copper foil (3EC-M2S-VLP (trade name), manufactured by mitsui metal mining co., ltd.) having a thickness of 350mm × 250mm × 12 μ M with a bar coater, and heat-dried at 130 ℃ for 5 minutes, thereby obtaining a copper foil with a B-stage layer comprising a resin composition, wherein the layer comprising a resin composition had a thickness of 20 μ M.
Comparative example 3
5 parts by mass of an α -naphthol aralkyl type cyanate ester compound synthesized by the method described in Synthesis example 1, 50 parts by mass of a polyphenylmethane maleimide compound (BMI-2300 (trade name)), 10 parts by mass of a biphenylaralkyl type epoxy resin (NC-3000-FH (trade name)), 35 parts by mass of an alkenyl-substituted nadimide compound (BANI-M (trade name), manufactured by Takayashi petrochemical Co., Ltd.), 100 parts by mass of slurry silica 1(SC2050-MB (trade name), average particle diameter of 0.7 μ M), 100 parts by mass of slurry silica 2(SC5050-MOB (trade name), average particle diameter of 1.5 μ M), 20 parts by mass of a silicone composite powder (KMP-600 (trade name)), 1 part by mass of a wetting dispersant 1(DISPERBYK (registered trademark) -161 (trade name)), 1 part by mass of a wetting dispersant, and a dispersant, 2 parts by mass of wetting dispersant 2(DISPERBYK (registered trademark) -111 (trade name)), 1 part by mass of silane coupling agent (KBM-403 (trade name)), and 0.5 part by mass of 2,4, 5-triphenylimidazole were mixed, and then diluted with methyl ethyl ketone to obtain a varnish (resin composition). The varnish (resin composition) was diluted with methyl ethyl ketone, applied to the matte side of a copper foil (3EC-M2S-VLP (trade name), manufactured by mitsui metal mining co., ltd.) having a thickness of 350mm × 250mm × 12 μ M with a bar coater, and heat-dried at 130 ℃ for 5 minutes, thereby obtaining a copper foil with a B-stage layer comprising a resin composition, wherein the layer comprising a resin composition had a thickness of 20 μ M.
Comparative example 4
30 parts by mass of an α -naphthol aralkyl type cyanate ester compound synthesized by the method described in synthesis example 1, 35 parts by mass of a polyphenylmethylenemaleimide compound (BMI-2300 (trade name)), 5 parts by mass of a naphthalene ether type epoxy resin (HP-6000 (trade name)), an acrylate rubber compound (TEISANRESIN (registered trademark) SG-P3 (trade name), 30 parts by mass of zakuwa chemical co., ltd., inc., slurry silica 1(SC2050-MB (trade name), average particle diameter of 0.7 μm)100 parts by mass, slurry silica 2(SC5050-MOB (trade name)) 100 parts by mass, a dispersant 1(DISPERBYK (registered trademark) -161 (trade name)) 1 part by mass, a dispersant 2(DISPERBYK (registered trademark) -111 (trade name)) 2 parts by mass, a silane coupling agent (KBM-403 (trade name)) 1 part by mass, a silane coupling agent (KBM-403 (trade name)) and a silane coupling agent, 0.5 parts by mass of 2,4, 5-triphenylimidazole was mixed, and then diluted with methyl ethyl ketone to obtain a varnish (resin composition). The varnish (resin composition) was diluted with methyl ethyl ketone, applied to the matte side of a copper foil (3EC-M2S-VLP (trade name), manufactured by mitsui metal mining co., ltd.) having a thickness of 350mm × 250mm × 12 μ M with a bar coater, and heat-dried at 130 ℃ for 5 minutes, thereby obtaining a copper foil with a B-stage layer comprising a resin composition, wherein the layer comprising a resin composition had a thickness of 20 μ M.
Comparative example 5
A copper foil with a B-staged layer comprising a resin composition was obtained in the same manner as in comparative example 4, except that the amount of the slurry silica 2(SC-5050MOB (trade name)) and the wetting dispersant 2(DISPERBYK (registered trademark) -111 (trade name)) were not used, and the amount of the slurry silica 1(SC-2050MB (trade name)) was changed from 100 parts by mass to 75 parts by mass, wherein the thickness of the layer comprising a resin composition was 20 μm.
[ evaluation of physical Properties measurement ]
Using the copper foils with B-staged layers comprising resin compositions obtained in examples 1 to 4 and comparative examples 1 to 5, samples for measurement and evaluation of physical properties were prepared according to the procedures shown in the following items, and mechanical properties (storage modulus at 40 ℃, 170 ℃, 230 ℃), glass transition temperature (Tg), amount of warpage, and heat resistance were measured and evaluated. The results of examples and comparative examples are shown in table 1.
