WO2009145083A1 - Film antiadhésif comprenant une résine de poly(sulfure de phénylène) et stratifié - Google Patents

Film antiadhésif comprenant une résine de poly(sulfure de phénylène) et stratifié Download PDF

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Publication number
WO2009145083A1
WO2009145083A1 PCT/JP2009/059182 JP2009059182W WO2009145083A1 WO 2009145083 A1 WO2009145083 A1 WO 2009145083A1 JP 2009059182 W JP2009059182 W JP 2009059182W WO 2009145083 A1 WO2009145083 A1 WO 2009145083A1
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Prior art keywords
film
polyphenylene sulfide
pps
release film
sulfide resin
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PCT/JP2009/059182
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English (en)
Japanese (ja)
Inventor
葵 宮崎
弘行 大場
友則 細田
正之 大倉
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株式会社クレハ
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Priority to JP2010514446A priority Critical patent/JP5587771B2/ja
Priority to CN2009801197921A priority patent/CN102046349B/zh
Priority to KR1020107026556A priority patent/KR101228745B1/ko
Publication of WO2009145083A1 publication Critical patent/WO2009145083A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/68—Release sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • 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
    • 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
    • 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
    • B32B27/286—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 polysulphones; polysulfides
    • 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
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2081/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material
    • B29K2081/04—Polysulfides, e.g. PPS, i.e. polyphenylene sulfide or derivatives thereof
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/04—Polysulfides
    • 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

Definitions

  • the present invention relates to a release film made of polyphenylene sulfide resin and a laminate using the film made of polyphenylene sulfide resin. More specifically, the present invention relates to a technique for improving the peelability of a polyphenylene sulfide resin film.
  • Circuit board is one of the main parts of electrical products for fixing and wiring electronic components.
  • Rigid board using inflexible insulating base material and thin and flexible insulating base material It is roughly divided into flexible substrates using
  • a release film that can be peeled after the process is completed is used.
  • Such a release film for a circuit board is not only adhered to the substrate material because it is peeled off after being subjected to processing such as heating and pressurization and chemical solution infiltration in a state of being attached to a substrate material such as a prepreg.
  • processing such as heating and pressurization and chemical solution infiltration in a state of being attached to a substrate material such as a prepreg.
  • Various characteristics such as heat resistance, chemical resistance and peelability are required.
  • PPS polyphenylene sulfide
  • Patent Documents 1 and 2 disclose polyarylene sulfide resin compositions in which a styrene polymer having a syndiotactic structure is mixed in order to improve moldability.
  • Patent Document 3 discloses a resin composition containing polyphenylene sulfide as a main component on both surfaces of a resin composition layer (B layer) having a heat deformation temperature of 70 to 150 ° C.
  • a laminated film in which a biaxially stretched film (A layer) is laminated and a ratio of the thickness of the A layer to the entire thickness is in the range of 0.05 to 0.5 has been proposed. .
  • the polyphenylene sulfide layer forming the release surface has an average surface roughness of 5 nm or more and a thickness of 0.1 to 200 ⁇ m, and the polyphenylene sulfide layer and another resin layer are laminated by coextrusion.
  • a substantially unstretched composite sheet has also been proposed.
  • the conventional PPS film is excellent in heat resistance and chemical resistance, but has a problem that it has high adhesion to the substrate material and is difficult to peel off.
  • the biaxially stretched film made of the polyarylene sulfide resin composition described in Patent Document 2 is excellent in moldability, but has not been studied for peelability from the substrate material.
  • the film described in Patent Document 3 has a laminated structure, curling is likely to occur due to a difference in thermal expansion coefficient between the resin constituting the A layer and the resin constituting the B layer, and the PPS is formed on the outermost layer. Since the film is disposed, there is a problem that the adhesion strength with the substrate material is large and it is difficult to peel off. Furthermore, since the film described in Patent Document 4 is an unstretched PPS film, it becomes brittle when heated, and has a problem that it cannot withstand the stress at the time of peeling and cracks.
  • the conventional PPS film has various problems in order to be used as a release film for circuit boards. Therefore, a PPS film having a good balance between adhesion to the substrate material and releasability, specifically, while performing treatment such as chemical infiltration, the substrate material is in close contact and the substrate is reliably protected, and There is a need for a PPS film that can be easily removed from the substrate material when it is no longer needed.
  • the present invention provides a release film and laminate made of polyphenylene sulfide resin that are excellent in heat resistance, chemical resistance, and adhesion to a substrate material, and also excellent in releasability from the substrate material after processing. Main purpose.
