WO2020262321A1 - レジンシート、金属箔張積層板、及びプリント配線板 - Google Patents

レジンシート、金属箔張積層板、及びプリント配線板 Download PDF

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Publication number
WO2020262321A1
WO2020262321A1 PCT/JP2020/024449 JP2020024449W WO2020262321A1 WO 2020262321 A1 WO2020262321 A1 WO 2020262321A1 JP 2020024449 W JP2020024449 W JP 2020024449W WO 2020262321 A1 WO2020262321 A1 WO 2020262321A1
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Prior art keywords
resin
resin composition
mass
compound
parts
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2020/024449
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English (en)
French (fr)
Japanese (ja)
Inventor
和晃 川下
禎啓 加藤
憲明 杉本
尊明 小柏
洋介 松山
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Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
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Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to CN202080046749.3A priority Critical patent/CN114127205B/zh
Priority to KR1020217037583A priority patent/KR20220022894A/ko
Priority to JP2021526986A priority patent/JP7593314B2/ja
Publication of WO2020262321A1 publication Critical patent/WO2020262321A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

Definitions

  • the present invention relates to a resin sheet, a metal foil-clad laminate, and a printed wiring board.
  • Patent Document 1 describes a resin sheet that has a support and an adhesive layer and whose warpage is reduced in a high temperature environment when applied to a printed wiring board.
  • Patent Document 1 since the warp is reduced by reducing the coefficient of thermal expansion, the warp of the printed wiring board cannot be sufficiently reduced. Therefore, further improvement is desired for the reduction of warpage.
  • a layer containing a resin composition (hereinafter, also referred to as "resin material") used for the printed wiring board is provided. It was found that it is effective to reduce the elastic modulus of the cured product of the resin composition and to develop the viscous behavior in the resin sheet. Therefore, the present inventors have studied the use of a resin material having a low elastic modulus and easily undergoing plastic deformation (exhibiting viscous behavior). However, when such a resin material is used, another problem arises that the handleability (handleability) in the manufacturing process of the printed wiring board is not sufficient due to the low rigidity. Further, such a resin material has a high water absorption rate and tends to have insufficient heat resistance and chemical resistance, which may cause further problems from the viewpoint of quality.
  • an object of the present invention is a resin sheet, a metal foil-clad laminate, and a printed wiring board, which can sufficiently reduce the warp of the printed wiring board (achieve low warpage) and can exhibit excellent rigidity and heat resistance.
  • the purpose is to provide.
  • the present inventors have set the physical characteristic parameters defined by the storage elastic modulus at a predetermined temperature within a predetermined range in the form of a cured product obtained by curing the resin composition.
  • the warpage of the printed wiring board can be sufficiently reduced and excellent rigidity and heat resistance can be exhibited by using a resin sheet having a layer containing the resin composition to be satisfied, and the present invention has been completed. It was.
  • a resin comprising a support and a layer arranged on the surface of the support and containing a resin composition satisfying the relationships represented by the following formulas (i), (ii), and (iii).
  • Sheet. 0.15 ⁇ b / a ⁇ 0.60 ... (i) 0.015 ⁇ c / a ⁇ 0.07 ... (ii) 3 ⁇ a ⁇ 10 ... (iii)
  • a, b, and c are storage elastic moduli at 40 ° C., 170 ° C., and 230 ° C.
  • the resin composition contains a filler, and the content of the filler is 100 parts by mass to 700 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. [1] ] To [8]. [10] The resin sheet according to [9], wherein the filler contains an inorganic filler and / or an organic filler.
  • the support is a resin sheet or a metal foil.
  • a metal foil comprising a layer containing a cured product of the resin composition according to any one of [1] to [11] and metal foils arranged on one or both sides of the layer containing the cured product. Zhang laminate.
  • a printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of [1] to [11] and a conductor layer arranged on the surface of the insulating layer.
  • a resin sheet, a metal foil-clad laminate, and a printed wiring board that can sufficiently reduce the warp of the printed wiring board (achieve low warpage) and can exhibit excellent rigidity and heat resistance can be obtained. It can be provided.
  • the present embodiment 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 to this, and various modifications can be made without departing from the gist thereof. It is possible.
  • the term "resin solid content” as used herein refers to additives (silane coupling agents, wet dispersants, curing accelerators, etc.), solvents, and fillers in the resin composition of the present embodiment.
  • the component excluding the material (organic filler and inorganic filler), and 100 parts by mass of the resin solid content means an additive (silane coupling agent, wet dispersant, curing accelerator, etc.) and solvent in the resin composition. It means that the total of the components excluding the filler (organic filler and inorganic filler) is 100 parts by mass.
  • the resin sheet of the present embodiment includes a support and a layer containing a resin composition arranged on the surface of the support and satisfying the relationships represented by the following formulas (i), (ii), and (iii). , Equipped with. That is, the resin sheet of the present embodiment is, for example, one in which the above-mentioned resin composition is applied to one side or both sides of the support. 0.15 ⁇ b / a ⁇ 0.60 ... (i) 0.015 ⁇ c / a ⁇ 0.07 ... (ii) 3 ⁇ a ⁇ 10 ... (iii)
  • a, b, and c are storage elastic moduli (units) at 40 ° C., 170 ° C., and 230 ° C. of the cured product obtained by curing the resin composition, respectively. : GPa) is shown.
  • the storage elastic modulus of the cured product at 40 ° C., 170 ° C., and 230 ° C. was obtained by curing the resin composition at a pressure of 30 kgf / cm 2 and a temperature of 230 ° C. for 100 minutes.
  • the specific measurement method is as in the examples.
  • the present embodiment by using a resin sheet including a layer containing the resin composition having the above-mentioned structure, the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (for example, the multilayer coreless substrate) are warped. It can be sufficiently reduced, and excellent rigidity and heat resistance can be exhibited. This factor is considered as follows. Although the following description includes consideration, the present embodiment is not limited in any way by this consideration.
  • the elastic modulus of the cured product of the resin composition is lowered. It is important to develop viscous behavior. Therefore, it is conceivable to use a resin material having a low elastic modulus and easily undergoing plastic deformation (exhibiting viscous behavior).
  • a resin material having a low elastic modulus and easily undergoing plastic deformation (exhibiting viscous behavior).
  • the handleability (handleability) in the manufacturing process of the printed wiring board is not sufficient due to the low rigidity.
  • such a resin material tends to have a high water absorption rate and insufficient heat resistance and chemical resistance, which causes a problem from the viewpoint of quality.
  • the resin sheet provided with the layer containing 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"), at 40 ° C. Sufficient rigidity can be ensured, and metal foil-clad laminated board, printed wiring board, and multi-layer printed wiring are mainly caused by keeping the storage elastic coefficient of the above within a predetermined range (satisfying the above formula (iii)). Warpage of a plate (for example, a multilayer coreless substrate) can be reduced. Further, in the cured form of the resin composition, the ratio of the storage elastic modulus at 170 ° C. to the storage elastic modulus at 40 ° C.
  • handleability can be imparted, for example, in the manufacturing process of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate).
  • a step including heat treatment for example, pressing. Viscous behavior can be exhibited during molding process, annealing process, etc.).
  • the warpage 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 storage elastic modulus at 40 ° C. is within the predetermined range (satisfying the above formula (iii)), and the ratio of the storage elastic modulus at 170 ° C. to the storage elastic modulus at 40 ° C. is within the predetermined range.
  • Excellent heat resistance can be imparted to the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring body mainly due to the above (satisfying the above formula (i)).
  • the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring are used. It is possible to impart better heat resistance to the body. Further, as described later, when the cured product of the resin composition has a storage elastic modulus at 260 ° C. within a predetermined range (satisfying the following formula (v)), the metal foil-clad laminate, the printed wiring board, and the like. Further, it is possible to impart more excellent heat resistance to the multilayer printed wiring body.
  • the resin sheet of the present embodiment is preferably one in which the resin composition in the layer containing the resin composition according to the present embodiment is applied to the support and then semi-cured (B-staged).
  • the semi-cured state (B stage) means that each component contained in the layer containing the resin composition does not actively start a reaction (curing), but the layer containing the resin composition is dried. It refers to a state in which the solvent is volatilized by heating to the extent that it is not sticky, and includes a state in which the solvent is only volatilized without being cured without heating.
  • the minimum melt viscosity in the semi-cured state (B stage) is usually 20,000 Pa ⁇ s or less.
  • the minimum melt viscosity is measured by the following method. That is, 1 g of resin powder collected from the layer containing the resin composition is used as a sample, and the minimum melt viscosity is measured with a rheometer (ARES-G2 (trade name) manufactured by TA Instruments). Here, a disposable plate having a plate diameter of 25 mm is used, and the resin powder is prepared under the conditions of a heating rate of 2 ° C./min, a frequency of 10.0 rad / sec, and a strain of 0.1% in the range of 40 ° C. to 180 ° C. Measure the minimum melt viscosity. The lower limit of the minimum melt viscosity is, for example, 10 Pa ⁇ s or more.
