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WO2025154721A1 - Feuille de résine présentant une couche de traitement de surface, composition d'apprêt, et procédé de production d'une feuille de résine présentant une couche de traitement de surface - Google Patents

Feuille de résine présentant une couche de traitement de surface, composition d'apprêt, et procédé de production d'une feuille de résine présentant une couche de traitement de surface

Info

Publication number
WO2025154721A1
WO2025154721A1 PCT/JP2025/000947 JP2025000947W WO2025154721A1 WO 2025154721 A1 WO2025154721 A1 WO 2025154721A1 JP 2025000947 W JP2025000947 W JP 2025000947W WO 2025154721 A1 WO2025154721 A1 WO 2025154721A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin sheet
mass
layer
silane compound
primer composition
Prior art date
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.)
Pending
Application number
PCT/JP2025/000947
Other languages
English (en)
Japanese (ja)
Inventor
朋 吉木
智晴 栗田
信正 木村
俊夫 猿山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daichi Inc
Toyobo Co Ltd
Original Assignee
Daichi Inc
Toyobo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Daichi Inc, Toyobo Co Ltd filed Critical Daichi Inc
Publication of WO2025154721A1 publication Critical patent/WO2025154721A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • 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 sheet with a surface treatment layer, a primer composition, and a method for manufacturing a resin sheet with a surface treatment layer.
  • the present invention relates to a resin sheet, a primer composition, and a method for manufacturing a resin sheet that can be suitably used as a material for printed wiring boards.
  • fluororesin e.g., polytetrafluoroethylene; PTFE
  • PTFE polytetrafluoroethylene
  • Syndiotactic polystyrene (hereinafter sometimes abbreviated as SPS) is known as a material with a low dielectric constant and dielectric tangent, and a laminate for electronic circuit boards using a syndiotactic polystyrene-based resin is described in Patent Document 2.
  • This laminate for electronic circuit boards includes a first resin layer containing a thermoplastic resin, a second resin layer containing a syndiotactic polystyrene-based resin laminated on the first resin layer, a first metal layer laminated on the second resin layer without any other layer therebetween, and a second metal layer formed on the first metal layer.
  • Plating and vapor deposition are given as examples of methods for forming the first metal layer.
  • the first metal layer is directly attached onto the second resin layer containing a syndiotactic polystyrene resin, so stress is generated due to the difference in linear expansion coefficient between the second resin layer and the first metal layer, and the first metal layer may peel off from the second resin layer, making it impractical.
  • syndiotactic polystyrene has excellent dielectric properties, it has low heat resistance and is not a material that can withstand the heat treatment conditions in the soldering process.
  • the first object of the present invention is to provide a resin sheet with a surface treatment layer, which contains a syndiotactic polystyrene resin and has good adhesion to the adhesive layer when a metal layer is laminated thereon via an adhesive layer, making the metal layer less likely to peel off, and which is also less likely to peel off even when subjected to heat treatment conditions simulating a soldering process.
  • the second object of the present invention is to provide a primer composition.
  • the third object of the present invention is to provide a method for producing a resin sheet with a surface treatment layer.
  • the present invention is as follows. [1] A resin sheet with a surface treatment layer, the resin sheet containing a syndiotactic polystyrene-based resin, the surface treatment layer being present on one or both sides of the resin sheet, when at least one of the surface treatment layers, a side not in contact with the resin sheet, is subjected to elemental analysis by X-ray photoelectron spectroscopy (ESCA), Si, C, N, and O are observed, and the amounts of these elements satisfy the relationships of the following formulas (1) to (4).
  • ESA X-ray photoelectron spectroscopy
  • a method for producing a resin sheet with a surface treatment layer comprising: a pretreatment step of performing a surface activation treatment on at least one surface of a resin sheet containing a syndiotactic polystyrene-based resin; a surface layer formation step of forming a primer layer on the surface that has been subjected to the surface activation treatment; and a surface layer reaction step of heating the resin sheet on which the primer layer has been formed.
  • the surface activation treatment is one or a combination of two or more of a corona discharge treatment, a plasma treatment, an ultraviolet irradiation treatment, a radiation treatment, and a flame treatment.
  • the present invention it is possible to provide a resin sheet with a surface treatment layer, in which when a metal layer is laminated on a resin sheet via an adhesive layer, the adhesion between the resin sheet and the adhesive layer is good, making the metal layer less likely to peel off, and even when subjected to heat treatment conditions simulating a soldering process, the metal layer is less likely to peel off. Furthermore, by using the primer composition according to the present invention, when a metal layer is laminated on a resin sheet via an adhesive layer, the adhesion between the resin sheet and the adhesive layer is good, making it possible to make the metal layer less likely to peel off, and even when subjected to heat treatment conditions simulating a soldering process, the metal layer is less likely to peel off. Furthermore, according to the present invention, it is possible to provide a method for producing a resin sheet with a surface treatment layer.
