WO2024034463A1 - Composition de résine, feuille de cuivre avec résine, et carte de circuit imprimé - Google Patents

Composition de résine, feuille de cuivre avec résine, et carte de circuit imprimé Download PDF

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Publication number
WO2024034463A1
WO2024034463A1 PCT/JP2023/028105 JP2023028105W WO2024034463A1 WO 2024034463 A1 WO2024034463 A1 WO 2024034463A1 JP 2023028105 W JP2023028105 W JP 2023028105W WO 2024034463 A1 WO2024034463 A1 WO 2024034463A1
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Prior art keywords
resin
copper foil
resin composition
group
weight
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PCT/JP2023/028105
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English (en)
Japanese (ja)
Inventor
和弘 大澤
国春 小川
遥 牧野
昭典 田村
歩 立岡
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三井金属鉱業株式会社
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Publication of WO2024034463A1 publication Critical patent/WO2024034463A1/fr

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Classifications

    • 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
    • B32B15/082—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 vinyl resins; comprising acrylic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a resin composition, a resin-coated copper foil, and a printed wiring board.
  • Printed wiring boards are widely used in electronic devices.
  • the frequency of signals has been increasing, making high-speed, large-capacity communication possible. Examples of such applications include communication servers, self-driving cars, and 5G-enabled mobile phones.
  • This high frequency printed wiring board is desired to have low transmission loss in order to be able to transmit high frequency signals without deteriorating their quality.
  • a printed wiring board is equipped with a copper foil processed into a wiring pattern and an insulating resin base material, but transmission loss is mainly a conductor loss due to the copper foil and a dielectric loss due to the insulating resin base material. It consists of. Therefore, in a copper foil with a resin layer applied to high frequency applications, it is desirable to suppress dielectric loss caused by the resin layer. For this purpose, the resin layer is required to have excellent dielectric properties, particularly a low dielectric loss tangent.
  • Patent Document 1 International Publication No. 2013/105650 discloses a copper foil with an adhesive layer that has an adhesive layer on one side of the copper foil, and this adhesive layer is made of a polyphenylene ether compound with a mass of 100% It is made of a resin composition containing 5 parts by mass or more and 65 parts by mass or less of a styrene-butadiene block copolymer.
  • Patent Document 2 International Publication No.
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2011-225639 discloses a thermosetting resin composition containing an uncured semi-IPN composite and (D) a radical reaction initiator.
  • This uncured semi-IPN type composite consists of (A) polyphenylene ether, (B) a butadiene polymer containing 40% or more of 1,2-butadiene units having a 1,2-vinyl group in the side chain; (C) A prepolymer formed from a crosslinking agent is said to be compatible and uncured.
  • the present inventors have studied resin compositions that can be attached to base materials such as prepregs as primer layers (adhesive layers) as resin compositions with excellent dielectric properties and the like.
  • the layer of this resin composition is provided in the form of a resin-coated copper foil, and this copper foil can be used as a circuit-forming copper foil.
  • Resin compositions for the above-mentioned applications are desired to have not only excellent dielectric properties but also excellent adhesion to low-roughness surfaces (for example, the surface of low-roughness copper foil).
  • low-roughness copper foil is desired from the perspective of reducing transmission loss, but because such copper foil has low roughness, it tends to have poor adhesion with resin compositions. It is in.
  • resin compositions for the above applications must not only exhibit excellent dielectric properties and high adhesion to low-roughness surfaces (for example, the surface of low-roughness copper foil), but also exhibit high adhesion even after heat load. It is desirable to be able to maintain stable sex.
  • the present inventors have recently discovered that by blending a predetermined arylene ether compound and/or a predetermined styrenic copolymer with an organic filler composed of a liquid crystal polymer, excellent dielectric properties (for example, a low dielectric loss tangent at 10 GHz) can be achieved. ) and low-roughness surfaces (for example, the surface of low-roughness copper foil), it is possible to provide a resin composition that not only exhibits high adhesion to low-roughness surfaces (for example, the surface of low-roughness copper foil) but also can stably maintain that high adhesion even after heat load. I gained knowledge.
  • an object of the present invention is to provide a resin composition that not only exhibits excellent dielectric properties and high adhesion to low-roughness surfaces, but also can stably maintain this high adhesion even after heat load. It is in.