  • the layer containing the support and the resin composition in the resin sheet of the present embodiment will be described.
  • the support according to the present embodiment is not particularly limited, but known materials used for various printed wiring board materials can be used, and a resin sheet or a metal foil is preferable.
  • the resin sheet is different from the layer containing the resin composition layer according to the present embodiment.
  • the resin sheet and metal foil include resin sheets such as polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, and polyethylene (PE) film.
  • metal foils such as aluminum foil, copper foil, and gold foil. Among them, copper foil and PET film are preferable.
  • 3EC-VLP (trade name) manufactured by Mitsui Mining & Smelting Co., Ltd.
  • 3EC-M2S-VLP (trade name) manufactured by Mitsui Mining & Smelting Co., Ltd.
  • Mitsui Mining & Smelting Co., Ltd. examples thereof include MT18Ex (trade name) manufactured by JX Nippon Mining & Smelting Co., Ltd. and JXUT-I (trade name) manufactured by JX Nippon Mining & Metals Co., Ltd.
  • the resin composition is a cured product obtained by curing the resin composition (hereinafter, also simply referred to as “cured product”) at a predetermined temperature as described above.
  • cured product obtained by curing the resin composition (hereinafter, also simply referred to as “cured product”) at a predetermined temperature as described above.
  • the physical property parameters defined by the storage elastic modulus of the above satisfy the predetermined range.
  • a, b, and c are storage elastic moduli (unit: GPa) at 40 ° C., 170 ° C., and 230 ° C. in the cured product of the resin composition, respectively. Is shown.
  • the cured product is obtained by thermosetting the resin composition under the conditions of a heating temperature of 180 ° C. to 270 ° C. and a heating time of 30 minutes to 210 minutes, and at least the above formula (i). , (Ii), and (iii).
  • the heating temperature is preferably 200 ° C. to 240 ° C., more preferably 225 ° C. to 235 ° C., and even more preferably 230 ° C.
  • the heating time is preferably 60 minutes to 180 minutes, more preferably 100 minutes.
  • the pressure conditions for curing are not particularly limited as long as they do not impair the effects of the present embodiment, and usually suitable conditions for curing the resin composition can be used.
  • Pressure conditions are preferably 10kgf / cm 2 ⁇ 50kgf / cm 2, more preferably from 20kgf / cm 2 ⁇ 40kgf / cm 2, more preferably from 30 kgf / cm 2.
  • the heating means for curing the resin composition is not particularly limited as long as it does not impair the action and effect of the present embodiment, and ordinary heating means (for example, a dryer or the like) may be used.
  • the storage elastic modulus of the cured product can be measured by the DMA method (Dynamic Mechanical Analysis method) in accordance with JIS C6481.
  • the specific measurement method is as in the examples.
  • a storage elastic modulus at 40 ° C.
  • a storage elastic modulus at 40 ° C.
  • a is preferably 4 GPa or more, and more preferably 4.5 GPa or more.
  • a is 10 GPa or less, it is considered that the warpage 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.
  • a is 8 GPa or less. It is preferably 7 GPa or less, and more preferably 7 GPa or less.
  • the handleability is excellent in the manufacturing process of, for example, a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate). It is conceivable that.
  • b / a is preferably 0.17 or more.
  • b / a is preferably 0.60 or less.
  • the lower limit of c / a is preferably 0.02 or more from the viewpoint of further excellent handleability (handleability) in the manufacturing process of a printed wiring board (for example, a thin substrate such as a multilayer coreless substrate).
  • the upper limit of c / a is more preferably 0.06 or less from the viewpoint of further reducing the warpage of the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (for example, the multilayer coreless substrate).
  • the glass transition temperature of the cured product obtained by curing the resin composition can improve the heat resistance, and the above formula (ii) is desired. It is preferable to satisfy the following equation (iv) from the viewpoint that it can be controlled within the range of. 175 ⁇ Tg ⁇ 215 ... (iv)
  • the glass transition temperature is more preferably 180 ° C. to 213 ° C.
  • the glass transition temperature of the cured product can be measured by the DMA method in accordance with JIS C6481.
  • the specific measurement method is as in the examples.
  • the 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)
  • d represents the storage elastic modulus (unit: GPa) at 260 ° C. in the cured product of the resin composition, and a is synonymous with the above.
  • the storage elastic modulus of the cured product at 260 ° C. can be obtained by the same method as the storage elastic modulus of the cured product, and can be measured by the DMA method in accordance with JIS C6481. .. The specific measurement method is as in the examples.
  • the heat resistance of the cured product is further improved. For example, it tends to show sufficient heat resistance even when exposed to a high temperature of 300 ° C., and further has a tendency to be more excellent in handleability in a mounting process for mounting a semiconductor chip on a printed wiring board (for example, a multilayer coreless substrate). It is in. From the same viewpoint, the lower limit of d / a is more preferably 0.018 or more.
  • the resin composition in the layer containing the resin composition according to the present embodiment is not particularly limited, but may contain an elastomer component.
  • the elastomer component is not particularly limited, but is, for example, acrylic rubber, silicone rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber, butadiene rubber, polyisoprene rubber, urethane rubber, and butyl rubber, which are different from the organic fillers and other additives described below.
  • And core-shell rubber One of these elastomer components may be used alone, or two or more thereof may be used in combination.
  • the acrylic rubber is not particularly limited, and examples thereof include acrylic acid alkyl esters such as ethyl acrylate and butyl acrylate.
  • the silicone rubber is not particularly limited, and examples thereof include a copolymer containing a dimethylsiloxane group, a methylvinyl group, a methylphenyl group, and a diphenylsiloxane group, and a polydimethylsiloxane composed of only a dimethylsiloxane group.
  • the core-shell rubber is not particularly limited, and is, for example, a methacrylate ester / styrene / butadiene rubber graft copolymer, an acrylonitrile / styrene / butadiene rubber graft copolymer, an acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and an acrylonitrile.
  • the content of the elastomer is not particularly limited, but is, for example, less than 30 parts by mass, preferably 25 parts by mass or less, and more preferably 20 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. It is less than or equal to, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.
  • the content is less than (less than) the above-mentioned value, the heat resistance and water absorption of the obtained cured product tend to be further improved.
  • the resin composition in the layer containing the resin composition according to the present embodiment is not particularly limited, but may contain short glass fibers having an average fiber length of 10 ⁇ m to 300 ⁇ m.
  • the short glass fibers having an average fiber length of 10 ⁇ m to 300 ⁇ m are different from the following inorganic fillers.
  • Such short glass fibers are mainly composed of SiO 2 , Al 2 O 3 , CaO, MgO, B 2 O 3 , Na 2 O, and K 2 O, and have an average fiber length of 10 ⁇ m to 300 ⁇ m. There is no particular limitation.
  • the average fiber length of the glass short fibers is preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, from the viewpoint of lowering the coefficient of thermal expansion. Further, from the viewpoint of improving the dispersibility of the short glass fibers, it is preferably 250 ⁇ m or less, more preferably 200 ⁇ m or less, and even more preferably 150 ⁇ m or less.
  • the average fiber diameter of the glass short fibers is not particularly limited, but is preferably 3 ⁇ m to 15 ⁇ m, more preferably 3 ⁇ m to 13 ⁇ m, and even more preferably 3.5 ⁇ m to 11 ⁇ m from the viewpoint that the coefficient of thermal expansion can be lowered.
  • the average fiber length and fiber diameter of the short glass fibers can be measured using an optical microscope, an electron microscope, or the like.
  • short glass fibers include milled fibers (also referred to as milled fibers), glass wool and microrods.
  • milled fiber is preferable because it can obtain excellent adhesion to copper foil and is inexpensive.
  • These short glass fibers may be used alone or in admixture of two or more.
  • Commercially available products may be used as the short glass fibers.
  • the commercially available short glass fiber is not particularly limited, but for example, "EFH30-01 (trade name)", “EFH50-01 (trade name)", and "EFH30-31 (product name)” manufactured by Central Glass Fiber Co., Ltd.
  • the content of the short glass fibers is not particularly limited, but is preferably 5 parts by mass to 450 parts by mass with respect to 100 parts by mass of the resin solid content from the viewpoint of imparting thermal expansion coefficient, toughness, and moldability. More preferably, it is 10 parts by mass to 400 parts by mass.
  • the resin composition in the layer containing the resin composition according to the present embodiment is not particularly limited, and includes at least one compound selected from the group consisting of cyanate ester compounds, phenol compounds, epoxy compounds, and maleimide compounds. Is preferable. When these compounds are contained in the resin composition, the glass transition temperature, chemical resistance, and peel strength of the obtained cured product tend to be improved. These compounds may be used alone or in combination of two or more. Among these, the compound includes a cyanate ester 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. Is preferable. From the same viewpoint, the compound more preferably contains a phenol compound and an epoxy compound and / or a maleimide compound.