  • the second silane compound has an alkenyl group and two or more alkoxy groups.
  • the alcohol (d) may be linear or branched.
  • the number of carbon atoms in the alcohol may be, for example, 1 or 2 or more.
  • the number of carbon atoms in the alcohol is, for example, preferably 4 or less, and more preferably 3 or less.
  • Examples of the alcohol (d) include methyl alcohol, ethyl alcohol, normal propyl alcohol, and isopropyl alcohol. Of these, only one type may be used alone, or two or more types may be mixed and used.
  • the amount of alcohol (d) contained in the primer composition is not particularly limited, but may be, for example, 1000 to 2000 parts by mass per 100 parts by mass of the first silane compound (a).
  • the amount of alcohol (d) is preferably 1100 parts by mass or more, more preferably 1200 parts by mass or more, per 100 parts by mass of the first silane compound (a).
  • the amount of alcohol (d) is preferably 1900 parts by mass or less, more preferably 1800 parts by mass or less, per 100 parts by mass of the first silane compound (a).
  • the amount of alcohol (d) is the total amount. That is, the amount of alcohol (d) in the primer composition is preferably 1100 to 1900 parts by mass, more preferably 1200 to 1800 parts by mass, per 100 parts by mass of the first silane compound (a).
  • polyvalent amine compound (c) examples include hydrocarbon polyvalent amine compounds such as 1,2-ethanediamine (ethylenediamine), 1,3-propanediamine, 2-methyl-2-propyl-1,3-propanediamine, 1,2-propanediamine, 2-methyl-1,3-propanediamine, 1,4-butanediamine (putrescine), 2,3-dimethyl-1,4-butanediamine, 1,3-butanediamine, 1,2-butanediamine, 2-ethyl-1,4-butanediamine, and 2-methyl-1,4-butanediamine. Of these, only one type may be used alone, or two or more types may be mixed and used. Of these, it is preferable to use ethylenediamine.
  • hydrocarbon polyvalent amine compounds such as 1,2-ethanediamine (ethylenediamine), 1,3-propanediamine, 2-methyl-2-propyl-1,3-propanediamine, 1,2-propanediamine, 2-methyl-1,3-propanediamine, 1,4-butanediamine (putre
  • the thickness of the surface treatment layer which is the treatment layer by the primer composition, can be adjusted.
  • water (e) for example, ion-exchanged water may be used.
  • dimethylsiloxane oligomer (f) examples include hexamethyldisiloxane, octamethyltrisiloxane, and octamethylcyclotetrasiloxane. Of these, only one type may be used alone, or two or more types may be mixed and used. Of these, it is preferable to use hexamethyldisiloxane.
  • the amount of dimethylsiloxane oligomer (f) is not particularly limited, but may be, for example, 10 to 500 parts by mass per 100 parts by mass of the first silane compound (a).
  • the amount of dimethylsiloxane oligomer (f) is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, per 100 parts by mass of the first silane compound (a).
  • the amount of dimethylsiloxane oligomer (f) is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, per 100 parts by mass of the first silane compound (a).
  • poly(alkylstyrene)s examples include poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(tert-butylstyrene), poly(phenylstyrene), poly(vinylnaphthalene), and poly(vinylstyrene).
  • poly(halogenated styrene)s examples include poly(chlorostyrene), poly(bromostyrene), and poly(fluorostyrene).
  • poly(halogenated alkylstyrene)s examples include poly(chloromethylstyrene).
  • the syndiotactic polystyrene resin (A) may be a copolymer of styrene having a syndiotactic structure and another monomer.
  • the content of styrene having a syndiotactic structure in the syndiotactic polystyrene resin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass, relative to 100% by mass of the syndiotactic polystyrene resin (A).
  • the syndiotactic polystyrene resin (A) may be a single type of styrene polymer, or a mixture of two or more types.
  • the melting point of the syndiotactic polystyrene resin (A) is preferably 250°C or higher, more preferably 260°C or higher, and is preferably 300°C or lower, more preferably 290°C or lower. In other words, the melting point of the syndiotactic polystyrene resin (A) is preferably 250 to 300°C, more preferably 260 to 290°C.
  • the content of syndiotactic polystyrene resin (A) in the resin sheet is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, because the dielectric properties are good.
  • the upper limit of the content of syndiotactic polystyrene resin (A) is not particularly limited, but is preferably less than 100% by mass, more preferably 99% by mass or less, and even more preferably 95% by mass or less, because the linear expansion coefficient and dimensional stability are good.