  • the reactive unsaturated bond is at least one selected from the group consisting of a cyanate group, a maleimide group, a terminal vinyl group, a (meth)acryloyl group, an ethynyl group, and a styryl group. thing.
  • Aspect 3 The resin composition according to aspect 1 or 2, wherein the styrenic copolymer has a styryl group as the reactive unsaturated bond.
  • Aspect 4 The resin composition according to any one of aspects 1 to 3, wherein the resin composition contains both the arylene ether compound and the styrenic copolymer.
  • Aspect 5 The resin composition according to any one of aspects 1 to 4, wherein the organic filler has a dielectric loss tangent of 0.001 or less at a frequency of 10 GHz.
  • a resin-coated copper foil comprising a copper foil and a resin layer containing the resin composition according to any one of aspects 1 to 5 provided on at least one surface of the copper foil.
  • the resin composition of the present invention contains at least one of an arylene ether compound and a styrene copolymer, and an organic filler.
  • the arylene ether compound has a weight average molecular weight of 30,000 or more, while the styrenic copolymer has a reactive unsaturated bond in its molecule that becomes reactive with heat or ultraviolet light.
  • the organic filler is composed of liquid crystal polymer.
  • the present inventors have studied resin compositions that can be attached to base materials such as prepregs as primer layers (adhesive layers) as resin compositions with excellent dielectric properties and the like.
  • the layer of this resin composition is provided in the form of a resin-coated copper foil, and this copper foil can be used as a circuit-forming copper foil.
  • Resin compositions for the above-mentioned applications are desired to have not only excellent dielectric properties but also excellent adhesion to low-roughness surfaces (for example, the surface of low-roughness copper foil).
  • low-roughness copper foil is desired from the perspective of reducing transmission loss, but because such copper foil has low roughness, it tends to have poor adhesion with resin compositions.
  • the resin composition of the present invention contains at least one of an arylene ether compound having a weight average molecular weight of 30,000 or more and a styrenic copolymer having a reactive unsaturated bond in the molecule that exhibits reactivity with heat or ultraviolet rays.
  • it contains both an arylene ether compound and the styrenic copolymer described above.
  • the resin composition of the present invention preferably has a dielectric loss tangent at a frequency of 10 GHz after curing of less than 0.0035, more preferably less than 0.0020, and still more preferably less than 0.0015.
  • the resin composition of the present invention preferably contains an arylene ether compound.
  • the weight average molecular weight of this arylene ether compound is 30,000 or more, preferably 30,000 or more and 300,000 or less, more preferably 40,000 or more and 200,000 or less, particularly preferably 45,000 or more and 120,000 or less.
  • the arylene ether compound having a weight average molecular weight of 30,000 or more is preferably a phenylene ether compound, such as polyphenylene ether.
  • the arylene ether compound or phenylene ether compound has the following formula: (In the formula, R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms) It is preferable that the compound contains a skeleton represented by the following in its molecule.
  • phenylene ether compounds include styrene derivatives of phenylene ether compounds, phenylene ether compounds containing a maleic anhydride structure in the molecule, terminal hydroxyl group-modified phenylene ether compounds, terminal methacrylic-modified phenylene ether compounds, and terminal glycidyl ether-modified phenylene ether compounds. Can be mentioned.
  • Examples of products of arylene ether compounds having a maleic anhydride structure in the molecule and having a weight average molecular weight of 30,000 or more include PME-80 and PME-82 manufactured by Mitsubishi Engineering Plastics Corporation.
  • the arylene ether compound of the present invention preferably has a reactive unsaturated bond.
  • the resin composition may further include an additional arylene ether compound having a reactive unsaturated bond.
  • the additional arylene ether compound does not need to have a weight average molecular weight of 30,000 or more. That is, the additional arylene ether compound can have a weight average molecular weight of less than 30,000 (although it may have a weight average molecular weight of 30,000 or more), for example, it can have a number average molecular weight of 500 or more and 10,000 or less.
  • a reactive unsaturated bond is defined as an unsaturated bond that exhibits reactivity with heat or ultraviolet light.
  • Preferred examples of reactive unsaturated bonds include cyanate groups, maleimide groups, vinyl groups, (meth)acryloyl groups, ethynyl groups, styryl groups, and combinations thereof.
  • a styryl group is particularly preferred because it has high reactivity and allows control of the reaction (reactions are difficult to occur over time, the resin can be stored, and a long product life can be ensured).