  • the "cyanic acid ester compound” refers to a compound having two or more cyanato groups (cyanic acid ester groups) in one molecule
  • the “compound” refers to a concept including a resin.
  • the cyanate ester compound is not particularly limited as long as it is a compound having two or more cyanato groups (cyanate groups) in one molecule, but for example, an aroma containing two or more cyanato groups in one molecule.
  • Group hydrocarbon compounds compounds in which two aromatic rings containing two or more cyanato groups are bonded by a linking group
  • novolak type cyanate ester compounds bisphenol type cyanate ester compounds, diallyl bisphenol type cyanate ester compounds (for example, Dialyl bisphenol A type cyanate ester compound, diallyl bisphenol E type cyanate ester compound, diallyl bisphenol F type cyanate ester compound, diallyl bisphenol S type cyanate ester compound, etc.), aralkyl type cyanate ester compound, these cyanate esters
  • Pre-polymers can be mentioned.
  • These cyanate ester compounds may be used alone or in combination of two or more.
  • the aralkyl-type cyanate ester compound is preferable from the viewpoint of further improving the glass transition temperature, chemical resistance, and peel strength of the obtained cured product, and the ⁇ -naphthol aralkyl-type cyanate ester compound and biphenyl aralkyl described later are preferable.
  • Type cyanate ester compounds are more preferred.
  • Examples of the aromatic hydrocarbon compound containing two or more cyanato groups in one molecule include formula (I): Ar- (OCN) p (in the formula, Ar is a benzene ring, a naphthalene ring, and a biphenyl ring.
  • a compound represented by (p) represents an integer of 2 or more.) Can be mentioned.
  • the compound represented by the above formula (I) is not particularly limited, and is, for example, 1,3-disianatbenzene, 1,4-disyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-disi.
  • Anatonaphthalene 1,4-disianatonaphthalene, 1,6-disianatonaphthalene, 1,8-disianatonaphthalene, 2,6-disianatonaphthalene, 2,7-disianatonaphthalene, 1,3,6-tri Examples thereof include synatonaphthalene and 4,4'-disamitobiphenyl.
  • the compound in which two aromatic rings containing two or more cyanato groups are bonded by a linking group is not particularly limited, and for example, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, and bis (4-cyanatophenyl) thioether, and Examples thereof include bis (4-cyanatophenyl) sulfone.
  • Examples of the novolak type cyanide ester compound include a compound represented by the following formula (1).
  • R 1a independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 1b each independently represent 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, but for example, bis (3,5-dimethyl4-cyanatophenyl) methane, bis (4-sinaatophenyl) methane, and 2,2'-. Examples thereof include bis (4-cyanatophenyl) propane.
  • cyanate ester compounds are used alone or in combination of two or more.
  • 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.
  • 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. Be done.
  • the bisphenol type cyanide ester compound a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Examples of commercially available bisphenol-type cyanide ester compounds include "CA210 (trade name)” manufactured by Mitsubishi Gas Chemical Company, Inc.
  • the aralkyl-type cyanate ester compound is not particularly limited, and examples thereof include an ⁇ -naphthol aralkyl-type cyanate ester compound and a biphenylaralkyl-type cyanate ester compound.
  • Examples of the ⁇ -naphthol aralkyl type cyanide ester compound include a compound represented by the following formula (1a).
  • R 1c independently represents a hydrogen atom or a methyl group, and preferably represents a hydrogen atom.
  • n1 represents an integer of 1 to 10, preferably an integer of 1 to 6.
  • biphenyl aralkyl type cyanide ester compound examples include a compound represented by the following formula (1b).
  • R 1d independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • Each of R 1e independently represents a hydrogen atom or a methyl group, and preferably represents a hydrogen atom.
  • n2 represents an integer of 1 to 10, preferably an integer of 1 to 6.
  • aralkyl type cyanide ester compound a commercially available product may be used, or a product synthesized by a known method may be used.
  • Examples of the method for synthesizing the aralkyl-type cyanate ester compound include a phenol resin corresponding to the target aralkyl-type cyanate ester compound (hereinafter, also referred to as “corresponding phenol resin”), cyanogen halide, and a basic compound.
  • Examples thereof include a method of reacting with an inert organic solvent, a method of reacting a salt formed by reacting a corresponding phenol resin with a basic compound in an aqueous solution, and a method of causing a two-phase interfacial reaction between cyanogen halide and the like. ..
  • an aralkyl-type cyanate ester compound can be obtained by cyanating the hydrogen atom of the phenolic hydroxyl group of the corresponding phenolic resin. More specifically, for example, the method described in Examples is used.
  • the content of the cyanide ester compound is not particularly limited, but is preferably 10 parts by mass to 45 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the storage elastic modulus during heating tends to be a value suitable for suppressing warpage, and metal foil-clad laminates, printed wiring boards and multilayer printed wiring boards (for example, multilayer coreless) There is a tendency that the warpage of the substrate) can be further reduced.
  • the lower limit of the content is more preferably 15 parts by mass, further preferably 20 parts by mass, still more preferably 30 parts by mass, and the upper limit of the content is more preferably. It is 40 parts by mass, more preferably 35 parts by mass.
  • the cyanate equivalent of the cyanate ester compound is preferably 100 g / eq to 500 g / eq, more preferably 400 g / eq or less, and even more preferably 300 g / eq or less.
  • 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 elastic modulus at the time of heating tend to be suitable values for suppressing warpage.
  • the "phenolic compound” means a compound having two or more phenolic hydroxyl groups in one molecule
  • the "compound” means a concept including a resin.
  • the phenol compound is not particularly limited as long as it is a compound having two or more phenolic hydroxyl groups in one molecule, but for example, phenols and bisphenols having two or more phenolic hydroxyl groups in one molecule (for example, bisphenol).
  • bisphenol E, bisphenol F, bisphenol S, etc. diallyl bisphenols (eg, diallyl bisphenol A, diallyl bisphenol E, diallyl bisphenol F, and diallyl bisphenol S, etc.), bisphenol type phenol resin (for example, bisphenol A type resin) , Bisphenol E type resin, bisphenol F type resin, bisphenol S type resin, etc.), phenols novolak resin (for example, phenol novolak resin, naphthol novolak resin, cresol novolak resin, etc.), glycidyl ester type phenol resin, naphthalene type phenol Examples thereof include resins, anthracene-type phenol resins, dicyclopentadiene-type phenol resins, biphenyl-type phenol resins, alicyclic phenol resins, polyol-type phenol resins, aralkyl-type phenol resins, and phenol-modified aromatic hydrocarbon formaldehyde resins.
  • bisphenol type phenol resin for
  • the phenol compound may be used alone or in combination of two or more.
  • the phenol compound is preferably an aralkyl type phenol resin and / or a phenol-modified aromatic hydrocarbon formaldehyde resin from the viewpoint of further excellent heat resistance and low water absorption of the obtained cured product, and is a biphenyl aralkyl type phenol. More preferably, it is a resin and / or a phenol-modified xylene resin.
  • aralkill type phenolic resin examples include compounds represented by the following formula (2a).
  • Ar 1 independently represents a benzene ring or a naphthalene ring.
  • Ar 2 represents a benzene ring, a naphthalene ring, or a biphenyl ring.
  • R 2a independently represents a hydrogen atom or a methyl group.
  • m represents an integer from 1 to 50.
  • Each ring may have a substituent other than the hydroxyl group (for example, an alkyl group having 1 to 5 carbon atoms or a phenyl group).
  • Ar 1 is a naphthalene ring and Ar 2 is a benzene ring in the above formula (2a) from the viewpoint of further excellent heat resistance and low water absorption of the obtained cured product.
  • Ar 1 is a benzene ring and Ar 2 is a biphenyl ring (also referred to as "biphenylaralkyl-type phenolic resin"). It is preferable to have.
  • the naphthol aralkyl type phenol resin is preferably a compound represented by the following formula (2b).
  • R 2a is the same as R 2a in the formula (2a), preferably a hydrogen atom.
  • m is the same as m in the above formula (2a), and is preferably an integer of 1 to 10, and more preferably an integer of 1 to 6.
  • the biphenyl aralkyl type phenol resin is preferably a compound represented by the following formula (2c).
  • R 2b independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and preferably represents a hydrogen atom.
  • m1 represents an integer of 1 to 20, preferably an integer of 1 to 6.
  • aralkyl type phenol resin a commercially available product may be used, or a product synthesized by a known method may be used.
  • Commercially available products of aralkyl-type phenolic resin include "SN-495 (trade name)” manufactured by Nippon Steel Chemical Co., Ltd. (naphthol aralkyl-type phenolic resin represented by the formula (2b)) and Nippon Kayaku Co., Ltd.
  • phenol-modified aromatic hydrocarbon formaldehyde resin refers to heating an aromatic hydrocarbon formaldehyde resin and phenols in the presence of an acidic catalyst (for example, paratoluenesulfonic acid, oxalic acid, etc.).
  • an acidic catalyst for example, paratoluenesulfonic acid, oxalic acid, etc.