  • the resin sheet may contain at least one selected from the group consisting of a rubber-like elastomer (B), a fibrous filler (C), a non-fibrous filler (D), and an antioxidant (E).
  • core-shell type particulate elastomer examples include isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), butadiene-acrylonitrile-styrene-core-shell rubber (ABS), methyl methacrylate-butadiene-styrene-core-shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core-shell rubber (MAS), octyl acrylate-butadiene-styrene-core-shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene-core-shell rubber (AABS), butadiene-styrene-core-shell rubber (SBR), and siloxane-containing core-shell rubbers such as methyl methacrylate-butyl acrylate-siloxane, or
  • inorganic or organic fibers can be used.
  • inorganic fibers for example, wollastonite (or whiskers) or glass fibers can be used, and it is more preferable to use glass fibers in terms of their dielectric properties.
  • organic fibers for example, resin fibers can be used.
  • the shape of the fibrous filler (C) is not particularly limited, and may be any shape, such as roving, surfacing mat, chopped strand mat, satin weave, lattice weave, plain weave, open-weave plain weave, twill weave, net, etc.
  • the fiber diameter is preferably 1 to 50 ⁇ m, more preferably 2 to 20 ⁇ m, and even more preferably 3 to 15 ⁇ m.
  • the D50 average fiber length of the fibrous filler (C) is preferably 40 to 4000 ⁇ m, more preferably 40 to 3200 ⁇ m, even more preferably 45 to 2000 ⁇ m, and most preferably 50 to 500 ⁇ m. If the D50 average fiber length of the fibrous filler (C) is 40 ⁇ m or more, the surface area of the fibrous filler (C) is sufficiently large, the adhesion of the interface between the matrix resin components (A) and (C) is improved, and the physical properties of the raw resin sheet are good.
  • the fibrous filler (C) may or may not have been surface-treated.
  • the coupling agent used for the surface treatment include a silane-based coupling agent and a titanium-based coupling agent.
  • a silane-based coupling agent for the surface treatment from the viewpoint of compatibility with component (A).
  • silane coupling agents include triethoxysilane, vinyltris( ⁇ -methoxyethoxy)silane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -(1,1-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyltriethoxysilane, and N-phenyl- ⁇ -aminopropyltrimethoxy
  • aminosilanes and epoxysilanes such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, and ⁇ -aminopropyltrimethoxysilane are preferred.
  • titanium-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(1,1-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, and bis(dioctyl pyrophosphate)oxyacetate.
  • isopropyl tri(N-amidoethyl, aminoethyl) titanate is preferred.
  • compatibilizers include modified polyphenylene ether polymers such as styrene-maleic anhydride copolymer (SMA), styrene-glycidyl methacrylate copolymer, terminal carboxylic acid modified polystyrene, terminal epoxy modified polystyrene, terminal oxazoline modified polystyrene, terminal amine modified polystyrene, sulfonated polystyrene, styrene-based ionomers, styrene-methyl methacrylate graft polymer, (styrene-glycidyl methacrylate)-methyl methacrylate graft copolymer, acid modified acrylic-styrene graft polymer, (styrene-glycidyl methacrylate)-styrene graft polymer, polybutylene terephthalate-polystyrene graft polymer, polyphenylene ether poly
  • fibrous filler (C) When fibrous filler (C) is contained, its amount is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and even more preferably 5 to 30 parts by mass, per 100 parts by mass of syndiotactic polystyrene resin (A) in order to balance the target linear expansion coefficient with dimensional stability and impact resistance/mechanical properties.
  • Typical commercially available fibrous fillers include, for example, HDT09100T manufactured by Tochu Co., Ltd., EPH80M-01N manufactured by Nippon Electric Glass Co., Ltd., ChopVantageHP-3610 manufactured by Nippon Electric Glass Co., Ltd., EFH30-01 manufactured by Central Glass Fiber Co., Ltd., and ECS301HP-3-H manufactured by Chongqing International Composite Materials Co., Ltd. One of these may be used alone, or two or more may be used in combination.
  • the resin sheet may contain a non-fibrous filler (D) (hereinafter also referred to as component (D)).
  • the non-fibrous filler (D) is a non-fibrous filler that is expected to have an effect of suppressing the linear expansion coefficient and dimensional change in the direction parallel to the extrusion direction (MD) and the direction perpendicular to the extrusion direction (TD) of the sheet that is a precursor of the resin sheet.
  • the shape of the non-fibrous filler (D) is not particularly limited and may be any shape, such as spherical, granular, or plate-like, with granular being preferred.
  • non-fibrous filler (D) an organic or inorganic filler may be used, and it is preferable to use an inorganic filler.