  • the reactive unsaturated bond in the arylene ether compound is preferably located at or adjacent to the end of the molecular structure, since it exhibits high reactivity.
  • a 1,2-vinyl group is an example of a functional group having an unsaturated bond at the end of its molecular structure, and since the 1,2-vinyl group exhibits high reactivity, it can be used as a functional group for radical polymerization. It is common as On the other hand, in the case of ethylenically unsaturated bonds (vinyl groups not located at the ends of the molecular structure) present in the molecular chain, the reactivity decreases.
  • the position of the reactive unsaturated bond may be a) the end of the molecular structure (regardless of whether it is the main chain or the side chain), or b) the end of the molecular structure (regardless of whether it is the main chain or the side chain). If a benzene ring is located at the position (not present), it may be located adjacent to the terminal benzene ring.
  • the arylene ether compound may have styryl groups as reactive unsaturated bonds at both ends of its molecular structure.
  • Examples of products of arylene ether compounds having styryl groups at both ends of the molecule include OPE-2St-1200 and OPE-2St-2200 manufactured by Mitsubishi Gas Chemical Co., Ltd. (However, the arylene ether compounds of these products have a weight average molecular weight is less than 30,000).
  • the content is not particularly limited, but from the viewpoint of achieving both compatibility (related to peel strength) and dielectric properties. , preferably 10 parts by weight or more and 90 parts by weight or less, more preferably 15 parts by weight or more and 80 parts by weight or less, even more preferably 20 parts by weight or more and 60 parts by weight, based on 100 parts by weight of the total amount of resin components (solid content). It is as follows. In this specification, the total amount of resin components (solid content) of 100 parts by weight includes not only the polymer and resin but also the weight of additives such as reaction initiators that constitute a part of the resin. However, organic fillers are not included in the calculation.
  • the resin composition of the present invention preferably contains a styrenic copolymer having a reactive unsaturated bond in the molecule that exhibits reactivity with heat or ultraviolet light.
  • the styrenic copolymer may be either hydrogenated or non-hydrogenated. That is, the styrenic copolymer is a compound containing a moiety derived from styrene, and may also contain a moiety derived from a compound having a polymerizable unsaturated group such as an olefin in addition to styrene.
  • a double bond is further present in a site derived from a compound having a polymerizable unsaturated group in the styrenic copolymer
  • the double bond may be hydrogenated or not hydrogenated. It may be.
  • styrenic copolymers include acrylonitrile-butadiene-styrene copolymer (ABS), methacrylate-butadiene-styrene copolymer (MBS), acrylonitrile-acrylate-styrene copolymer (AAS), and acrylonitrile-butadiene-styrene copolymer (AAS).
  • Ethylene-styrene copolymer AES
  • SBR styrene-butadiene copolymer
  • SBS styrene-butadiene-styrene copolymer
  • SEBS styrene-ethylene-butadiene-styrene copolymer
  • SBR styrene-butadiene block copolymer
  • styrene/4-methylstyrene/isoprene/butadiene block copolymer Especially preferred is a styrene/4-methylstyrene/isoprene/butadiene block copolymer.
  • the weight average molecular weight of the styrenic copolymer is not particularly limited, but is preferably 40,000 or more and 400,000 or less, more preferably 60,000 or more and 370,000 or less, particularly preferably 80,000 or more and 340,000 or less.
  • the styrenic copolymer used in the present invention has a reactive unsaturated bond in its molecule that becomes reactive with heat or ultraviolet light.
  • Preferred examples of reactive unsaturated bonds include cyanate groups, maleimide groups, terminal vinyl groups, (meth)acryloyl groups, ethynyl groups, styryl groups, and combinations thereof.
  • a styryl group is particularly preferred because it has high reactivity and allows control of the reaction (reactions are difficult to occur over time, the resin can be stored, and a long product life can be ensured).
  • the reactive unsaturated bonds in the styrenic copolymer are preferably located at or adjacent to the ends of the molecular structure in view of exhibiting high reactivity.
  • a 1,2-vinyl group is an example of a functional group that has an unsaturated bond at the end of its molecular structure, but the 1,2-vinyl group (terminal vinyl group) is highly reactive and therefore difficult to radically polymerize. It is a common functional group that can be used. Therefore, a styrenic copolymer having such a functional group can be said to be a styrenic copolymer having a reactive unsaturated bond in its molecule that exhibits reactivity with heat or ultraviolet rays.