  • a resin obtained by subjecting formaldehyde to a condensation reaction modified condensation reaction.
  • the aromatic hydrocarbon formaldehyde resin is not particularly limited, and is, for example, an aromatic hydrocarbon compound (for example, toluene, ethylbenzene, xylene, mesitylene, pseudocumene, a monocyclic aromatic hydrocarbon compound having 10 or more carbon atoms, and methylnaphthalene. Etc.) and a compound obtained by subjecting formaldehyde to a condensation reaction.
  • an aromatic hydrocarbon compound for example, toluene, ethylbenzene, xylene, mesitylene, pseudocumene, a monocyclic aromatic hydrocarbon compound having 10 or more carbon atoms, and methylnaphthalene. Etc.
  • a xylene formaldehyde resin obtained by subjecting xylene to formaldehyde in a condensation reaction is preferable.
  • the phenols are not particularly limited, and examples thereof include phenol, cresols, bisphenol propane, bisphenol methane, resorcin, pyrocatechol, hydroquinone, parallel butylphenol, bisphenol sulfone, bisphenol ether, and para-phenylphenol. .. These phenols may be used alone or in combination of two or more.
  • the phenol-modified aromatic hydrocarbon formaldehyde resin is preferably a phenol-modified xyleneformaldehyde resin obtained by heating the xyleneformaldehyde resin and the above-mentioned phenols in the presence of the above-mentioned acidic catalyst and causing a condensation reaction. More preferably, it is a phenol-modified xylene resin.
  • phenol-modified aromatic hydrocarbon formaldehyde resin a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Commercially available products of phenol-modified aromatic hydrocarbon formaldehyde resin include, for example, "HP-120 (trade name)", “HP-100 (trade name)", which are the Zyster (registered trademark) series manufactured by Fudo Co., Ltd. "HP-210 (product name)", “HP-70 (product name)”, “NP-100 (product name)", “GP-212 (product name)", “P-100 (product name)", Examples thereof include “GP-100 (trade name)", "GP-200 (trade name)", and "HP-30 (trade name)”.
  • Known methods include, for example, the methods described in Japanese Patent Application Laid-Open No. 2015-174874.
  • the content of the phenol compound is not particularly limited, but is preferably 10 parts by mass to 60 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the storage elastic modulus during heating tends to be a value suitable for suppressing warpage, and the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (for example, the multilayer)
  • the warpage of the coreless substrate can be further reduced.
  • the lower limit of the content is more preferably 20 parts by mass, further preferably 30 parts by mass
  • the upper limit of the content is more preferably 55 parts by mass, still more preferably 50 parts by mass. It is a part, and even more preferably 40 parts by mass.
  • the phenol equivalent of the phenolic compound (hydroxyl equivalent of the phenolic hydroxyl group) is preferably 500 g / eq or less, more preferably 400 g / eq or less, still more preferably 350 g / eq or less, and particularly preferably 300 g / eq. It is as follows. When the phenol equivalent is within the above range, the rigidity of the obtained cured product is more excellent, and the glass transition temperature and the storage elastic modulus at the time of heating tend to be suitable values for suppressing warpage.
  • the lower limit is not particularly limited, but is 100 g / eq or more.
  • epoxy compound refers to a compound having two or more epoxy groups in one molecule
  • compound refers to a concept including a resin.
  • the epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, and is, for example, a bisphenol type epoxy resin (for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type).
  • Epoxy resin and bisphenol S type epoxy resin Epoxy resin and bisphenol S type epoxy resin
  • diallyl bisphenol type epoxy resin for example, diallyl bisphenol A type epoxy resin, diallyl bisphenol E type epoxy resin, diallyl bisphenol F type epoxy resin, diallyl bisphenol S type epoxy resin, etc.
  • Containing phenols novolac type epoxy resin for example, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and cresol novolac type epoxy resin
  • aralkyl type epoxy resin biphenyl type epoxy resin containing biphenyl skeleton, and naphthalene skeleton.
  • Epoxy resins consisting of units and halogen compounds thereof can be mentioned. These epoxy compounds may be used alone or in combination of two or more.
  • aralkyl type epoxy resin from the viewpoint of further excellent heat resistance and low water absorption of the obtained cured product, aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol A type structural unit and hydrocarbon-based structure It is preferably one or more selected from the group consisting of epoxy resins consisting of units.
  • a naphthalene-type epoxy containing two or more types of epoxy compounds and two or more types of epoxy compounds containing a naphthalene skeleton.
  • a resin and / or an aralkyl type epoxy resin it is preferable to contain a resin and / or an aralkyl type epoxy resin, and more preferably to contain a naphthalene type epoxy resin and an aralkyl type epoxy resin.
  • aralkyl type epoxy resin a biphenyl aralkyl type epoxy resin is more preferable.
  • aralkill type epoxy resin examples include compounds represented by the following formula (3a).
  • Ar 3 independently represents a benzene ring or a naphthalene ring.
  • Ar 4 represents a benzene ring, a naphthalene ring, or a biphenyl ring.
  • R 3a independently represents a hydrogen atom or a methyl group.
  • k represents an integer from 1 to 50.
  • Each ring may have a substituent other than the glycidyloxy group (for example, an alkyl group having 1 to 5 carbon atoms or a phenyl group).
  • Ar 3 is a naphthalene ring and Ar 4 is benzene.
  • the ring compound (also referred to as “naphthalene aralkyl type epoxy resin”) and Ar 3 are benzene rings, and Ar 4 is a biphenyl ring compound (also referred to as "biphenyl aralkyl type epoxy resin”). It is preferable, and it is more preferable that it is a biphenylaralkyl type epoxy resin.
  • aralkyl type epoxy resin a commercially available product may be used, or a preparation prepared by a known method may be used.
  • examples of commercially available naphthalene aralkyl type epoxy resins include "Epototo (registered trademark) ESN-155 (trade name)” and “Epototo (registered trademark) ESN-355 (trade name)” manufactured by Nippon Steel & Sumitomo Metal Corporation.
  • the biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (3b) from the viewpoint of further excellent heat resistance and low water absorption of the obtained cured product.
  • ka represents an integer of 1 or more, an integer of 1 to 20 is preferable, and an integer of 1 to 6 is more preferable.
  • the aralkyl type epoxy resin is a compound represented by the following formula (3c).
  • ky represents an integer from 1 to 10.
  • Me represents a methyl group.
  • the naphthalene type epoxy resin is not particularly limited, and for example, an epoxy resin excluding the above naphthalene aralkyl type epoxy resin, which is 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 (3e)) can be mentioned.
  • Specific examples of the naphthalene type epoxy resin include naphthylene ether type epoxy resin, which is a naphthalene ether type epoxy resin from the viewpoint of further excellent heat resistance and low water absorption of the obtained cured product. Is preferable.
  • Ar 31 independently represents a benzene ring or a naphthalene ring.
  • Ar 41 represents a benzene ring, a naphthalene ring, or a biphenyl ring.
  • Each of R 31a independently represents a hydrogen atom or a methyl group.
  • p represents an integer of 0 to 2, preferably an integer of 0 or 1.
  • kz represents an integer from 1 to 50.
  • Each ring may have a substituent other than the glycidyloxy group (for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a phenyl group), and at least one of Ar 31 and Ar 41 represents a naphthalene ring. ..
  • Examples of the compound represented by the above formula (3d) include a compound represented by the following formula (3f).
  • kz is synonymous with kz in the above formula (3d).
  • naphthalene skeleton-containing polyfunctional epoxy resin a commercially available product may be used, 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.
  • epoxy resin represented by the above formula (3e) a commercially available product may be used, or a preparation prepared by a known method may be used. Examples of commercially available products include "HP-4710 (trade name)" manufactured by DIC Corporation.
  • naphtylene ether type epoxy resin examples include compounds represented by the following formula (3 g).
  • R 3b independently represents a naphthyl group containing a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aralkyl group, a naphthyl group or a glycidyloxy group.
  • k1 represents an integer from 1 to 10.
  • the number of glycidyloxy groups containing an epoxy group in the molecule is preferably 2 to 6, and more preferably 2 to 4.
  • k1 represents an integer of 0 to 10, and from the viewpoint of more effectively and surely performing the effects of the present embodiment, it is preferable to represent an integer of 0 to 6, and an integer of 0 to 4. Is more preferable, and an integer of 2 to 3 is further preferable.
  • R 3b is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aralkyl group, and a naphthyl group from the viewpoint of more effectively and surely exerting the action and effect of the present embodiment. It is preferable to represent.
  • the naphthylene ether type epoxy resin contains the compound represented by the above formula (3 g), it may contain a plurality of types of compounds having the same k1 or may contain a plurality of types of compounds having different k1s.
  • the naphthylene ether type epoxy resin contains a plurality of types of compounds having different k1
  • it is preferable that the naphthylene ether type epoxy resin contains a compound in which k1 is an integer of 0 to 4 in the above formula (3 g), and a compound having an integer of 2 to 3. It is more preferable to include.