  • organic filler for example, organic spherical, granular or plate-like fillers may be used.
  • the type of polymer used as the organic filler is not particularly limited, but considering the processing temperature of the syndiotactic polystyrene resin (A), if the polymer is a crystalline resin, it is preferable that the melting point exceeds 280°C, and more preferably exceeds 300°C. If the polymer is an amorphous resin, it is preferable that the glass transition temperature exceeds 150°C, and more preferably exceeds 180°C. By setting the melting point and glass transition temperature within the above ranges, the shape of the filler can be maintained during processing into a raw resin sheet, and the effect of suppressing the linear expansion coefficient of the resin sheet can be exerted.
  • inorganic fillers for example, inorganic spherical, granular or plate-like fillers may be used.
  • inorganic fillers include talc, carbon black, graphite, titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flakes, glass beads, etc.
  • silica is particularly preferred from the viewpoints of productivity, cost and the dielectric properties of the filler itself, and amorphous silica or fused silica is more preferred.
  • Amorphous silica has a lower hardness than crystalline silica, so that the use of amorphous silica can suppress wear of machines and screws.
  • Fused silica is sphericalized by surface tension by melting the raw material in a flame and rapidly cooling and solidifying the volatilized gas, so there are few sharp parts, the filler itself does not collapse, and it is easy to form a stable shape.
  • the silica is preferably granular or spherical in shape, and more preferably granular.
  • the granular or spherical shape of the silica makes it easier to mix when added to molten resin.
  • the silica since the silica is stable regardless of the direction from which force is applied, the silica is less likely to be broken and less likely to fall off during the production of the raw resin sheet.
  • the silica may be hollow.
  • the D50 average particle size of the non-fibrous filler (D) is preferably 0.1 to 45 ⁇ m, more preferably 0.2 to 30 ⁇ m, even more preferably 0.3 to 20 ⁇ m, and even more preferably 0.5 to 10 ⁇ m.
  • the D50 average particle size of the non-fibrous filler (D) is 0.1 ⁇ m or more, aggregation between the (D) components is suppressed, they do not become foreign matter within the resin sheet, and mechanical properties are less likely to deteriorate.
  • the D50 average particle size of the non-fibrous filler (D) is 45 ⁇ m or less, the spacing between the (D) components does not become too narrow, and the propagation of cracks at the interface when stress is generated can be suppressed. In addition, heat resistance can be maintained during the soldering process.
  • the hollow silica preferably has a D50 average particle size of 3 to 45 ⁇ m.
  • a D50 average particle size of 3 ⁇ m or more is expected to have the effect of lowering the dielectric constant.
  • a D50 average particle size of 45 ⁇ m or less will result in a decrease in the mechanical properties of the raw resin sheet.
  • the non-fibrous filler (D) may or may not be surface-treated.
  • a known surface treatment agent may be used for the surface treatment.
  • a silane coupling agent or a titanate coupling agent may be used for hydrophobization, which improves the dispersion state in the syndiotactic polystyrene resin (A) and suppresses the generation of aggregates in the resin sheet.
  • the resin sheet may contain an antioxidant (E) (hereinafter also referred to as component (E)) from the viewpoint of processability.
  • the antioxidant (E) may be either a primary antioxidant that captures generated radicals to prevent oxidation, or a secondary antioxidant that decomposes generated peroxides to prevent oxidation.
  • the primary antioxidant include phenol-based antioxidants and amine-based antioxidants.
  • the secondary antioxidant include phosphorus-based antioxidants and sulfur-based antioxidants.
  • antioxidants alone or in combination, it is possible to suppress the molecular weight reduction of component (A) or component (B) during the production of the SPS resin composition, and to suppress the generation of gas derived from component (A) or component (B) during the heat pressing process during the production of the resin sheet.
  • antioxidants examples include polymeric phenolic antioxidants such as benzene, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid] glycol ester, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-sec-triazine-2,4,6-(1H,3H,5H)trione, and d- ⁇ -tocopherol.
  • polymeric phenolic antioxidants such as benzene, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid] glycol ester, 1,3,5
  • phosphorus-based antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl ditridecyl) phosphite, octadecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • the thermal decomposition temperature of the antioxidant (E) is preferably 250°C or higher.
  • the thermal decomposition temperature of the antioxidant (E) is more preferably 280°C or higher, even more preferably 300°C or higher, and particularly preferably 320°C or higher.
  • the upper limit of the thermal decomposition temperature of the antioxidant (E) is, for example, about 500°C or lower.
  • the raw resin sheet is an unstretched sheet containing the component (A) or a film obtained by biaxially stretching the unstretched sheet.
  • the unstretched sheet may not only not be completely stretched, but may also have some residual strain.