  • a styrenic copolymer having such an unsaturated bond cannot be said to be a styrenic copolymer having a reactive unsaturated bond in its molecule that exhibits reactivity with heat or ultraviolet rays.
  • An example of a product of a styrene copolymer having no unsaturated bond at the end of its molecular structure is TR2003 manufactured by JSR Corporation.
  • the position of the reactive unsaturated bond may be a) the end of the molecular structure (regardless of whether it is the main chain or the side chain), or b) the end of the molecular structure (regardless of whether it is the main chain or the side chain). If a benzene ring is located at the position (not present), it may be located adjacent to the terminal benzene ring.
  • Examples of products of styrenic copolymers having reactive unsaturated bonds include Septon (R) V9461 (contains a styryl group) manufactured by Kuraray Co., Ltd., and Ricon (R) 100, 181 and 184 (1,2- Styrene-butadiene copolymers having vinyl groups), Epofriend AT501 and CT310 (styrene-butadiene copolymers having 1,2-vinyl groups) manufactured by Daicel Corporation.
  • "exhibiting reactivity with heat or ultraviolet light” means exhibiting reactivity under heating conditions or ultraviolet irradiation conditions that are sufficient to cure the base material (for example, prepreg) that is suitably used in combination with the resin composition of the present invention. This means that the heating temperature under such conditions is typically about 160 to 230°C.
  • the styrenic copolymer has modified styrene butadiene.
  • the resin composition may further include an additional styrenic copolymer with modified styrene butadiene.
  • the additional styrenic copolymer the same styrenic copolymer described above can be used, except that it does not need to have a reactive unsaturated bond. That is, the additional styrenic copolymer can be one that does not have reactive unsaturated bonds (although it may have reactive unsaturated bonds).
  • the modified styrene-butadiene may be any styrene-butadiene that has been chemically modified by introducing various functional groups, such as amine-modified, pyridine-modified, carboxy-modified, etc., but amine-modified is preferred.
  • An example of a styrenic copolymer having modified styrene-butadiene includes Tuftec (R) MP10 manufactured by Asahi Kasei Corporation, which is a hydrogenated styrene-butadiene block copolymer and is an amine-modified product.
  • TR2003 manufactured by JSR Corporation, which is a styrene-butadiene block copolymer. (not a styrenic copolymer with bonds in the molecule).
  • the content of the styrenic copolymer having a reactive unsaturated bond that exhibits reactivity with heat or ultraviolet rays in the resin composition of the present invention is not particularly limited, but from the viewpoint of achieving both compatibility and dielectric properties, the resin component (solid) 20 parts by weight or more and 99.5 parts by weight or less, more preferably 30 parts by weight or more and 90 parts by weight or less, even more preferably 40 parts by weight or more and 70 parts by weight or less, based on 100 parts by weight of the total amount of .
  • the total content of the arylene ether compound having a weight average molecular weight of 30,000 or more and the styrenic copolymer having a reactive unsaturated bond in the molecule that exhibits reactivity with heat or ultraviolet rays is not particularly limited. , preferably 30 parts by weight or more and 99.5 parts by weight or less, more preferably 40 parts by weight or more and 90 parts by weight or less, even more preferably 50 parts by weight or more and 85 parts by weight, based on 100 parts by weight of the total amount of resin components (solid content). Parts by weight or less.
  • the resin composition of the present invention includes an organic filler made of liquid crystal polymer (LCP).
  • LCP liquid crystal polymer
  • a liquid crystal polymer By adding a liquid crystal polymer as a filler, not only can excellent dielectric properties be imparted to the resin composition, but also high adhesion to low roughness surfaces can be prevented from deteriorating even after heat load. This ability to suppress thermal deterioration is an advantage that cannot be obtained with inorganic fillers.
  • fillers made of liquid crystal polymers have excellent dispersibility in other resin components.
  • an organic filler made of polytetrafluoroethylene (PTFE) is very difficult to disperse in a resin component, but an organic filler made of a liquid crystal polymer is advantageous in that it does not have such drawbacks.
  • the organic filler is in the form of liquid crystal polymer particles.
  • liquid crystal polymer particles can be used, and for example, XYDAR (R) LF-31P (manufactured by ENEOS Corporation) can be preferably used as a powder grade liquid crystal polymer.