  • Examples of the compound represented by the above formula (3 g) include a compound represented by the following formula (3h).
  • epoxy resin represented by the above formula (3h) a commercially available product may be used, or a preparation prepared by a known method may be used. Examples of commercially available products include "HP-4032 (trade name)" manufactured by DIC Corporation.
  • naphthylene ether type epoxy resin a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Commercially available products of naphthylene ether type epoxy resin include, for example, "HP-4032 (trade name)", “HP-6000 (trade name)", “EXA-7300 (trade name)", and “EXA-7300 (trade name)” manufactured by DIC Corporation. Examples thereof include “EXA-7310 (trade name)", “EXA-7311 (trade name)”, “EXA-7311L (trade name)", and "EXA7311-G3 (trade name)”.
  • dicyclopentadiene type epoxy resin examples of the dicyclopentadiene type epoxy resin include compounds represented by the following formula (3i).
  • R 3c independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • k2 represents an integer from 0 to 10.
  • k2 represents an integer of 0 to 10, and from the viewpoint of more effectively and surely performing the effects of the present embodiment, it is preferable to represent an integer of 0 to 6, and an integer of 0 to 2. Is more preferable, and 0 to 1 is more preferable.
  • the dicyclopentadiene type epoxy resin contains the compound represented by the above formula (3i), it may contain a plurality of types of compounds having the same k2, or may contain a plurality of types of compounds having different k2.
  • the dicyclopentadiene type epoxy resin contains a plurality of types of compounds having different k2, it is preferable to include a compound in which k2 is an integer of 0 to 2 in the above formula (3i).
  • dicyclopentadiene type epoxy resin a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Commercially available products of dicyclopentadiene type epoxy resin include "EPICRON (registered trademark) HP-7200L (trademark)” and “EPICRON (registered trademark) HP-7200 (trademark)” manufactured by Dainippon Ink and Chemicals Co., Ltd. , "EPICRON (registered trademark) HP-7200H (trademark)", “EPICRON (registered trademark) HP-7000HH (trademark)” and the like.
  • Epoxy resin consisting of bisphenol A type structural unit and hydrocarbon structural unit An epoxy resin composed of a bisphenol A type structural unit and a hydrocarbon-based structural unit (also referred to as “specific epoxy resin”) has one or more bisphenol A type structural units and one or more hydrocarbon-based structural units in the molecule. Has a structural unit.
  • specific epoxy resin include compounds represented by the following formula (3j).
  • R 1x and R 2x each independently represent a hydrogen atom or a methyl group.
  • R 3x to R 6x independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom.
  • X is 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 2 to 2 carbon atoms.
  • k3 represents an integer.
  • k3 represents an integer, and is preferably an integer of 1 to 10 from the viewpoint of more effectively and surely performing the effects of the present embodiment, and is preferably an integer of 1 to 6. More preferably, it is further preferably an integer of 1 to 2, and particularly preferably 1.
  • X is preferably an ethylene group from the viewpoint of more effectively and surely exerting the action and effect of the present embodiment.
  • the specific epoxy resin a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Examples of commercially available specific epoxy resins include "EPICLON (registered trademark) EXA-4850-150 (trademark)” and “EPICLON (registered trademark) EXA-4816 (trademark)” manufactured by DIC Corporation. Be done.
  • the content of the epoxy compound is not particularly limited, but is preferably 10 parts by mass to 80 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the storage elastic modulus during heating tends to be a value suitable for suppressing warpage, and the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (for example, the multilayer)
  • the warpage of the coreless substrate can be further reduced.
  • the rigidity, heat resistance, and low water absorption of the obtained cured product tend to be further improved.
  • the lower limit of the content is more preferably 20 parts by mass, further preferably 25 parts by mass, still more preferably 30 parts by mass, and particularly preferably 45 parts by mass, and the content.
  • the upper limit of is more preferably 75 parts by mass, further 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 500 g / eq or less, more preferably 400 g / eq or less, and further preferably 350 g / eq or less.
  • the lower limit is not particularly limited, but is preferably 100 g / eq or more.
  • the amount of phenol groups in the resin composition (parts by mass / epoxy equivalent) relative to the amount of epoxy groups in the resin composition (parts of content / epoxy equivalent).
  • the ratio of the content mass part / phenol equivalent) and / or the cyanate ester group amount (content mass part / cyanate ester equivalent) is preferably 0.5 to 1.5.
  • the above ratio is the ratio of the total amount of the phenol group amount and the cyanate group amount to the epoxy group amount.
  • the storage elastic modulus during heating tends to be a value suitable for suppressing warpage.
  • the lower limit of the ratio is preferably 0.5, more preferably 0.6, still more preferably 0.7, and even more preferably 0.9. ..
  • the upper limit of the ratio is preferably 1.5, more preferably 1.4, even more preferably 1.3, and even more preferably 1.2.
  • the above-mentioned phenol group amount means the total value of the phenol group amounts of each phenol compound, and when there are a plurality of types of cyanate ester compounds, the above cyanate The group amount refers to the total value of the cyanate groups of each cyanate ester compound, and when there are a plurality of types of epoxy compounds, the above epoxy group amount is the total value of the epoxy group amounts of each epoxy compound.
  • the "maleimide compound” means a compound having one or more maleimide groups in one molecule
  • the "compound” means a concept including a resin.
  • the maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule, but for example, a monomaleimide compound having one maleimide group in one molecule (for example, N-phenylmaleimide, and N-hydroxyphenylmaleimide, etc.)
  • Polymaleimide compounds having two or more maleimide groups in one molecule eg, bis (4-maleimidephenyl) methane, bis (3,5-dimethyl-4-maleimidephenyl) methane, bis (3-Ethyl-5-methyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, and polyphenylmethane maleimide compounds), and pre-forms of these maleimide and
  • polymaleimide compound examples include a compound in which a plurality of maleimide groups are bonded to a benzene ring (for example, phenylene bismaleimide such as m-phenylene bismaleimide, and 4-methyl-1,3-phenylene bismaleimide, etc.) and linear.
  • a compound in which a maleimide group is bonded to both ends of the branched alkyl chain for example, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, etc.
  • bisphenol A diphenyl ether bismaleimide examples thereof include compounds represented by.
  • R 4a and R 5a each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and preferably represent a hydrogen atom.
  • Each of R 4b independently represents a hydrogen atom or a methyl group, and preferably represents 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 above formula (4a) include bis (4-maleimidephenyl) methane, 2,2-bis ⁇ 4- (4-maleimidephenoxy) -phenyl ⁇ propane, and bis (3-ethyl-). 5-Methyl-4-maleimidephenyl) methane can be mentioned.
  • the maleimide compound contains the maleimide compound represented by the above formula (4a)
  • the coefficient of thermal expansion of the obtained cured product is further lowered, and the heat resistance and the glass transition temperature (Tg) tend to be further improved.
  • the maleimide compound may be used alone or in combination of two or more.
  • maleimide compound a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Commercially available maleimide compounds include "BMI-70 (trade name)” and “BMI-80 (trade name)” manufactured by KAI Kasei Co., Ltd., and "BMI-2300 (commodity name)” manufactured by Daiwa Kasei Kogyo Co., Ltd. "Name”, "BMI-1000P (product name)", “BMI-3000 (product name)", “BMI-4000 (product name)”, “BMI-5100 (product name)", "BMI-7000 (product name)” First name) ”and so on.
  • the content of the maleimide compound is not particularly limited, but is preferably 1 part by mass to 45 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the content is within the above range, the obtained cured product tends to be more excellent in low water absorption and the warp of the printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) can be further reduced.
  • the lower limit of the content is more preferably 4 parts by mass, further preferably 10 parts by mass, still more preferably 15 parts by mass, and the upper limit of the content is more preferably. It is 40 parts by mass, more preferably 30 parts by mass, even more preferably 25 parts by mass, and particularly preferably 20 parts by mass.
  • the resin composition in the layer containing the resin composition according to the present embodiment is not particularly limited, but may contain other resins.
  • other resins include alkenyl-substituted nadiimide compounds, oxetane resins, benzoxazine compounds, and compounds having polymerizable unsaturated groups. These resins may be used alone or in combination of two or more.
  • alkenyl-substituted nadiimide compound refers to a compound having one or more alkenyl-substituted nadiimide groups in the molecule.
  • alkenyl-substituted nadiimide compound include a compound represented by the following formula (5a).
  • R 6a independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 6b represents 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 (5c).
  • R 6c represents a methylene group, an isopropylidene group, or a divalent substituent represented by CO, O, S, or SO 2 .
  • R 6d independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.
  • alkenyl-substituted nadiimide compound also includes a compound represented by the following formulas (6) and / or (7).
  • alkenyl-substituted nadiimide compound a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Commercially available products of the alkenyl-substituted nadiimide compound are not particularly limited, and examples thereof include "BANI-M (trade name)” and "BANI-X (trade name)” manufactured by Maruzen Petrochemical Co., Ltd. These alkenyl-substituted nadiimide compounds may be used alone or in combination of two or more.