  • the stretch ratio is preferably 1.3 or less in both the direction parallel to the extrusion direction of the sheet (machine direction, MD) and the direction perpendicular to the extrusion direction of the sheet (transverse direction, TD).
  • the roll temperature when manufacturing the raw resin sheet is preferably 30°C to 100°C, more preferably 40°C to 98°C, and even more preferably 60°C to 95°C.
  • the roll temperature is preferably 30°C to 100°C, more preferably 40°C to 98°C, and even more preferably 60°C to 95°C.
  • the roll winding properties can be made uniform and small. If the roll temperature is below 30°C, condensation may form on the roll surface, and water droplets may adhere to the sheet and be transferred as surface unevenness. If the roll temperature exceeds 100°C, the molten resin may stick to the roll, making it difficult to stretch and wind the sheet.
  • the material of the two rolls used to manufacture the raw resin sheet is not particularly limited and may be rubber, metal, resin, etc., but metal is preferred from the viewpoint of applying pressure evenly.
  • the stretching ratio, stretching temperature, and stretching speed are not particularly limited as long as the object of the present invention can be achieved, but it is preferable to set them in the following ranges.
  • Stretching improves the heat-resistant dimensional stability of the raw resin sheet and the resin sheet.
  • There are uniaxial stretching, sequential biaxial stretching, and simultaneous biaxial stretching methods but it is preferable to perform sequential biaxial stretching or simultaneous biaxial stretching, and more preferably simultaneous biaxial stretching.
  • uniaxial stretching the linear expansion coefficient in the direction not stretched does not decrease, and the heat-resistant dimensional stability may decrease.
  • sequential biaxial stretching the reduction in the thermal expansion coefficient in the direction first stretched becomes small, and the heat-resistant dimensional stability may decrease, so this tendency becomes stronger unless the stretching speed is reduced.
  • the stretch ratio is within a range where breakage does not occur of 2.0 times or more in both the MD and TD directions, and is preferably 2.0 to 5.0 times, and more preferably 2.3 to 4.0 times. It is preferable that the stretch ratios in the MD and TD directions are similar. Specifically, when the stretch ratio in the MD direction is PMD and the stretch ratio in the TD direction is PTD, "PTD-PMD" is preferably -0.6 to +0.6, and more preferably -0.3 to +0.3.
  • the stretch ratio in the MD direction is a ratio based on the MD length immediately before stretching.
  • the stretch ratio in the TD direction is a ratio based on the TD length immediately before stretching.
  • the stretching temperature is preferably TgP or more and TgP + 30°C or less, and more preferably TgP°C or more and TgP + 25°C or less from the viewpoint of further improving heat-resistant dimensional stability, tensile strength and tensile elongation.
  • TgP glass transition temperature
  • the stretching temperature is preferably TgP or more and TgP + 30°C or less, and more preferably TgP°C or more and TgP + 25°C or less from the viewpoint of further improving heat-resistant dimensional stability, tensile strength and tensile elongation.
  • the stretching temperature is the temperature of the raw resin sheet when stretching.
  • the TgP of the syndiotactic polystyrene resin (A) can be confirmed from an endothermic peak (relaxation of the amorphous part) observed by differential scanning calorimetry (DSC).
  • the stretching speed is 50 to 10,000%/min in both the MD and TD directions, preferably 100 to 5,000%/min, and more preferably 100 to 3,000%/min.
  • the stretching speed is a value calculated by ⁇ (dimension after stretching/dimension before stretching)-1 ⁇ x 100(%)/stretching time.
  • the thickness of the resin sheet is preferably 10 to 2000 ⁇ m, more preferably 15 to 1000 ⁇ m, even more preferably 20 to 500 ⁇ m, and most preferably 25 to 300 ⁇ m. If the thickness of the resin sheet is 10 ⁇ m or more, the resin sheet is less likely to crack. If the thickness of the resin sheet is 2000 ⁇ m or less, the occurrence of partial shrinkage (sink marks) is suppressed, and thickness unevenness does not occur.
  • the thickness of the raw resin sheet is preferably 10 to 2000 ⁇ m, more preferably 15 to 1000 ⁇ m, even more preferably 20 to 500 ⁇ m, and most preferably 25 to 300 ⁇ m.
  • An adhesive layer may be laminated on the surface of the surface treatment layer.
  • the form of the adhesive layer there is no restriction on the form of the adhesive layer, and it may be, for example, a coating of adhesive or a laminate of an adhesive sheet.
  • the composition of the adhesive layer there is no particular restriction on the composition of the adhesive layer, but for example, polyolefin, maleimide, polyphenylene ether, polyphenylene sulfide, styrene-based elastomer, etc. can be used as the base material. Of these, it is preferable that the adhesive layer contains a styrene-based elastomer.