  • the particle size of the liquid crystal polymer particles is not particularly limited as long as it can be dispersed in the resin composition as an organic filler and exhibit the desired performance, but it is preferable that the average particle size D50 of the liquid crystal polymer particles is 0.1 to 10 ⁇ m. , more preferably 0.5 to 9 ⁇ m, still more preferably 1 to 8 ⁇ m.
  • the average particle diameter D50 of the liquid crystal polymer particles can be measured using a laser diffraction scattering particle size distribution analyzer.
  • the content of the organic filler is not particularly limited, but from the viewpoint of ease of filler dispersion, fluidity of the resin composition, etc., the content of the organic filler is 5 parts by weight based on 100 parts by weight of the total amount of the resin components (solid content) mentioned above. 300 parts by weight or less, more preferably 10 parts by weight or more and 200 parts by weight or less, still more preferably 15 parts by weight or more and 200 parts by weight, particularly preferably 15 parts by weight or more and 150 parts by weight or less, most preferably 25 parts by weight. The amount is 75 parts by weight or less.
  • the organic filler preferably has a dielectric loss tangent of 0.001 or less at a frequency of 10 GHz, more preferably 0.0009 or less, and still more preferably 0.0008 or less.
  • the resin composition of the present invention may contain additives commonly added to resins and polymers.
  • additives include reaction initiators, reaction promoters, flame retardants, silane coupling agents, dispersants, antioxidants, and the like.
  • Resin-coated copper foil The resin composition of the present invention is preferably used as a resin for resin-coated copper foil. That is, according to a preferred embodiment of the present invention, a resin-coated copper foil is provided that includes a copper foil and a resin layer containing a resin composition provided on at least one surface of the copper foil. Typically, the resin composition is in the form of a resin layer, and the resin composition is applied to the copper foil using a gravure coating method so that the thickness of the resin layer after drying becomes a predetermined value. Dry to obtain resin-coated copper foil.
  • the method of this coating is arbitrary, but in addition to the gravure coating method, a die coating method, a knife coating method, etc. can be adopted. In addition, it is also possible to apply using a doctor blade, bar coater, or the like.
  • the resin composition of the present invention not only has excellent dielectric properties (e.g., low dielectric loss tangent at 10 GHz) and high adhesion to low-roughness surfaces (e.g., the surface of low-roughness copper foil). , it is possible to maintain stable high adhesion to low-roughness surfaces even after heat load. Therefore, the resin-coated copper foil has various advantages brought about by such a resin composition.
  • the lower limit of the peel strength between the resin layer and the copper foil (that is, the normal peel strength) measured in accordance with JIS C 6481-1996 when the resin layer is cured is as follows: Preferably it is 0.5 kgf/cm or more, more preferably 0.8 kgf/cm or more, still more preferably 1.0 kgf/cm or more, particularly preferably 1.2 kgf/cm or more.
  • the higher the peel strength, the better, and its upper limit is not particularly limited, but is typically 2.0 kgf/cm or less.
  • the thickness of the resin layer is not particularly limited, but a thicker one is preferable in order to ensure peel strength, and a thinner thickness of the laminated substrate is preferable, so an appropriate thickness exists.
  • the thickness of the resin layer is preferably 1 ⁇ m or more and 50 ⁇ m or less, more preferably 1.5 ⁇ m or more and 30 ⁇ m or less, particularly preferably 2 ⁇ m or more and 20 ⁇ m or less, and most preferably 2.5 ⁇ m or more and 10 ⁇ m or less.
  • the copper foil may be an electrolytic foil or a rolled metal foil (so-called raw foil), or it may be in the form of a surface-treated foil that has been surface-treated on at least one side.
  • Surface treatment is a variety of surface treatments performed to improve or impart certain properties to the surface of metal foil (for example, rust prevention, moisture resistance, chemical resistance, acid resistance, heat resistance, and adhesion to a substrate). It can be.
  • the surface treatment may be performed on one side of the metal foil or on both sides of the metal foil. Examples of surface treatments performed on copper foil include rust prevention treatment, silane treatment, roughening treatment, barrier formation treatment, and the like.