  • oxetane resin examples include alkyl oxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3.
  • the "benzoxazine compound” as used herein refers to a compound having two or more dihydrobenzoxazine rings in one 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 Konishi Chemical Co., Ltd. These Beingzoxazine compounds may be used alone or in combination of two or more.
  • Compound having a polymerizable unsaturated group examples include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl.
  • examples thereof include (meth) acrylates of monovalent or polyhydric alcohols; epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate and bisphenol F type epoxy (meth) acrylate; benzocyclobutene resin and the like. These compounds having a polymerizable unsaturated group may be used alone or in combination of two or more.
  • These other resins are not particularly limited, but are preferably 1 part by mass to 30 parts by mass, respectively, with respect to 100 parts by mass of the resin solid content.
  • the resin composition in the layer containing the resin composition according to the present embodiment is not particularly limited, but preferably contains a filler.
  • the filler include an inorganic filler and / or an organic filler.
  • the inorganic filler is not particularly limited, and is, for example, silica, a silicon compound (for example, white carbon, etc.), a metal oxide (for example, alumina, titanium white, zinc oxide, magnesium oxide, zirconium oxide, etc.), a metal.
  • Nitridees eg, boron nitride, coagulated boron nitride, silicon nitride, and aluminum nitride, etc.
  • metal sulfates eg, barium sulfate, etc.
  • metal hydroxides eg, aluminum hydroxide, and aluminum hydroxide heat treated products.
  • the filler is silica or metal hydroxide from the viewpoint of further improving the rigidity of the obtained cured product and further reducing the warp of the printed wiring board (for example, a thin substrate such as a multilayer coreless substrate).
  • the filler is silica or metal hydroxide from the viewpoint of further improving the rigidity of the obtained cured product and further reducing the warp of the printed wiring board (for example, a thin substrate such as a multilayer coreless substrate).
  • the filler is silica or metal hydroxide from the viewpoint of further improving the rigidity of the obtained cured product and further reducing the warp of the printed wiring board (for example, a thin substrate such as a multilayer coreless substrate).
  • at least one selected from the group consisting of metal oxides more preferably at least one selected from the group consisting of silica, boehmite, and alumina, further preferably silica. preferable.
  • silica examples include natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, hollow silica and the like.
  • spherical fused silica is preferable from the viewpoint of further improving the rigidity of the obtained cured product and further reducing the warp of the printed wiring board (for example, a thin substrate such as a multilayer coreless substrate).
  • SC2050-MB trade name
  • SC5050-MOB trade name
  • SC2500-SQ trade name
  • SC4500-SQ trade name
  • SO-C2 trade name
  • SO-C1 trade name
  • SFP-130MC trade name
  • the organic filler is not particularly limited, and examples thereof include rubber powders such as styrene type powder, butadiene type powder, and acrylic type powder; core shell type rubber powder; and silicone type powder. These organic fillers may be used alone or in combination of two or more. Among these, the silicone type powder is preferable from the viewpoint of further reducing the warp of the printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) which is more excellent in the rigidity of the obtained cured product.
  • silicone type powder examples include silicone resin powder, silicone rubber powder, and silicone composite powder. These silicone-type powders may be used alone or in combination of two or more. Among these, the silicone composite powder is preferable from the viewpoint of further reducing the warp of the printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) which is more excellent in the rigidity of the obtained cured product.
  • the silicone composite powder examples include KMP-600 (trade name), KMP-601 (trade name), KMP-602 (trade name), KMP-605 (trade name), and X-, manufactured by Nissin Chemical Co., Ltd. Examples thereof include 52-7030 (trade name).
  • the content of the silicone powder is not particularly limited, but is preferably 0 parts by mass to 100 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the content is within the above range, the rigidity of the obtained cured product tends to be further improved, and the warp of the printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) tends to be further reduced.
  • the lower limit of the content is more preferably 10 parts by mass, more preferably 15 parts by mass
  • the upper limit of the content is more preferably 50 parts by mass, 40 parts by mass. It is more preferably parts by mass, and even more preferably 30 parts by mass.
  • the filler of the present embodiment preferably contains an inorganic filler and an organic filler.
  • the content of the inorganic filler is not particularly limited, but is preferably 90 parts by mass to 700 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the rigidity of the obtained cured product tends to be further improved, and the warp of the printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) tends to be further reduced, and further.
  • the above formulas (i), (ii), and (iii) can be controlled within a desired range.
  • the lower limit of the content is more preferably 120 parts by mass, further preferably 140 parts by mass
  • the upper limit of the content is more preferably 600 parts by mass, 500 parts by mass. It is more preferably parts by mass, and even more preferably 250 parts by mass.
  • the content of the organic filler is not particularly limited, but is preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the content is within the above range, the rigidity of the obtained cured product tends to be further improved, and the warp of the printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) tends to be further reduced.
  • the lower limit of the content is more preferably 5 parts by mass, further preferably 10 parts by mass
  • the upper limit of the content is more preferably 40 parts by mass, 30 parts by mass. It is more preferably parts by mass, and even more preferably 25 parts by mass.
  • the total content of the filler is not particularly limited, but is preferably 100 parts by mass to 700 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the content is within the above range, the rigidity of the obtained cured product tends to be further improved, and the warp of the printed wiring board (for example, a thin substrate such as a multilayer coreless substrate) tends to be further reduced.
  • the lower limit of the content is more preferably 130 parts by mass, further preferably 150 parts by mass
  • the upper limit of the content is more preferably 600 parts by mass, 500 parts by mass. It is more preferably parts by mass, and even more preferably 250 parts by mass.
  • the resin composition in the layer containing the resin composition according to the present embodiment is not particularly limited, but preferably contains a silane coupling agent.
  • a silane coupling agent by containing the silane coupling agent, the dispersibility of the filler is further improved, and the components of the resin composition in the layer containing the resin composition according to the present embodiment and the base material described later are used. There is a tendency that the adhesive strength of silane can be further improved.
  • the silane coupling agent is not particularly limited, and examples thereof include a silane coupling agent generally used for surface treatment of inorganic substances, and examples thereof include aminosilane compounds (for example, ⁇ -aminopropyltriethoxysilane and N- ⁇ - (aminoethyl).
  • aminosilane compounds for example, ⁇ -aminopropyltriethoxysilane and N- ⁇ - (aminoethyl).
  • the silane coupling agent is preferably an epoxy silane compound.
  • the epoxy silane compound include "KBM-403 (trade name)”, “KBM-303 (trade name)”, “KBM-402 (trade name)”, and “KBE-” manufactured by Shin-Etsu Chemical Co., Ltd. 403 (trade name) ”and the like.
  • the content of the silane coupling agent is not particularly limited, but is preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the resin composition in the layer containing the resin composition according to the present embodiment is not particularly limited, but preferably contains a wetting dispersant.
  • a wetting dispersant by containing the wet dispersant, the dispersibility of the filler is further improved, the rigidity of the obtained cured product is further improved, and the metal foil-clad laminate, the printed wiring board, and the multilayer print are further improved.
  • the warpage of the wiring board for example, a multilayer coreless substrate
  • the wet dispersant may be a known dispersant (dispersion stabilizer) used for dispersing the filler.
  • DISPERBYK registered trademark
  • -110 trade name
  • 111 Product Name
  • 118 Product Name
  • 180 Product Name
  • 161 Product Name
  • W996 Product Name
  • W9010 Product Name
  • W903 Product Name
  • the content of the wet dispersant is not particularly limited, but is preferably 1 part by mass to 5 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the content is within the above range, the dispersibility of the filler is further improved, the rigidity of the obtained cured product is further improved, and the metal foil-clad laminate, the printed wiring board and the multilayer printed wiring board (for example, , The warp of the multilayer coreless substrate) tends to be further reduced.
  • the lower limit of the content is more preferably 1.5 parts by mass and further preferably 2 parts by mass.
  • the resin composition in the layer containing the resin composition according to the present embodiment is not particularly limited, but preferably contains a curing accelerator.
  • the curing accelerator is not particularly limited, and is, for example, imidazoles (for example, triphenylimidazole, etc.), organic peroxides (for example, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and the like.
  • Organic tin compounds (for example, dioctyl tin oxide, other alkyl tin, alkyl tin oxide, etc.) can be mentioned.
  • These curing accelerators may be used alone or in combination of two or more.
  • 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 obtained cured product.
  • the content of the curing accelerator is not particularly limited, but is preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the resin composition in the layer containing the resin composition according to the present embodiment is not particularly limited, but the thermosetting resin and the thermoplastic resin which have not been mentioned so far are not particularly limited as long as the characteristics of the present embodiment are not impaired. , And various polymer compounds such as oligomers and elastomers; and additives not mentioned above may be included. These are not particularly limited as long as they are generally used. Additives are not particularly limited, but are, for example, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, flow modifiers, lubricants, and erasers.
  • foaming agents examples thereof include foaming agents, dispersants, leveling agents, brighteners, and polymerization inhibitors.