(mechanical characteristics)
First, a copper clad laminate (HL832NS (trade name) T/T0.8 mmt, manufactured by Mitsubishi gas chemical) was hollowed out to a size of 100mm × 150mm in the central portion thereof, and the copper clad laminate was superposed on a copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metal mining Co., Ltd.; thickness: 12 μ M). Next, 25g of the resin portion in the layer containing the resin composition in the laminated copper foil obtained in example 1 was placed in the hollowed portion, and a copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metal mining Co., Ltd.) was placed so as to cover the resin portionManufacturing; thickness 12 μm) was placed on the copper clad laminate, and the resin portion was sandwiched by copper foils on the front and back surfaces. Then, the pressure was set at 30kgf/cm2And a temperature of 230 ℃ for 100 minutes to obtain a laminate having a copper foil, an insulating layer in which the resin portion is cured, and a copper foil. The thickness of the insulating layer was about 800 μm. The obtained laminate was cut with a dicing saw into dimensions of 13mm × 35mm (after miniaturization) so as to include the insulating layer, and then the copper foils provided on both surfaces of the laminate were removed by etching to obtain a sample for measurement. By repeating this series of operations, 3 measurement samples were prepared.
The 3 measurement samples were subjected to dynamic viscoelasticity measurement (DMA) using a dynamic viscoelasticity analyzer (manufactured by TA instruments) in accordance with JIS C6481, and mechanical properties (storage modulus E' at 40 ℃, 170 ℃, 230 ℃ and 260 ℃) were measured. The storage modulus E ' obtained from each measurement sample was used to calculate the added average value of the storage modulus E ' at each temperature, and these values were defined as the storage modulus E '.
The mechanical properties of the copper foils with B-staged layers comprising the resin compositions obtained in examples 2 to 4 and comparative examples 1 to 5 were also measured in the same manner, and the respective storage moduli E' were calculated.
(glass transition temperature (Tg))
First, a copper clad laminate (HL832NS (trade name) T/T0.8 mmt, manufactured by Mitsubishi gas chemical) was hollowed out to a size of 100mm × 150mm in the central portion thereof, and the copper clad laminate was superposed on a copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metal mining Co., Ltd.; thickness: 12 μ M). Next, a resin portion 25g of the layer containing the resin composition in the laminated copper foil obtained in example 1 was placed in the hollowed portion, and a copper foil (3EC-M2S-VLP (trade name; manufactured by mitsui metal mining corporation; thickness 12 μ M)) was placed on the copper-clad laminate so as to cover the resin portion, and the resin portion was sandwiched by the copper foils on the front and back surfaces. Then, the pressure was set at 30kgf/cm2And a temperature of 230 ℃ for 100 minutes to obtain a laminate having a copper foil, an insulating layer in which the resin portion is cured, and a copper foil. Insulation boardThe thickness of the insulating layer was about 800 μm. The obtained laminate was cut with a dicing saw into dimensions of 13mm × 35mm (after miniaturization) so as to include the insulating layer, and then the copper foils provided on both surfaces of the laminate were removed by etching to obtain a sample for measurement. By repeating this series of operations, 3 measurement samples were prepared.
The glass transition temperature (Tg) of each of the 3 measurement samples was measured by a DMA method using a dynamic viscoelasticity analyzer (manufactured by TA instruments) according to JIS C6481. The glass transition temperatures obtained from the respective measurement samples were used to calculate an added average value, and this value was defined as the glass transition temperature.
The glass transition temperatures of the copper foils with B-staged layers comprising the resin compositions obtained in examples 2 to 4 and comparative examples 1 to 5 were measured and calculated in the same manner.
(amount of warpage: bimetal method)
First, 2 copper foils with B-staged layers containing a resin composition were prepared.
Using 1 of the clad copper foils, a copper foil (3EC-M2S-VLP (trade name; manufactured by Mitsui Metal mining Co., Ltd.; thickness: 12 μ M) was provided on the surface of the layer containing the resin composition in the clad copper foil under a pressure of 30kgf/cm2And a temperature of 220 ℃ for 120 minutes to obtain a copper clad laminate 1 having copper foils on both sides of the cured insulating layer. The thickness of the insulating layer is about 20 μm. Next, only one of the double-sided copper foils of the copper clad laminate 1 is removed by etching, thereby obtaining a copper clad laminate 2. Then, on the surface of the insulating layer of the copper clad laminate 2, the surface of another layer containing the resin composition in the copper clad laminate was superposed and pressed at a pressure of 30kgf/cm2And a temperature of 220 ℃ for 120 minutes to obtain a copper clad laminate 3. The total thickness of the 2 insulating layers was about 40 μm. The copper clad laminate 3 was etched to remove the copper foil on both sides, thereby obtaining a laminate. Then, a 20mm × 200mm strip-shaped board was cut out from the obtained laminated board. Then, one end of the strip-shaped plate in the width direction is attracted to a plane perpendicular to the plane by a magnet, andthe plane is parallel to the straight edge and the maximum separation length of the perpendicular plane from the strip is measured and taken as the "amount of warpage". The case where the warpage amount was less than 4mm was evaluated as "AA", and the other cases were evaluated as "CC".
The amounts of warpage were also measured and evaluated for the copper foils with B-staged layers comprising the resin compositions obtained in examples 2 to 4 and comparative examples 1 to 5, respectively.