  • the adhesive layer may further contain a curing agent.
  • curing agents include aliphatic epoxies, alicyclic epoxies, benzoxazines, carbodiimides, and isocyanates.
  • the adhesive layer may also contain additives such as fillers, such as silica and mica, and flame retardants.
  • the adhesive layer may be formed using an adhesive sheet, which is a precursor.
  • the adhesive sheet may be a sheet in which an adhesive composition is applied onto a release substrate, dried to partially harden, and a release substrate is further laminated thereon.
  • a specific configuration may be a release substrate/adhesive layer/release substrate.
  • the release substrate is laminated to function as a protective layer for the substrate or adhesive layer.
  • the release substrate can be released from the adhesive sheet, and the adhesive layer can be transferred to another substrate.
  • the thickness of the adhesive sheet is, for example, preferably 5 to 200 ⁇ m, more preferably 8 to 150 ⁇ m, even more preferably 10 to 100 ⁇ m, and most preferably 12 to 80 ⁇ m.
  • the adhesive sheet 5 ⁇ m or thicker By making the adhesive sheet 5 ⁇ m or thicker, the occurrence of pinholes can be prevented.
  • the adhesive strength can be increased.
  • thickness unevenness By making the adhesive sheet 200 ⁇ m or thinner, thickness unevenness can be reduced.
  • residual solvent can be reduced, and blisters can be prevented from occurring during pressing in the manufacture of printed wiring boards.
  • the release substrate is not particularly limited, but examples include high-quality paper, craft paper, roll paper, glassine paper, etc., on both sides of which a coating layer of a filler such as clay, polyethylene, or polypropylene is applied, and then a silicone-, fluorine-, or alkyd-based release agent is applied on each coating layer.
  • a coating layer of a filler such as clay, polyethylene, or polypropylene
  • a silicone-, fluorine-, or alkyd-based release agent is applied on each coating layer.
  • Other examples include various olefin films such as polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer, propylene- ⁇ -olefin copolymer, etc. alone, and films such as polyethylene terephthalate on which the above release agents are applied.
  • polypropylene-treated high-quality paper on both sides and an alkyd-based release agent on the polypropylene, or an alkyd-based release agent on polyethylene terephthalate.
  • a primer composition that contains a first silane compound (a) having an aminoalkyl group and two or more alkoxy groups, a second silane compound (b) having an alkenyl group and two or more alkoxy groups, and an alcohol (d), in which the amount of the second silane compound (b) is 100 to 250 parts by mass per 100 parts by mass of the first silane compound (a).
  • the method for forming the primer layer is not particularly limited, and examples include a method of applying a primer composition to the surface of a resin sheet, and a method of immersing a resin sheet in a primer composition.
  • the primer composition may be diluted with water (e).
  • curing After heating, curing (hardening treatment) may be performed.
  • the curing temperature is not particularly limited and may be, for example, 80°C to 120°C. Curing may be performed, for example, using a thermostatic bath. The curing temperature may be relatively lower than the heating temperature.
  • raw materials and raw material characteristics The raw materials used in the examples are described below together with the raw material characteristics for each component of the laminate.
  • the melting points of the raw materials were measured using a differential scanning calorimeter (hereinafter, DSC, "Q-2000" manufactured by TA Instruments Japan) at a rate of 20°C/min, melted by heating, cooled to resin, and then melted by heating again, from the top temperature and area of the melting peak.
  • the glass transition temperature of the raw material was taken as the temperature at the start (rise) of the endothermic peak during the heating process. For other characteristics, the nominal values listed in the catalog values of the raw material manufacturer were listed.
  • Fibrous filler HDT09100T (12% by mass, D glass, fiber diameter 9 ⁇ m, D50 average fiber length 100 ⁇ m) manufactured by Tochu Co., Ltd.
  • Non-fibrous filler Silica particles FB-3SDC (10% by mass, D50 average particle size 3.1 ⁇ m) manufactured by Denka Co., Ltd.
  • Antioxidant ANOX20 (0.2 mass%, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], melting point 118°C) manufactured by BASF Japan Ltd.
  • ANOX20 decreased by 1 mass% at 166°C, by 3 mass% at 335°C, by 5 mass% at 350°C, and by 10 mass% at 369°C.
  • the thermal decomposition temperature of ANOX20 was 350°C.
  • Adhesive layer A low dielectric adhesive film "Aron Mighty AF-711" (flame retardant grade, thickness 25 ⁇ m) manufactured by Toa Gosei Co., Ltd.