  • the ten-point average roughness Rzjis of the surface of the copper foil on the resin layer side measured in accordance with JIS B0601-2001 is preferably 2.0 ⁇ m or less, more preferably 1.5 ⁇ m or less, and even more preferably 1 .0 ⁇ m or less, particularly preferably 0.7 ⁇ m or less, and most preferably 0.5 ⁇ m or less.
  • transmission loss in high frequency applications can be desirably reduced. That is, it is possible to reduce the conductor loss caused by the copper foil, which can increase due to the skin effect of the copper foil, which becomes more pronounced as the frequency increases, and further reduce the transmission loss.
  • the lower limit of the ten-point average roughness Rzjis on the surface of the copper foil on the resin layer side is not particularly limited, but from the viewpoint of improving adhesion with the resin layer and heat resistance, Rzjis is preferably 0.01 ⁇ m or more, more preferably 0. It is .03 ⁇ m or more, more preferably 0.05 ⁇ m or more.
  • the thickness of the copper foil is not particularly limited, but is preferably 0.1 ⁇ m or more and 100 ⁇ m or less, more preferably 0.5 ⁇ m or more and 70 ⁇ m or less, even more preferably 1 ⁇ m or more and 50 ⁇ m or less, and particularly preferably 1.5 ⁇ m or more and 30 ⁇ m or less. , most preferably 2 ⁇ m or more and 20 ⁇ m or less. A thickness within these ranges has the advantage that fine circuitry can be formed.
  • the resin-coated copper foil of the present invention may be coated with a resin layer on the copper foil surface of the carrier-coated copper foil, which is provided with a release layer and a carrier to improve handling properties. It may also be formed by
  • the base material such as prepreg preferably contains a resin having a reactive unsaturated bond in the molecule, and from the viewpoint of compatibility with the resin layer, polyphenylene ether is preferably used. Preferably, it contains a resin.
  • base materials that satisfy both the requirements of containing a resin having a reactive unsaturated bond in the molecule and containing a polyphenylene ether resin include the MEGTRON 6 series, MEGTRON 7 series, and MEGTRON 8 series manufactured by Panasonic Corporation. It will be done.
  • a base material for example, prepreg
  • a resin layer containing the resin composition of the present invention or resin-coated copper foil of the present invention
  • the resin composition or resin-coated copper foil of the present invention is preferably used for producing a printed wiring board. That is, according to a preferred embodiment of the present invention, a printed wiring board including the resin-coated copper foil or a printed wiring board manufactured using the resin-coated copper foil is provided. In this case, the resin layer of the resin-coated copper foil is hardened.
  • the printed wiring board according to this embodiment includes a layered structure in which an insulating resin layer and a copper layer are laminated in this order. A known layer structure can be used for the printed wiring board.
  • printed wiring boards include single-sided or double-sided printed wiring boards in which the resin-coated copper foil of the present invention is adhered to one or both sides of a prepreg to form a cured laminate, and circuits are formed on the same, and multilayers made of these.
  • Examples include printed wiring boards.
  • Other specific examples include flexible printed wiring boards in which a circuit is formed by forming the resin-coated copper foil of the present invention on a resin film, COF, TAB tape, build-up multilayer wiring boards, and resin-coated copper foils on semiconductor integrated circuits. Examples include direct build-up on wafer, in which lamination of coated copper foil and circuit formation are alternately repeated.
  • the resin-coated copper foil of the present invention can be preferably applied as an insulating layer and a conductive layer for printed wiring boards for high-frequency digital communications in network equipment.
  • network devices include (i) in-base station servers, routers, etc., (ii) in-company networks, and (iii) backbone systems for high-speed mobile communications.
  • Examples 1 to 12 (1) Preparation of resin varnish First, the following arylene ether compound, styrene copolymer, additive, organic filler, and inorganic filler were prepared as raw materials for resin varnish.
  • ⁇ Arylene ether compound> -OPE-2St-1200 manufactured by Mitsubishi Gas Chemical Co., Ltd., phenylene ether compound having styryl groups at both ends of the molecule, number average molecular weight approximately 1200
  • -OPE-2St-2200 manufactured by Mitsubishi Gas Chemical Co., Ltd., phenylene ether compound having styryl groups at both ends of the molecule, number average molecular weight approximately 2200
  • -PME-82 manufactured by Mitsubishi Engineering Plastics Co., Ltd., a phenylene ether compound containing a maleic anhydride structure in the molecule, weight average molecular weight approximately 56,000
  • the number average molecular weight and weight average molecular weight of the above-mentioned arylene ether compound and styrene copolymer are values obtained by measurement using GPC (gel permeation chromatography) method under the following conditions.