  • the release film made of polyphenylene sulfide resin according to the present invention is a release film formed by stretching a polyphenylene sulfide resin composition, and the polyphenylene sulfide resin composition contains 0.1 to 30 volumes of syndiotactic polystyrene. %, And the film thickness is in the range of 20 to 100 ⁇ m.
  • regulated here is the conversion value calculated
  • the present invention since it contains a specific amount of syndiotactic polystyrene, the releasability from the substrate material is improved, and the workability is improved because the film has a specific thickness. As a result, the strength is increased. Thereby, peelability improves from the substrate material after processing. As a result, an excellent release film having easy peelability in addition to the heat resistance, chemical resistance, and moderate adhesion with the substrate material possessed by the PPS resin can be obtained.
  • the elemental ratio (C / S) of carbon (C) and sulfur (S) on the film surface can be made larger than the central portion in the thickness direction, and particularly in the polyphenylene sulfide resin composition.
  • the syndiotactic polystyrene content is 1.0% by volume or more, and the elemental ratio (C / S) of carbon (C) to sulfur (S) on the film surface is 7.5 or more.
  • the film surface in this invention means the area
  • the said polyphenylene sulfide resin composition may contain 25 mass parts or less of saturated hydrocarbon copolymers with respect to 100 mass parts of syndiotactic polystyrenes.
  • the said polyphenylene sulfide resin composition can also contain calcium carbonate: 0.3 mass part or less and calcium stearate: 0.2 mass part or less with respect to 100 mass parts of polyphenylene sulfide.
  • these release films can be used in the manufacturing process of a rigid board
  • the laminate according to the present invention has a polyphenylene sulfide resin release film in contact with at least one surface of a rigid substrate, or a plurality of rigid substrates through these polyphenylene sulfide resin release films. Are laminated.
  • the film thickness is set to a specific range, and further formed by stretching, adhesion to a substrate material, chemical resistance and heat resistance It is possible to realize a release film and a laminate excellent in not only the properties but also the releasability from the processed substrate material.
  • (A) and (b) are formed using a PPS resin composition containing a total of 7.7% by volume of s-PS and saturated hydrocarbon copolymer and having a s-PS content of 6.0% by volume. It is a cross-sectional TEM photograph of the release film made from PPS resin. (A) And (b) is the cross-sectional TEM photograph of the PPS resin release film formed using the PPS resin composition containing 7.5 volume% of s-PS.
  • PPS polyphenylene sulfide
  • s-PS syndiotactic polystyrene
  • the present inventor has (3) adjusting the element ratio (C / S) of carbon (C) and sulfur (S) on the film surface in the PPS resin release film, or (4) PPS resin. It has been found that the releasability from the substrate material can be controlled by adding an elastomer component (saturated hydrocarbon copolymer) to the composition. Furthermore, the present inventor does not deteriorate properties such as peelability even when a filler such as calcium carbonate and calcium stearate is added to the PPS resin composition. It has also been found that it is suitable for use in the manufacturing process of rigid substrates.
  • the PPS resin release film of the present invention is a film formed by stretching a PPS resin composition containing 0.1 to 30% by volume of s-PS, and its thickness is 20 to 100 ⁇ m. .
  • the film surface is preferably larger in the element ratio (C / S) of carbon (C) and sulfur (S) than in the center in the thickness direction,
  • the s-Ps content in the PPS resin composition is 1.0% by volume or more, and the elemental ratio (C / S) of carbon (C) to sulfur (S) on the film surface is 7.5 or more. It is more preferable that
  • the PPS resin composition constituting the PPS resin release film of the present invention preferably contains 25 parts by mass or less of a saturated hydrocarbon copolymer per 100 parts by mass of s-PS. Accordingly, calcium carbonate: 0.3 parts by mass or less and calcium stearate: 0.2 parts by mass or less can be blended per 100 parts by mass of PPS. And by these structures, the release film excellent not only in the adhesiveness with respect to board
  • the peelability of the release film for substrates depends on the chemical and physical properties of the substrate material to be bonded.
  • the prepreg to be attached with the PPS resin release film of the present invention is a kind of substrate material, and is obtained by impregnating a base material with a resin.
  • the substrate used in this case include inorganic fiber substrates such as glass woven fabric (glass cloth) and glass nonwoven fabric, and organic fiber substrates such as aramid woven fabric, aramid nonwoven fabric, paper fiber, and carbon fiber. .