(Heat resistance)
First, a copper clad laminate 1(HL832NS (trade name) T/T0.8 mmt, mitsubishi gas chemical) was prepared.
The copper foil surfaces of both surfaces of the copper-clad laminate 1 were etched to a degree of 1 μm to 3 μm (inner layer roughening treatment, CZ-8100 (trade name), manufactured by MEC corporation), and the surface of the resin composition-containing layer of the copper foil with a layer obtained in example 1 was superposed on each of the copper foil surfaces of both surfaces of the copper-clad laminate under a pressure of 30kgf/cm2And a temperature of 230 ℃ for 100 minutes to obtain a copper clad laminate 2. Next, the copper clad laminate 2 was cut into a size of 50mm × 50mm (reduced in size) with a dicing saw to obtain a sample for measurement. The obtained sample was left to stand in a thermostatic bath at 120 ℃ for 1 hour, and then immersed in a solder bath at 260 ℃ for 30 seconds to evaluate heat resistance. After 30 seconds, it was confirmed whether or not interlayer delamination occurred between the copper foil on the surface of the copper-clad laminate 1 and the cured layer formed by curing the layer containing the resin composition, on both surfaces of the copper-clad laminate 1. The case where no interlayer delamination occurred on both sides was evaluated as "AA", and the case where interlayer delamination occurred on either side was evaluated as "CC".
The copper foils with B-staged layers comprising resin compositions obtained in examples 2 to 4 and comparative examples 1 to 5 were also evaluated for heat resistance by the same procedure.
[ Table 1]
Figure BDA0003433176350000471
The present application is based on japanese patent application published on 26/6/2019 (japanese application 2019-118888), the contents of which are hereby incorporated by reference.
Industrial applicability
The resin sheet of the present invention can be used for, for example, a metal foil-clad laminate, a printed circuit board, and a multilayer printed circuit board.

Claims (14)

1. A resin sheet comprising: a support; and the number of the first and second groups,
a layer comprising a resin composition provided on the surface of the support, the resin composition satisfying the relationships represented by the following formulae (i), (ii), and (iii),
0.15≤b/a≤0.60···(i)
0.015≤c/a≤0.07···(ii)
3≤a≤10···(iii)
in the formulae (i), (ii) and (iii), a, b and c represent storage moduli at 40 ℃, 170 ℃ and 230 ℃, respectively, of a cured product of the resin composition, in units of: GPa.
2. The resin sheet according to claim 1, wherein the resin composition further satisfies the relationship represented by the following formula (iv),
175≤Tg≤215…(iv)
in the formula (iv), Tg represents a glass transition temperature of a cured product of the resin composition, unit: DEG C.
3. The resin sheet according to claim 1 or 2, wherein the resin composition further satisfies the relationship represented by the following formula (v),
0.015≤d/a≤0.08…(v)
in the formula (v), d represents a storage modulus at 260 ℃ of a cured product of the resin composition, unit: GPa, a is as defined above.
4. The resin sheet according to any one of claims 1 to 3, wherein the resin composition contains an elastomer component.
5. The resin sheet according to any one of claims 1 to 4, wherein the resin composition comprises at least 1 compound selected from the group consisting of a cyanate compound, a phenol compound, an epoxy compound, and a maleimide compound.
6. The resin sheet according to claim 5, wherein the resin composition comprises:
the cyanate ester compound and/or the phenol compound; and the number of the first and second groups,
the epoxy compound and/or the maleimide compound.
7. The resin sheet according to claim 5 or 6, wherein the resin composition comprises:
the phenol compound; and the number of the first and second groups,
the epoxy compound and/or the maleimide compound.
8. The resin sheet according to any one of claims 5 to 7, wherein the resin composition comprises 2 or more of the epoxy compounds,
the 2 or more epoxy compounds include naphthalene type epoxy resins and/or aralkyl type epoxy resins having a naphthalene skeleton.
9. The resin sheet according to any one of claims 1 to 8, wherein the resin composition contains a filler material,
the content of the filler is 100 to 700 parts by mass per 100 parts by mass of the resin solid content in the resin composition.
10. The resin sheet according to claim 9, wherein the filling material contains an inorganic filling material and/or an organic filling material.
11. The resin sheet according to claim 10, wherein the inorganic filler material contains at least 1 selected from the group consisting of silica, boehmite, and alumina.
12. The resin sheet according to any one of claims 1 to 11, wherein the support is a resin sheet or a metal foil.
13. A metal-clad laminate comprising:
a layer comprising a cured product of the resin composition according to any one of claims 1 to 11; and the number of the first and second groups,
and a metal foil provided on one or both surfaces of the layer containing the cured product.
14. A printed circuit board is provided with:
an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 11; and the number of the first and second groups,
and the conductor layer is arranged on the surface of the insulating layer.
CN202080046749.3A 2019-06-26 2020-06-22 Resin sheet, metal foil-clad laminate, and printed wiring board Active CN114127205B (en)

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KR20220022894A (en) 2022-02-28

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