  • These other additives may be used alone or in admixture of two or more.
  • the content of the other additives is not particularly limited, but is usually 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the resin composition in the layer containing the resin composition according to the present embodiment is not particularly limited, but may contain a solvent.
  • the resin composition of the present embodiment contains a solvent, the viscosity of the resin composition at the time of preparation is lowered, the handleability (handleability) is further improved, and the impregnation property into the base material is further improved. There is a tendency.
  • the solvent is not particularly limited as long as it can dissolve a part or all of the resin component in the resin composition, but is not particularly limited, and for example, ketones (acetone, methyl ethyl ketone, methyl cell solve, etc.), aromatic hydrocarbons (such as methyl cell solve) For example, toluene, xylene, etc.), amides (eg, dimethylformaldehyde, etc.), propylene glycol monomethyl ether, acetate thereof, and the like can be mentioned. These solvents may be used alone or in combination of two or more.
  • a varnish in which each component is collectively or sequentially blended with a solvent, stirred, and dissolved or dispersed in the solvent As a method for producing a resin composition in a layer containing the resin composition according to the present embodiment, for example, a varnish in which each component is collectively or sequentially blended with a solvent, stirred, and dissolved or dispersed in the solvent. A method of obtaining the above can be mentioned. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading are used.
  • the solvent is as described above. Examples can be referred to for specific manufacturing methods.
  • the method for producing the resin sheet of the present embodiment a method for producing a composite of a layer and a support containing a B-staged resin composition is generally preferable.
  • the resin composition according to the present embodiment is used as a varnish in the form of a varnish, and the varnish is applied to a support such as a copper foil by using a known method such as a bar coater, and then the temperature is 100 ° C. to 200 ° C.
  • a method of producing a resin sheet by semi-curing by a method of heating for 1 to 60 minutes in the dryer of the above can be mentioned. Examples can be referred to for specific manufacturing methods.
  • the thickness of the layer containing the resin composition is not particularly limited, but is preferably in the range of 1.0 ⁇ m to 300 ⁇ m.
  • the resin sheet of the present embodiment can sufficiently reduce the warpage of the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (for example, the multilayer coreless substrate), and has excellent rigidity and heat resistance. Can express sex. Therefore, the resin sheet of the present embodiment is used for, for example, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board.
  • the resin composition of the present embodiment is also suitably used as an insulating layer such as a printed wiring board or a laminated board.
  • the resin sheet of the present embodiment may be used for the laminated board.
  • the laminated board contains one or more layers containing a cured product of the resin composition, and when a plurality of layers are contained, the layer containing the cured product is laminated or a metal. It has a form of being laminated via a conductive layer such as a foil.
  • the laminated board has sufficiently reduced warpage, and has excellent rigidity and heat resistance.
  • the metal foil-clad laminate of the present embodiment includes a layer containing a cured product of the resin composition and metal foils arranged on one or both sides of the layer containing the cured product in the resin sheet of the present embodiment. ..
  • the metal leaf-clad laminate of the present embodiment includes one 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 the cured product is one, the metal foil-clad laminate has a form in which the metal foil is arranged on one side or both sides of the layer containing the cured product.
  • the metal foil-clad laminate has a form in which the metal foil is arranged on one side or both sides of the layer containing the laminated cured product.
  • the metal leaf-clad laminate of the present embodiment has sufficiently reduced warpage, and has excellent rigidity and heat resistance.
  • the metal foil may be any metal foil used for various printed wiring board materials, and examples thereof include metal foils such as copper and aluminum. Copper metal foils include rolled copper foil and Examples thereof include copper foil such as electrolytic copper foil.
  • the thickness of the conductor layer is, for example, 1 ⁇ m to 70 ⁇ m, preferably 1.5 ⁇ m to 35 ⁇ m.
  • the molding method of the laminated board and the metal foil-clad laminated board, and the molding conditions thereof are not particularly limited, and general methods and conditions for the laminated board for printed wiring boards and the multilayer board can be applied.
  • a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, or the like can be used when forming a laminated plate or a metal leaf-clad laminate.
  • the temperature is 100 ° C. to 300 ° C.
  • the pressure is a surface pressure of 2 kgf / cm 2 to 100 kgf / cm 2
  • the heating time is 0.05 hours to 5 hours.
  • the time range is common. Further, if necessary, post-curing can be performed at a temperature of 150 ° C. to 300 ° C.
  • the temperature is 200 ° C. to 250 ° C.
  • the pressure is 10 kgf / cm 2 to 40 kgf / cm 2
  • the heating time is 80 minutes from the viewpoint of sufficiently promoting the curing of the resin composition on the resin sheet.
  • the temperature is preferably 215 ° C. to 235 ° C.
  • the pressure is 25 kgf / cm 2 to 35 kgf / cm 2
  • the heating time is 90 minutes to 120 minutes.
  • the printed wiring board of the present embodiment includes an insulating layer formed of a cured product of the resin composition thereof and a conductor layer formed on the surface of the insulating layer in the resin sheet of the present embodiment.
  • the printed wiring board of the present embodiment can be formed, for example, by etching the metal foil of the metal foil-clad laminate of the present embodiment into a predetermined wiring pattern to form a conductor layer.
  • the printed wiring board of the present embodiment has sufficiently reduced warpage, and has excellent rigidity and heat resistance.
  • the printed wiring board of this 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 create an inner layer substrate having a conductor layer (inner layer circuit).
  • a laminate is obtained by integral molding (laminate molding).
  • the laminating molding method and the molding conditions thereof are the same as the laminating molding method and the molding conditions for the above-mentioned laminated board and the metal leaf-clad laminated board.
  • the laminated body is subjected to drilling for through holes and via holes, and a plated metal film for conducting the conductor layer (interior circuit) and the metal foil for the outer layer circuit on the wall surface of the formed holes.
  • the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to prepare an outer layer substrate having a conductor layer (outer layer circuit). In this way, the printed wiring board is manufactured.
  • the prepreg contains a base material and a resin composition impregnated or coated on the base material.
  • the prepreg may be a prepreg obtained by a known method. Specifically, the prepreg is obtained by impregnating or coating the base material with the resin composition and then heating and drying it under the conditions of 100 ° C to 200 ° C. Obtained by curing (B-stage).
  • the resin composition is not particularly limited, and examples thereof include known resin compositions used as materials for various printed wiring boards.
  • the base material is not particularly limited, and examples thereof include known base materials used as materials for various printed wiring boards.
  • a conductor layer to be a circuit may be formed on the layer containing the resin composition in the resin sheet to produce a printed wiring board.
  • an electroless plating method can also be used to form the conductor layer.
  • the resin sheet of the present embodiment may be used for the multilayer printed wiring board.
  • the multilayer printed wiring board is not particularly limited, and for example, a plurality of insulating layers including a first insulating layer and one or a plurality of second insulating layers laminated on one side of the first insulating layer. It has a plurality of conductor layers including a first conductor layer arranged between each of the plurality of insulating layers and a second conductor layer arranged on the surface of the outermost layer of the plurality of insulating layers. Examples thereof include a form in which the first insulating layer and the second insulating layer are each an insulating layer formed of a cured product of the resin composition in the resin sheet of the present embodiment.
  • the multilayer printed wiring board examples include a so-called coreless type multilayer printed wiring board (multilayer coreless substrate) in which a second insulating layer is laminated only in one side direction of the first insulating layer.
  • the multilayer printed wiring board since the insulating layer formed of the cured product of the resin composition in the resin sheet of the present embodiment is used, the multilayer printed wiring board has sufficiently reduced warpage, and has excellent rigidity and heat resistance. Have. Therefore, in the present embodiment, the warp can be sufficiently reduced (low warpage is achieved) in the multilayer coreless substrate, so that the multilayer coreless substrate can be effectively used as a multilayer coreless substrate for a semiconductor package.
  • Biphenyl aralkyl type phenol resin (KAYAHARD (registered trademark) GPH-103 (trade name), manufactured by Nippon Kayaku Co., Ltd., hydroxyl group equivalent: 231 g / eq., Represented by the above formula (2c), R 2b in the formula 36 parts by mass (all hydrogen atoms), biphenyl aralkyl type epoxy resin (NC-3000FH (trade name), epoxy equivalent: 320 g / eq., Manufactured by Nippon Kayaku Co., Ltd., represented by the above formula (3b)) 39 parts by mass, aralkyl type epoxy resin (HP-9900 (trade name), epoxy equivalent: 274 g / eq., DIC Co., Ltd., represented by the above formula (3c)) 7 parts by mass, bis (3-ethyl) -5-Methyl-4-maleimidephenyl) methane (BMI-70 (trade name), manufactured by Kei
  • This varnish (resin composition) is diluted with methyl ethyl ketone and applied to the matte surface side of a 350 mm ⁇ 250 mm ⁇ 12 ⁇ m thick copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metal Mining Co., Ltd.) with a bar coater.