  • Examples of the matrix resin impregnated in these base materials include, for example, epoxy resins, phenol resins, acrylic resins, amino resins, olefin resins, vinyl resins, imide resins, amide resins, and ester resins.
  • Various thermosetting resins or thermoplastic resins such as resins, ether resins, fluorine resins, cyanate resins and isocyanate resins are used. And such a prepreg is bonded to a copper foil and processed into a base material copper-clad laminate, and used as a circuit board.
  • PPS which is a main component of the PPS resin release film of the present invention will be described.
  • PPS is a polymer having p-phenylene sulfide represented by the following chemical formula 1 as a repeating unit, and in the release film made of PPS resin of the present invention, adhesion to the substrate material, heat resistance and chemical resistance are ensured. It is an important ingredient to do.
  • the PPS used in the present invention preferably contains 70 mol% or more of p-phenylene sulfide units as repeating units in the polymer.
  • the p-phenylene sulfide unit is less than 70 mol%, the crystallinity and glass transition point of the polymer are lowered, so that the heat resistance and mechanical strength, which are the characteristics of the polymer film mainly composed of PPS, are not fully exhibited. Because there is.
  • the p-phenylene sulfide unit is more preferably contained in 90 mol% or more.
  • the PPS may contain a repeating unit having a polymerizable sulfide bond as long as it is less than 30 mol%, preferably less than 10 mol%, among the repeating units of the polymer. Good.
  • the repeating unit having a polymerizable sulfide bond is not particularly limited, but an aromatic sulfide unit represented by the following chemical formula 2 is particularly preferable.
  • Ar in the following chemical formula 2 is an aryl group, and examples thereof include functional groups represented by the following chemical formulas 3 to 10.
  • the polymer when the PPS is a copolymer containing the monomer unit represented by the chemical formula 2, the polymer may be in any form of a random polymer and a block polymer. Moreover, the monomer unit other than the said Chemical formula 1 may exist in the polymer terminal or near the terminal.
  • the PPS in the present invention is obtained by the method described in, for example, US Pat. No. 4,645,826, that is, an alkali metal sulfide and dichlorobenzene are present in a polar solvent such as N-methyl 2-pyrrolidone. Under certain conditions, it can be obtained by a specific two-step temperature rising polymerization method. By applying this polymerization method, a substantially linear and high molecular weight PPS can be obtained. Further, by adding a small amount of an aromatic halogen compound having 3 or more halogen substituents at the time of polymerization, it is possible to obtain a PPS having some branched or crosslinked structure. Further, as a method for producing the block copolymer, for example, methods described in JP-A-2-225535 and JP-A-4-213328 can be applied.
  • the melt viscosity of PPS is preferably 20 to 2000 Pa ⁇ s when measured at a temperature of 310 ° C. and a shear rate of 1200 / sec.
  • the melt viscosity is less than 20 Pa ⁇ s, the mechanical properties and heat resistance of the film are lowered, and the characteristics as a PPS film may not be obtained.
  • the melt viscosity exceeds 2000 Pa ⁇ s, the extruder This is because the addition of a manufacturing device such as a filter or a filtration device may increase, causing problems.
  • the melt viscosity of the PPS is more preferably 30 to 1800 Pa ⁇ s.
  • the shear rate here is a value defined as a gradient rate when a viscous fluid passes between parallel plates.
  • s-PS is a styrene polymer mainly having a syndiotactic structure represented by the following chemical formula 11 in a repeating unit.
  • the syndiotactic structure refers to a three-dimensional structure in which phenyl groups and substituted phenyl groups as side chains are alternately located in opposite directions with respect to a main chain formed from carbon-carbon bonds.
  • s-PS is a method described in, for example, JP-A-62-187708, that is, condensation of a titanium compound and water with a trialkylaluminum in an inert hydrocarbon solvent or in the absence of a solvent. It can be obtained by polymerizing a styrene monomer using the product as a catalyst.
  • the s-PS content in the PPS resin composition is less than 0.1 volume, the effect of addition cannot be obtained, the adhesion due to PPS becomes dominant, and it becomes difficult to peel off from the substrate material.
  • the s-PS content exceeds 30% by volume, the amount of PPS in the composition decreases, and thus the adhesiveness to the substrate material, heat resistance and chemical resistance decrease, and it is practical as a release film. Low.
  • the s-PS content exceeds 30% by volume, the moldability is deteriorated, so that breakage may occur during transverse stretching. Therefore, the s-PS content in the PPS resin composition is 0.1 to 30% by volume.