  • the above molecular weights are relative values based on polystyrene.
  • ⁇ Detector Differential refractive index detector RI (manufactured by Tosoh Corporation, RI-8020, sensitivity 32)
  • Column TSKgel GMH HR -M, 2 (7.8mm x 30cm, manufactured by Tosoh Corporation)
  • Solvent Chloroform ⁇ Flow rate: 1.0mL/min ⁇ Column temperature: 40°C ⁇ Injection volume: 0.2mL
  • Standard sample Manufactured by Tosoh Corporation, monodisperse polystyrene
  • Data processing Manufactured by Toray Research Center Corporation, GPC data processing system
  • This mixed solvent is a mixture of methyl ethyl ketone (MEK) and toluene so that the MEK ratio (wt%) is shown in Tables 1 and 2.
  • MEK methyl ethyl ketone
  • a mantle heater, a stirring blade, and a flask lid with a reflux condenser tube were installed in a round flask containing the raw material components and mixed solvent, and the temperature was raised to 60 °C while stirring, and stirring was continued at 60 °C for 2 hours. The raw material components were dissolved or dispersed. The resin varnish obtained after stirring was allowed to cool. In this way, resin varnishes having solid content concentrations shown in Tables 1 and 2 were obtained.
  • Electrolytic copper foil was produced by the following method. Electrolysis was carried out in a copper sulfate solution using a titanium rotating electrode (surface roughness Ra: 0.20 ⁇ m) as the cathode and a dimensionally stable anode (DSA) as the anode at a solution temperature of 45°C and a current density of 55A/ dm2 . , an electrolytic copper foil was produced as a raw foil.
  • a titanium rotating electrode surface roughness Ra: 0.20 ⁇ m
  • DSA dimensionally stable anode
  • the composition of this copper sulfate solution is: copper concentration 80 g/L, free sulfuric acid concentration 140 g/L, bis(3-sulfopropyl) disulfide concentration 30 mg/L, diallyldimethylammonium chloride polymer concentration 50 mg/L, and chlorine concentration 40 mg/L. And so. Particulate protrusions were formed on the surface of the raw foil on the electrolyte side. The formation of particulate protrusions was performed in a copper sulfate solution (copper concentration: 13 g/L, free sulfuric acid concentration 55 g/L, 9-phenylacridine concentration 140 mg/L, chlorine concentration: 35 mg/L) at a solution temperature of 30°C and an electric current. This was carried out by electrolyzing at a density of 50 A/dm 2 .
  • a zinc-nickel coating, a chromate layer, and a silane layer were sequentially formed on the electrolyte side of the raw foil obtained in this manner under the conditions shown below.
  • ⁇ Zinc-nickel film formation> ⁇ Potassium pyrophosphate concentration: 80g/L ⁇ Zinc concentration: 0.2g/L ⁇ Nickel concentration: 2g/L ⁇ Liquid temperature: 40°C ⁇ Current density: 0.5A/ dm2 ⁇ Chromate layer formation> ⁇ Chromic acid concentration: 1g/L, pH 11 ⁇ Solution temperature: 25°C ⁇ Current density: 1A/dm 2 ⁇ Silane layer formation> ⁇ Silane coupling agent: 3-aminopropyltrimethoxysilane (3 g/L aqueous solution) ⁇ Liquid processing method: shower processing
  • the surface treated surface of this electrolytic copper foil has a ten-point average roughness Rzjis of 0.5 ⁇ m (according to JIS B0601-2001), and the particle-like protrusions have an average particle diameter of 100 nm as determined by a scanning electron microscope image.
  • the density was 205 pieces/ ⁇ m2 .
  • the total thickness of the electrolytic copper foil including the surface treated surface was 18 ⁇ m.
  • the peel strength measured here reflects four peeling modes: prepreg/resin interface peeling, resin cohesive failure, phase interface peeling within the resin layer, and resin/copper foil interface peeling.
  • ⁇ Dielectric loss tangent> The dielectric loss tangent of the resin film at 10 GHz was measured by the perturbation cavity resonator method. This measurement was performed in accordance with JIS R 1641 using a measuring device (a resonator manufactured by KEYCOM and a network analyzer manufactured by KEYSIGHT) after cutting the resin film according to the sample size of the resonator. The results were as shown in Tables 1 and 2.