  • the obtained cylindrical resin pellets were fed into a hopper of a single-screw extruder having a diameter of 20 mm, and remelted at a resin temperature of 300° C., extruded from a T-die into a sheet, sandwiched between two rolls, a metal touch roll and a winding roll (both roll temperatures were 90° C.), compressed and cooled to solidify, and then wound around a paper tube having a diameter of 80 mm at a speed of 1 m/min to produce an unstretched sheet (raw resin sheet) having a thickness of 300 ⁇ m.
  • the pressure of the touch roll was a linear pressure of 100 N/cm.
  • MD the direction parallel to the extrusion direction of the sheet
  • TD direction perpendicular to the extrusion direction
  • the obtained unstretched sheet (raw resin sheet) was subjected to heat treatment and annealing treatment to produce a resin sheet.
  • an unstretched sheet was prepared by cutting it appropriately according to the face plate size of a vacuum press (MHPC-V-450-450, manufactured by Japan Steel Works), and a release film PEEK (Shin-Etsu Sepia Film, thickness 50 ⁇ m), a SUS plate (#400, thickness 1.5 mm, SUS304), and a cushioning material (Yamauchi Original Mat, YOM type) were laminated on both sides of this sheet in that order, and the laminate was placed in the vacuum press.
  • MHPC-V-450-450 manufactured by Japan Steel Works
  • a release film PEEK Shin-Etsu Sepia Film, thickness 50 ⁇ m
  • SUS plate #400, thickness 1.5 mm, SUS304
  • a cushioning material Yamauchi Original Mat, YOM type
  • the sheet was heated from room temperature to 200°C at a heating rate of 7°C/min, and pressed under vacuum (less than 4 mmHg) at a pressure of 2 MPa for 30 minutes. After that, the sheet was slowly cooled to about 50°C, and the vacuum was released to obtain a heat-treated sheet. The heat-treated sheet was then annealed. The annealing was performed by leaving the heat-treated sheet in a thermostatic chamber set at 180°C for 30 minutes, after which the sheet was removed from the thermostatic chamber and left to cool to room temperature. The laminated release film, SUS plate, and cushioning material were removed to obtain a resin sheet.
  • Example 6 A resin sheet 6 was produced under the same conditions as in Experiment 1, except that the surface treatment layer, which was a treatment layer made of primer composition 1, was not formed.
  • Table 1 shows the types of solutions (Solution 1, Solution 2) used when forming a surface treatment layer on the surface of the resin sheet.
  • Solution 1, Solution 2 used when forming a surface treatment layer on the surface of the resin sheet.
  • a - indicates that a surface treatment layer was not formed.
  • the surfaces of the resin sheets obtained in Experiments 1 and 3 to 6 were subjected to elemental analysis using ESCA (X-ray photoelectron spectrometry).
  • ESCA X-ray photoelectron spectrometry
  • K-Alpha+ made by Thermo Fisher SCIENTIFIC was used.
  • Table 1 The results of the elemental analysis are also shown in Table 1 above. Based on the results of the elemental analysis, the value of Si/(C+N+O+Si) defined by formula (1), the value of O/Si defined by formula (2), the value of C/Si defined by formula (3), and the value of N/Si defined by formula (4) were each calculated. The calculated values are also shown in Table 1 above.
  • the laminate structure obtained in Experiments 1, 2, and 5 was metal layer/adhesive layer/resin sheet with surface treatment layer/adhesive layer/metal layer.
  • the laminate structure obtained in Experiments 3, 4, and 6 was metal layer/adhesive layer/resin sheet/adhesive layer/metal layer.
  • the obtained laminate was subjected to a heat treatment.
  • a curing (hardening) process was also performed after the heat treatment.
  • the heat treatment was carried out by laminating a SUS plate (#400, thickness 1.5 mm, SUS304) and a cushioning material (Yamauchi Original Mat, YOM type) in this order on both sides of the obtained laminate, and placing the obtained laminate in a vacuum press.
  • Vacuum pressing was carried out in the vacuum press under the following condition 1 or condition 2.
  • Table 1 shows the vacuum pressing conditions (condition 1, condition 2) used in each experiment.
  • Condition 1 The temperature was raised from room temperature to 180° C. at a rate of 6° C./min, and the sample was pressed for 60 minutes under a vacuum at a pressure of 2 MPa.
  • Condition 2 The temperature was raised from room temperature to 120° C. at a rate of 6° C./min, and the sample was pressed for 15 minutes under vacuum at a pressure of 2 MPa.
  • the material was slowly cooled to about 50°C, the vacuum was released, and the heat-treated laminate was removed.