  • the s-PS content in the PPS resin composition is preferably 0.3 to 25% by volume, more preferably 0.5 to 20% by volume.
  • the volume% is a converted value, which is a value obtained from the blending amount (mass) and density of s-PS.
  • the PPS density is 1.35 g / cm 3 and the s-PS density is 1.04 g / cm 3 .
  • the film thickness is preferably 22.5 to 80 ⁇ m, more preferably 25 to 70 ⁇ m. Thereby, workability
  • the elemental ratio of carbon (C) to sulfur (S) on the film surface (hereinafter referred to as C / S ratio) is as follows. It is desirable that the ratio is larger than the C / S ratio in the central portion in the thickness direction. Thus, by making carbon unevenly distributed on the film surface, good releasability from the substrate material can be stably obtained.
  • the film surface refers to a region from the film surface to a depth of several nm.
  • the s-PS content in the PPS resin composition is preferably 1.0% by volume or more, and the C / S ratio on the film surface is preferably 7.5 or more, thereby improving the peelability on the film surface. be able to.
  • the peel strength with respect to the general-purpose multilayer printed wiring board material (FR-4) can be set to 200 N / m or less.
  • the s-PS content in the PPS resin composition is set to 1.0% by volume or more because when the s-PS content is less than 1.0% by volume, the C / S ratio on the film surface is 7. This is because it may be less than 5.
  • C / S ratio in the film surface and thickness direction center part can be measured by XPS (X-ray photoelectron spectroscopy: X-ray photoelectron spectroscopy), for example. Further, the C / S ratio on the film surface can be adjusted by the blending amount of s-PS in the PPS resin composition and the production conditions described later.
  • FIGS. 1 and 2 are cross-sectional TEM (Transmission Electron Microscope) photographs of a PPS resin release film.
  • FIG. 1 shows a film formed using a PPS resin composition containing 7.7% by volume of s-PS and saturated hydrocarbon copolymer in total, and having an s-PS content of 6.0% by volume.
  • FIG. 2 is a photograph of a film formed using a PPS resin composition containing 7.5% by volume of s-PS.
  • the bulk s-PS phase is dispersed throughout the film, and its C / S ratio (theoretical value) is about 6.6.
  • the C / S ratio of the surface is about 10 to 13. From this, it is considered that low molecular weight s-PS and an elastomer component (saturated hydrocarbon copolymer) are unevenly distributed on the surface.
  • the saturated hydrocarbon copolymer may be mix
  • PPS and s-PS have low compatibility, but by adding an elastomer component (saturated hydrocarbon copolymer) to the PPS resin composition, the saturated hydrocarbon copolymer acts as a compatibilizer. The compatibility of is improved. Thereby, the dispersion
  • the peelability between the PPS resin release film and the substrate material is also changed. That is, in the PPS resin release film of the present invention, the releasability from the substrate material can be controlled by adjusting the blending amount of the saturated hydrocarbon copolymer in the PPS resin composition.
  • the thermal stability decreases, and a sheet (unstretched film) is formed by extrusion. May decompose.
  • the saturated hydrocarbon copolymer is 25 parts by mass or less with respect to s-PS: 100 parts by mass.
  • the PPS resin release film of the present invention may contain calcium carbonate and calcium stearate.
  • Calcium carbonate and calcium stearate act as lubricants.
  • the blending amount of calcium carbonate exceeds 0.3 parts by mass with respect to 100 parts by mass of PPS, the agglomeration may occur, or the elongation at break may be reduced, making stretching difficult.
  • the compounding quantity of a calcium stearate exceeds 0.2 mass part, the extrusion defect may generate
  • the release film made of the PPS resin of the present invention includes PPS, s-PS: 0.1 to 30% by volume, and an elastomer component such as a saturated hydrocarbon copolymer, calcium carbonate and calcium stearate, if necessary. It can be produced by stretching an unstretched film formed by melting a PPS resin composition containing a predetermined amount of additives.
  • the film is formed by stretching in order to impart strength to the film.
  • the release film needs to be strong enough to withstand the force applied when peeling from the substrate material, but unstretched film becomes brittle when heated, so it cannot withstand the strength when peeled, and the film cracks. End up. For this reason, the film is formed by stretching.