  • Example 2 The amount of biphenyl aralkyl type epoxy resin (NC-3000-FH (trade name)) was changed from 39 parts by mass to 19 parts by mass, and the naphthylene ether type epoxy resin (HP-6000 (trade name), epoxy equivalent: 250 g). / Eq., DIC Co., Ltd., represented by the above formula (3 g), all R 3b in the formula are hydrogen atoms, and the number of repeating units k1 is 2.) Examples except that 20 parts by mass was blended. In the same manner as in No. 1, a B-staged (minimum melt viscosity: about 1000 Pa ⁇ s) layered copper foil containing the resin composition having a thickness of the layer containing the resin composition of 20 ⁇ m was obtained.
  • NC-3000-FH trade name
  • Example 3 20 parts by mass of biphenyl aralkyl type phenol resin (KAYAHARD (registered trademark) GPH-103 (trade name)), phenol-modified xylene resin (Zyster (registered trademark) GP-100 (trade name), Fudo Co., Ltd., phenol equivalent: 194 g / Eq.) 15 parts by mass, 34 parts by mass of biphenyl aralkyl type epoxy resin (NC-3000-FH (trade name)), 5 parts by mass of naphthalene aralkyl type epoxy resin (HP-9900 (trade name)), dicyclopentadiene type Epoxy resin (EPICRON (registered trademark) HP-7200L (trade name), epoxy equivalent: 249 g / eq., Manufactured by DIC Co., Ltd., represented by the above formula (3i), and all R 3c in the formula are hydrogen atoms.
  • This varnish (resin composition) is diluted with methyl ethyl ketone and applied to the matte surface side of a 350 mm ⁇ 250 mm ⁇ 12 ⁇ m thick copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metal Mining Co., Ltd.) with a bar coater.
  • Example 4 34 parts by mass of ⁇ -naphthol aralkyl type cyanate ester compound (cyanate equivalent: 261 g / eq) synthesized by the method described in Synthesis Example 1, 15 parts by mass of biphenyl aralkyl type epoxy resin (NC-3000-FH (trade name)) , Naftyrene ether type epoxy resin (HP-6000 (trade name)) 5 parts by mass, dicyclopentadiene type epoxy resin (EPICRON (registered trademark) HP-7200L (trade name)) 26 parts by mass, bisphenol A type structural unit Epoxy resin composed of hydrocarbon-based structural units (EPICLON (registered trademark) EXA-4816 (trade name), manufactured by DIC Co., Ltd., epoxy equivalent: 403 g / eq., Represented by the above formula (3j)) 15 parts by mass , Bis (3-ethyl-5-methyl-maleimidephenyl) methane (BMI-70
  • This varnish (resin composition) is diluted with methyl ethyl ketone and applied to the matte surface side of a 350 mm ⁇ 250 mm ⁇ 12 ⁇ m thick copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metal Mining Co., Ltd.) with a bar coater.
  • This varnish (resin composition) is diluted with methyl ethyl ketone and placed on the matte surface side of a 350 mm ⁇ 250 mm ⁇ 12 ⁇ m thick copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metal Mining Co., Ltd.) with a bar coater. By coating and heating and drying at 130 ° C. for 5 minutes, a B-staged layered copper foil containing the resin composition having a thickness of the layer containing the resin composition of 20 ⁇ m was obtained.
  • 3EC-M2S-VLP trade name
  • This varnish (resin composition) is diluted with methyl ethyl ketone and placed on the matte surface side of a 350 mm ⁇ 250 mm ⁇ 12 ⁇ m thick copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metal Mining Co., Ltd.) with a bar coater. By coating and heating and drying at 130 ° C. for 5 minutes, a B-staged layered copper foil containing the resin composition having a thickness of the layer containing the resin composition of 20 ⁇ m was obtained.
  • 3EC-M2S-VLP trade name
  • This varnish (resin composition) is diluted with methyl ethyl ketone and placed on the matte surface side of a 350 mm ⁇ 250 mm ⁇ 12 ⁇ m thick copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metal Mining Co., Ltd.) with a bar coater. By coating and heating and drying at 130 ° C. for 5 minutes, a B-staged layered copper foil containing the resin composition having a thickness of the layer containing the resin composition of 20 ⁇ m was obtained.
  • 3EC-M2S-VLP trade name
  • -VLP (trade name), manufactured by Mitsui Kinzoku Mining Co., Ltd., thickness 12 ⁇ m) was placed on a copper foil-clad laminate, and the resin component was sandwiched between the copper foils on the front and back. Then, laminating molding (thermosetting) was performed at a pressure of 30 kgf / cm 2 and a temperature of 230 ° C. for 100 minutes to obtain a laminated plate having a copper foil, an insulating layer in which the resin component was cured, and the copper foil. The thickness of the insulating layer was about 800 ⁇ m.
  • the storage elastic modulus E'obtained from each measurement sample the arithmetic mean value of the storage elastic modulus E'at each temperature was calculated, and these values were taken as the storage elastic modulus E'.
  • the mechanical properties were measured in the same manner, and the storage elastic modulus E'was calculated for each. did.
  • -VLP (trade name), manufactured by Mitsui Kinzoku Mining Co., Ltd., thickness 12 ⁇ m) was placed on a copper foil-clad laminate, and the resin component was sandwiched between the copper foils on the front and back. Then, laminating molding (thermosetting) was performed at a pressure of 30 kgf / cm 2 and a temperature of 230 ° C. for 100 minutes to obtain a laminated plate having a copper foil, an insulating layer in which the resin component was cured, and the copper foil. The thickness of the insulating layer was about 800 ⁇ m.
  • the copper foils on both sides arranged on the laminate are removed by etching to obtain a sample for measurement. It was.
  • three measurement samples were prepared.
  • the glass transition temperature (Tg) of each of these three measurement samples was measured by the DMA method with a dynamic viscoelastic analyzer (manufactured by TA Instruments) in accordance with JIS C6481.
  • the arithmetic mean value was calculated using the glass transition temperature obtained from each measurement sample, and this value was taken as the glass transition temperature.
  • the glass transition temperature was measured in the same manner for the B-staged layered copper foil containing the resin compositions obtained in Examples 2 to 4 and Comparative Examples 1 to 5, and the glass transition temperature was calculated.
  • the copper foil-clad laminate 1 only one side of the copper foils on both sides was removed by etching to obtain a copper foil-clad laminate 2.
  • the surface of the layer containing the resin composition in another layered copper foil was placed on the surface of the insulating layer of the copper foil-clad laminate 2 so as to be placed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes.
  • the copper foil-clad laminate 3 was obtained by laminating molding (thermosetting). The total thickness of the two insulating layers was about 40 ⁇ m.
  • the copper foil was removed by etching on both sides to obtain a laminate.
  • a strip-shaped plate having a size of 20 mm ⁇ 200 mm was cut out from the obtained laminated plate.
  • one end of the strip-shaped plate in the lateral direction is attached to a surface perpendicular to the plane with a magnet, a straightedge is applied parallel to the plane, and the maximum distance between the vertical surface and the strip-shaped plate is measured.
  • the value was set as the "warp amount”.
  • the amount of warpage was less than 4 mm, it was evaluated as "AA”, and in other cases, it was evaluated as "CC”.
  • the amount of warpage of the B-staged layered copper foil containing the resin compositions obtained in Examples 2 to 4 and Comparative Examples 1 to 5 was measured and evaluated in the same manner.
  • a copper foil-clad laminate 1 (HL832NS (trade name) T / T 0.8 mmt, manufactured by Mitsubishi Gas Chemical Company) was prepared.
  • the copper foil surfaces on both sides of the copper foil-clad laminate 1 are etched by about 1 ⁇ m to 3 ⁇ m (inner layer roughening treatment, CZ-8100 (trade name), manufactured by MEC Co., Ltd.), and the copper foil surfaces on both sides are subjected to etching.
  • the surfaces of the layers containing the resin composition in the layered copper foil obtained in Example 1 were placed on top of each other, and laminated molding (thermosetting) was performed at a pressure of 30 kgf / cm 2 and a temperature of 230 ° C. for 100 minutes.
  • a copper foil-clad laminate 2 was obtained. Next, the copper foil-clad laminate 2 was cut (downsized) into a size of 50 mm ⁇ 50 mm with a dicing saw to obtain a sample for measurement. The obtained sample was left in a constant temperature bath at 120 ° C. for 1 hour and then immersed in a solder bath at 260 ° C. for 30 seconds to evaluate heat resistance. After 30 seconds, delamination occurs between the copper foil on the surface of the copper foil-clad laminate 1 and the cured product layer obtained by curing the layer containing the resin composition on both sides of the copper foil-clad laminate 1. I confirmed the presence or absence of.
  • the resin sheet of the present invention can be used, for example, for a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board.

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Physics & Mathematics (AREA)
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  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
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CN119060038A (zh) * 2024-11-06 2024-12-03 成都科宜高分子科技有限公司 烯丙基纳迪克苯并噁嗪衍生物及其制备方法、树脂

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