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Abstract

L'invention concerne une composition de résine qui non seulement présente une adhésivité élevée contre des surfaces moins rugueuses et présente d'excellentes propriétés diélectriques, mais peut également maintenir de manière stable l'adhésivité élevée même après qu'une charge thermique y est appliquée. La composition de résine contient : un composé d'éther d'arylène ayant un poids moléculaire moyen en poids de 30 000 ou plus, et/ou un copolymère à base de styrène qui a, à l'intérieur de la molécule, une liaison insaturée réactive qui exprime une réactivité due à la chaleur ou aux rayons ultraviolets ; et une charge organique formée d'un polymère à cristaux liquides.
PCT/JP2023/028105 2022-08-08 2023-08-01 Composition de résine, feuille de cuivre avec résine, et carte de circuit imprimé WO2024034463A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1192566A (ja) * 1997-09-18 1999-04-06 Otsuka Chem Co Ltd ポリスチレン系樹脂ペレット
JP2002502678A (ja) * 1998-02-11 2002-01-29 アクシュネット カンパニー 液晶ポリマーを含有するゴルフボール
JP2002069290A (ja) * 2000-08-30 2002-03-08 Asahi Kasei Corp 耐熱部品
JP2002121377A (ja) * 2000-08-08 2002-04-23 Asahi Kasei Corp 耐衝撃性に優れた樹脂組成物及び成形体
JP2002317111A (ja) * 2001-04-20 2002-10-31 Asahi Kasei Corp ポリフェニレンエーテル系樹脂組成物
WO2005073264A1 (fr) * 2004-01-30 2005-08-11 Nippon Steel Chemical Co., Ltd. Composition à base de résine durcissable
JP2006232952A (ja) * 2005-02-23 2006-09-07 Matsushita Electric Works Ltd ポリフェニレン樹脂組成物を含有するプリプレグ及び積層体
US20140187674A1 (en) * 2012-12-28 2014-07-03 Samsung Electro-Mechanics Co., Ltd. Resin composition with enhanced heat-releasing properties, heat-releasing film, insulating film, and prepreg
WO2017150336A1 (fr) * 2016-02-29 2017-09-08 ポリプラスチックス株式会社 Composition de résine comprenant des particules de polymère à cristaux liquides, objet moulé obtenu en utilisant cette composition, et procédés de production associés
CN107964203A (zh) * 2017-12-26 2018-04-27 浙江华正新材料股份有限公司 一种低介电预浸料组合物、覆铜板及其制作方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1192566A (ja) * 1997-09-18 1999-04-06 Otsuka Chem Co Ltd ポリスチレン系樹脂ペレット
JP2002502678A (ja) * 1998-02-11 2002-01-29 アクシュネット カンパニー 液晶ポリマーを含有するゴルフボール
JP2002121377A (ja) * 2000-08-08 2002-04-23 Asahi Kasei Corp 耐衝撃性に優れた樹脂組成物及び成形体
JP2002069290A (ja) * 2000-08-30 2002-03-08 Asahi Kasei Corp 耐熱部品
JP2002317111A (ja) * 2001-04-20 2002-10-31 Asahi Kasei Corp ポリフェニレンエーテル系樹脂組成物
WO2005073264A1 (fr) * 2004-01-30 2005-08-11 Nippon Steel Chemical Co., Ltd. Composition à base de résine durcissable
JP2006232952A (ja) * 2005-02-23 2006-09-07 Matsushita Electric Works Ltd ポリフェニレン樹脂組成物を含有するプリプレグ及び積層体
US20140187674A1 (en) * 2012-12-28 2014-07-03 Samsung Electro-Mechanics Co., Ltd. Resin composition with enhanced heat-releasing properties, heat-releasing film, insulating film, and prepreg
WO2017150336A1 (fr) * 2016-02-29 2017-09-08 ポリプラスチックス株式会社 Composition de résine comprenant des particules de polymère à cristaux liquides, objet moulé obtenu en utilisant cette composition, et procédés de production associés
CN107964203A (zh) * 2017-12-26 2018-04-27 浙江华正新材料股份有限公司 一种低介电预浸料组合物、覆铜板及其制作方法

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