  • PPS pellets and s-PS pellets are weighed so that the s-PS content is 0.1 to 30% by volume (converted value). Further, if necessary, a predetermined amount of saturated hydrocarbon copolymer pellets are blended, dry blended, and supplied to an extruder (hereinafter, this method is referred to as a dry blend method). Alternatively, s-PS pellets are blended in the PPS powder so as to be 0.1 to 30% by volume (converted value), and further, if necessary, blended with a predetermined amount of saturated hydrocarbon copolymer pellets and then mixed. Then, it is remelted and pelletized, and supplied to an extruder (hereinafter, this method is referred to as a compound method).
  • calcium carbonate and calcium stearate may be blended, or instead of PPS pellets, a resin composition obtained by blending PPS with calcium carbonate and calcium stearate may be used.
  • a resin composition obtained by blending PPS with calcium carbonate and calcium stearate may be used instead of s-PS pellets.
  • pellets of a resin composition in which a saturated hydrocarbon polymer is blended with s-PS may be used.
  • PPS pellets or PPS resin pellets containing a predetermined amount of calcium carbonate and calcium stearate, and s-PS pellets or resin pellets containing a saturated hydrocarbon polymer in s-PS include lubricants, plasticizers, oxidation Various additives such as an inhibitor and an impact resistance agent may be blended.
  • each supplied resin is melted at 280 to 340 ° C., formed into a desired film shape with a die, and discharged.
  • the melting temperature is less than 280 ° C.
  • PPS is not sufficiently melted
  • a decomposition product of the resin is generated during extrusion. Therefore, the melting temperature is 280 to 340 ° C.
  • an unstretched film is obtained by pressing the film discharged from die
  • the unstretched film thus obtained is stretched to give strength to the film.
  • the PPS resin release film of the present invention may be a stretched film, but is more preferably a biaxially stretched film.
  • biaxial stretching refers to stretching in order to give molecular orientation in the longitudinal direction and the transverse direction. Stretching may be performed in two directions separately (hereinafter referred to as sequential biaxial stretching) or simultaneously in two directions. Moreover, you may redraw in the vertical and / or horizontal direction.
  • the stretching in the machine direction is usually performed by the peripheral speed difference of the roll. This stretching may be performed in one stage, or may be performed in multiple stages using a plurality of roll pairs.
  • the surface temperature of the film during stretching in the machine direction is preferably 80 to 110 ° C. When the film surface temperature at the time of stretching is less than 80 ° C., the film becomes less than the glass transition temperature of PPS, so that the film is hardly stretched uniformly. On the other hand, when the film surface temperature exceeds 110 ° C., a stick slip in which the film intermittently adheres to the stretching roll occurs, and uniform stretching becomes difficult.
  • the film temperature when stretching in the longitudinal direction is more preferably 85 to 105 ° C.
  • stretching can be suitably adjusted by changing the temperature of a roll.
  • the draw ratio in the longitudinal direction is 2.0 to 5.0 times.
  • the draw ratio in the longitudinal direction is preferably 2.5 to 4.0 times.
  • the film stretched in the longitudinal direction by the above-described method and conditions is introduced into a tenter stretching machine, and the film is stretched in the lateral direction by pulling the both ends of the film with clips.
  • the film surface temperature during stretching in the transverse direction is preferably 80 to 110 ° C. When the temperature at the time of stretching is less than 80 ° C., it cannot be uniformly stretched, and it tends to be difficult to obtain good flatness. On the other hand, when the film surface temperature exceeds 110 ° C., orientational crystallization does not proceed sufficiently and the elastic modulus and heat resistance tend to be insufficient.
  • the film temperature during stretching in the transverse direction is more preferably 85 to 105 ° C.
  • the draw ratio in the transverse direction is 2.0 to 5.0 times.
  • the draw ratio is less than 2.0 times, it cannot be drawn uniformly, which may cause poor flatness.
  • the draw ratio exceeds 5.0 times, the frequency of occurrence of breakage increases and the productivity tends to decrease.
  • the distance between the clips immediately sandwiching the film is reduced by about 0.1 to 10%, preferably about 0.5 to 7%. It is preferable to perform the heat setting treatment at a temperature not lower than the stretching temperature and not higher than the melting point. Thereby, a heat-resistant dimension can be stabilized.
  • the temperature of the heat setting treatment is preferably 240 to 290 ° C. If the heat setting treatment temperature is less than 240 ° C., the efficiency of relaxation in the transverse direction is lowered, and it may be difficult to obtain a film having excellent dimensional stability at high temperatures, and the heat setting treatment temperature is 290 ° C. This is because exceeding the melting point of the PPS film makes it difficult to form a film.
  • the heat setting treatment temperature is more preferably 250 to 285 ° C.