  • the heat-treated laminate was placed in a thermostatic chamber set at 100°C and left to stand for 24 hours in a nitrogen atmosphere (approximately 20 L/min) to cure. If curing was performed, it is indicated as ⁇ in Table 1, and if curing was not performed, it is indicated as - in Table 1. After curing, the laminate was removed from the thermostatic chamber and left to stand until it cooled to room temperature, obtaining a resin sheet in which a metal layer was laminated via an adhesive layer.
  • the laminate obtained by heat treatment or the laminate after curing was made into a resin sheet, and the peel strength and heat resistance of the obtained resin sheet were evaluated.
  • the heat resistance of the resin sheet in which the metal layer was laminated via the adhesive layer was evaluated by a solder float test.
  • the resin sheet was cut into a size of 25 x 25 mm to prepare a test piece.
  • a solder bath (POT-103C manufactured by Taiyo Electric Industry Co., Ltd.) containing lead-free solder (lead-free bar solder, M705-BAR manufactured by Taiyo Electric Industry Co., Ltd.) was set to 260 ° C., and the test piece was floated on the molten solder. After leaving it for 1 minute, the test piece was removed from the solder bath and left to stand until it cooled down to room temperature.
  • the appearance of the test piece was visually observed to confirm whether there was any swelling due to air bubbles and foreign matter in the metal layer, and whether there was any peeling in the metal layer. If there was no swelling due to air bubbles and foreign matter in the metal layer and no peeling in the metal layer, it was considered to have passed, and the heat resistance was evaluated as good, and the evaluation result was indicated as ⁇ in Table 1. When the metal layer had blisters due to air bubbles, blisters due to foreign matter, or peeling, the sample was deemed to have failed the test and was evaluated as having poor heat resistance. The evaluation result was indicated as x in Table 1.
  • the resin sheets obtained in Experiments 1, 2, and 5 had a surface treatment layer that satisfied the requirements specified in the present invention, so when a metal layer was laminated on the resin sheet via an adhesive layer, the peel strength at the interface between the resin sheet and the adhesive layer was high, the adhesion between the resin sheet and the adhesive layer was good, and the metal layer was not easily peeled off.
  • the resin sheet with the metal layer laminated on the adhesive layer had excellent heat resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille de résine qui présente une couche de traitement de surface, la feuille de résine comportant une résine de polystyrène syndiotactique et, lorsqu'elle est stratifiée sur une couche métallique au moyen d'une couche adhésive, présentant une adhérence favorable à la couche adhésive et ne libérant pas facilement la couche métallique, même lorsqu'elle est soumise à des conditions de traitement thermique qui simulent un processus de brasage.　Une feuille de résine qui présente une couche de traitement de surface selon la présente invention, comporte une résine de polystyrène syndiotactique. La couche de traitement de surface se trouve sur une surface ou sur les deux surfaces de la feuille de résine, et, au niveau d'au moins une surface, lorsque la surface de la couche de traitement de surface qui n'est pas en contact avec la feuille de résine est soumise à une analyse élémentaire par spectroscopie photoélectronique à rayons x (ESCA), Si, C, N et O sont observées, et leurs quantités satisfont une relation prescrite.
PCT/JP2025/000947 2024-01-18 2025-01-15 Feuille de résine présentant une couche de traitement de surface, composition d'apprêt, et procédé de production d'une feuille de résine présentant une couche de traitement de surface Pending WO2025154721A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001329088A (ja) * 1999-10-18 2001-11-27 Nippon Sheet Glass Co Ltd 二酸化珪素被覆ポリオレフィン樹脂及びその製造方法
WO2019093380A1 (fr) * 2017-11-10 2019-05-16 横浜ゴム株式会社 Méthode pour la fabrication d'un corps stratifié
JP2022097959A (ja) * 2020-12-21 2022-07-01 日本バイリーン株式会社 積層構造体
WO2023120579A1 (fr) * 2021-12-24 2023-06-29 国立大学法人岩手大学 Procédé de production de produit stratifié
JP2024117412A (ja) * 2023-02-17 2024-08-29 株式会社朝日Ｆｒ研究所 基材の親水化処理方法及び親水性改質基材

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001329088A (ja) * 1999-10-18 2001-11-27 Nippon Sheet Glass Co Ltd 二酸化珪素被覆ポリオレフィン樹脂及びその製造方法
WO2019093380A1 (fr) * 2017-11-10 2019-05-16 横浜ゴム株式会社 Méthode pour la fabrication d'un corps stratifié
JP2022097959A (ja) * 2020-12-21 2022-07-01 日本バイリーン株式会社 積層構造体
WO2023120579A1 (fr) * 2021-12-24 2023-06-29 国立大学法人岩手大学 Procédé de production de produit stratifié
JP2024117412A (ja) * 2023-02-17 2024-08-29 株式会社朝日Ｆｒ研究所 基材の親水化処理方法及び親水性改質基材

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