  • the film after the heat setting treatment is cooled to room temperature at the exit of the tenter stretching machine, and then wound up by a winder to obtain a biaxially stretched PPS resin release film.
  • the PPS resin release film of the present invention is formed from a PPS resin composition containing 0.1 to 30% by volume of s-PS, it is a substrate material as compared with a conventional PPS film.
  • Excellent peelability from In the PPS resin release film of the present invention since the thickness of the film obtained by stretching is in the range of 20 to 100 ⁇ m, excellent workability and strength as a release film can be obtained. As a result, the chemical resistance and heat resistance of the PPS can be reduced, and further, the peelability from the substrate material after processing can be improved while maintaining the adhesion to the substrate material such as prepreg.
  • the PPS resin release film of the present invention can control the peel strength from the substrate material by adjusting the C / S ratio on the film surface.
  • the C / S ratio on the film surface can be adjusted, for example, by changing the amount of s-PS blended in the PPS resin composition or the mixing method and conditions during preparation of the PPS resin composition.
  • the C / S ratio on the film surface is set to 7.5 or more by such a method, so that the release film for the general-purpose multilayer printed wiring board material (FR-4) is peeled off.
  • the strength can be 200 N / m or less. Thereby, the favorable peelability with respect to a board
  • the composition of the substance existing on the film surface can be changed by blending the saturated hydrocarbon copolymer with the PPS resin composition.
  • the blending amount of the hydrogen copolymer it becomes possible to control the peelability from the substrate material.
  • the PPS resin release film of the present invention described above is suitable for use in the manufacturing process of a rigid substrate.
  • the PPS resin release film of the present invention is adhered to at least one surface of the rigid substrate.
  • a plurality of rigid substrates can be laminated via the PPS resin release film of the present invention. And this laminated body can peel a PPS resin release film from a board
  • Example 1 resin pellets (hereinafter referred to as PPS resin pellets) in which calcium carbonate and calcium stearate were blended with PPS were prepared. Specifically, a mixed powder obtained by adding calcium carbonate: 0.3 part by mass and calcium stearate: 0.2 part by mass with an average particle diameter of 0.7 ⁇ m to 100 parts by mass of PPS powder is pelletized, and PPS resin A pellet was prepared. Next, the PPS resin pellets and s-PS pellets were weighed and blended so that the volume ratio was 95: 5, and then mixed using a blender to obtain a PPS resin composition.
  • PPS resin pellets resin pellets in which calcium carbonate and calcium stearate were blended with PPS were prepared.
  • the volume ratio here is a value converted from the mass and density of PPS and s-PS, assuming that the density of PPS is 1.35 g / cm 3 and the density of s-PS is 1.04 g / cm 3 .
  • the PPS resin composition was melted by heating to 310 ° C. using an extruder having a diameter of 50 mm, and filtered through a disk filter having an opening of 10 ⁇ m. Subsequently, the melted PPS resin composition was extruded from a die having a linear lip having a length of 560 mm and a gap of 1.1 mm, and was cooled by casting on a metal drum whose surface was maintained at 40 ° C. The thickness was 380 ⁇ m. An unstretched film was prepared.
  • this unstretched film was preheated by contacting a metal roll whose surface temperature was adjusted to about 85 ° C., and then the length in the vertical direction on the metal roll whose surface temperature was adjusted to about 90 ° C. was stretched between rolls so as to be 3.4 times. Subsequently, the film stretched in the longitudinal direction was introduced into a tenter stretching machine, and stretched 2.8 times in the transverse direction in an atmosphere at 93 ° C. Immediately after stretching, the film was heat-set at 250 ° C. for about 90 seconds while being relaxed by about 4% in the transverse direction to obtain a biaxially stretched film having a thickness of about 40 ⁇ m.
  • Example 2 Extrusion under the same conditions as in Example 1 using a PPS resin composition in which PPS resin pellets and s-PS pellets were mixed at a volume ratio of 93: 7 in the same manner as in Example 1 described above. An unstretched film having a thickness of 380 ⁇ m was obtained. Next, this unstretched film was stretched in the longitudinal and lateral directions under the same conditions as in Example 1, and then relaxed to obtain a biaxially stretched film having a thickness of about 40 ⁇ m.
  • Example 3 Extrusion under the same conditions as in Example 1 using a PPS resin composition in which PPS resin pellets and s-PS pellets were mixed at a volume ratio of 90:10 in the same manner as in Example 1 described above. An unstretched film having a thickness of 380 ⁇ m was obtained. Next, this unstretched film was stretched in the longitudinal and lateral directions under the same conditions as in Example 1, and then relaxed to obtain a biaxially stretched film having a thickness of about 40 ⁇ m.
  • Example 4 Extrusion under the same conditions as in Example 1 using a PPS resin composition in which PPS resin pellets and s-PS pellets were mixed at a volume ratio of 90:10 in the same manner as in Example 1 described above. An unstretched film having a thickness of 300 ⁇ m was obtained. Next, this unstretched film was stretched in the longitudinal and lateral directions under the same conditions as in Example 1, and then relaxed to obtain a biaxially stretched film having a thickness of about 32 ⁇ m.
  • Example 5 Extrusion under the same conditions as in Example 1 using a PPS resin composition in which PPS resin pellets and s-PS pellets were mixed at a volume ratio of 90:10 in the same manner as in Example 1 described above. An unstretched film having a thickness of 500 ⁇ m was obtained. Next, this unstretched film was stretched in the longitudinal and lateral directions under the same conditions as in Example 1, and then relaxed to obtain a biaxially stretched film having a thickness of about 53 ⁇ m.
  • Example 6 Extrusion under the same conditions as in Example 1 using a PPS resin composition in which PPS resin pellets and s-PS pellets were mixed at a volume ratio of 80:20 in the same manner as in Example 1 described above. An unstretched film having a thickness of 380 ⁇ m was obtained. Next, this unstretched film was stretched in the longitudinal and lateral directions under the same conditions as in Example 1, and then relaxed to obtain a biaxially stretched film having a thickness of about 40 ⁇ m.
  • Example 7 In the same manner as in Example 1 above, a PPS resin composition in which PPS resin pellets and s-PS pellets were mixed at a volume ratio of 99.8: 0.2 was used, and the same as in Example 1. The film was extruded under the above conditions to obtain an unstretched film having a thickness of 380 ⁇ m. Next, this unstretched film was stretched in the longitudinal and lateral directions under the same conditions as in Example 1, and then relaxed to obtain a biaxially stretched film having a thickness of about 40 ⁇ m.
  • Example 8 Extrusion under the same conditions as in Example 1 using a PPS resin composition in which PPS resin pellets and s-PS pellets were mixed at a volume ratio of 75:25 in the same manner as in Example 1 described above. An unstretched film having a thickness of 380 ⁇ m was obtained. Next, this unstretched film was stretched in the longitudinal and lateral directions under the same conditions as in Example 1, and then relaxed to obtain a biaxially stretched film having a thickness of about 40 ⁇ m.
  • Comparative Example 1 A PPS resin composition prepared by mixing PPS resin pellets and s-PS pellets in a volume ratio of 50:50 in the same manner as in Example 1 described above as Comparative Example 1 of the present invention was used. Extrusion was performed under the same conditions as in No. 1 to obtain an unstretched film having a thickness of 380 ⁇ m. Next, this unstretched film was stretched in the longitudinal and lateral directions under the same conditions as in Example 1, and then relaxed to obtain a biaxially stretched film having a thickness of about 40 ⁇ m. However, in this comparative example, breakage occurred frequently during transverse stretching, and continuous film formation was difficult.
  • Comparative Example 2 As Comparative Example 2 of the present invention, a release film made of PPS resin without adding s-PS was prepared. Specifically, resin pellets mainly composed of PPS prepared by the same method as in Example 1 described above were melted and filtered by the same method as in Example 1, then cast, and unstretched with a thickness of 440 ⁇ m. A film was prepared.
  • the unstretched film was preheated by contacting a metal roll whose surface temperature was adjusted to about 85 ° C., and then the length of the longitudinal direction was increased on the metal roll whose surface temperature was adjusted to about 90 ° C.
  • the film was stretched between rolls so that the length became 3.4 times.
  • the film stretched in the longitudinal direction was introduced into a tenter stretching machine, stretched 3.2 times in the transverse direction in an atmosphere at 93 ° C., and immediately relaxed by about 3% in the transverse direction. Thereafter, the film was heat-set at 260 ° C. for about 50 seconds to obtain a biaxially stretched film having a thickness of about 40 ⁇ m.
  • Comparative Example 3 As Comparative Example 3 of the present invention, a PPS resin composition in which PPS resin pellets and s-PS pellets were mixed at a volume ratio of 90:10 in the same manner as in Example 1 was used. Extrusion was performed under the same conditions as in Example 1 to obtain an unstretched film having a thickness of 200 ⁇ m. Next, this unstretched film was stretched 3.4 times in the longitudinal direction and 3.6 times in the transverse direction, and then relaxed to obtain a biaxially stretched film having a thickness of about 16 ⁇ m.
  • Comparative Example 4 As Comparative Example 4 of the present invention, a PPS resin composition in which PPS resin pellets and s-PS pellets were mixed at a volume ratio of 90:10 by the same method as in Example 1 described above was extruded. Then, winding with a cooling drum was performed at a high speed to obtain an unstretched film having a thickness of 40 ⁇ m.
  • each film thermally bonded to the prepreg was peeled off by hand, and the ease of peeling was evaluated.
  • the evaluation results are ⁇ that the film was easily peeled off from the prepreg without tearing or tearing, ⁇ that the film was peeled off from the prepreg, but the peel strength was strong, and the film was low and the film was torn when peeled
  • those that were inferior in workability and those that had high adhesion strength with the prepreg and could not be peeled off were marked with x.
  • Table 1 summarized in Table 1 below.
  • the films of Examples 1 to 8 in which s-PS is added to PPS within the scope of the present invention can be easily peeled, and in particular, the s-PS content is 0.5.
  • the films of Examples 1 to 6 in the range of ⁇ 20% by volume exhibited an excellent peelability that has not been conventionally obtained.
  • the film of Comparative Example 1 having an s-PS content of 50% by volume frequently broke during transverse stretching and was difficult to form.
  • the film of Comparative Example 2 to which s-PS was not added had high adhesion to the prepreg and could not be peeled off.
  • the film of Comparative Example 3 having a film thickness of 16 ⁇ m was thin, the film was easily torn at the time of peeling, and was unsuitable as a release film.
  • the unstretched film of Comparative Example 4 had low strength and became brittle by heating, the film was broken when peeled.
  • the release film made of PPS resin of the present example was formed by stretching so that s-PS was added to PPS within the scope of the present invention and the film thickness was within the scope of the present invention.
  • Example No. 1 differs in the C / S ratio on the film surface by the following methods and conditions. Films 11 to 19 were prepared, and the peel strength with respect to the substrate material was measured.
  • PPS resin composition was prepared by blending PPS with s-PS or the like by dry blend method (D) or compound method (P).
  • No. prepared by dry blend method In the films 11 to 16 and 19, PPS pellets (No. 11) or PPS resin pellets (No. 12 to 16 and 19) prepared by blending PPS with calcium carbonate and calcium stearate and s-PS pellets In addition, some of the samples (Nos. 15 to 19) were also blended with saturated hydrocarbon copolymer pellets, dry blended, and supplied to the extruder. On the other hand, No. prepared by the compound method. In the films Nos. 17 and 18, s-PS pellets and saturated hydrocarbon copolymer pellets were blended into the PPS powder. About No. 17, the film was mixed with calcium carbonate and calcium stearate, mixed, then remelted and pelletized, and supplied to the extruder.
  • s-PS types A to C
  • the s-PS content in the PPS resin composition was 0.1 to 30% by volume (converted Value).
  • a styrene ethylene butylene styrene block copolymer was used as the saturated hydrocarbon copolymer, and the blending amount was 25 parts by mass with respect to 100 parts by mass of s-PS.
  • the compounding amount of calcium carbonate was 0.3 parts by mass per 100 parts by mass of PPS, and the compounding amount of calcium stearate was 0.2 parts by mass per 100 parts by mass of PPS.
  • the PPS resin composition was melted by heating to 310 ° C. using an extruder having a diameter of 50 mm, and filtered through a disk filter having an opening of 10 ⁇ m. Subsequently, the melted PPS resin composition was extruded from a die having a linear lip having a length of 560 mm and a gap of 1.1 mm, cast on a metal drum having a surface maintained at 40 ° C., and cooled to form an unstretched film. Produced.
  • the unstretched film was preheated by contacting a metal roll whose surface temperature was adjusted to about 85 ° C., and then the length of the longitudinal direction was increased on the metal roll whose surface temperature was adjusted to about 90 ° C. Stretching between rolls was performed so that the length was 3.4 times or 3.5 times. Subsequently, the film stretched in the longitudinal direction was introduced into a tenter stretching machine, and stretched in an atmosphere of 93 ° C. so as to be 2.9 times or 3.0 times in the transverse direction. Immediately after stretching, while being relaxed by about 3%, 4% or 4.7% in the transverse direction, the film is heat-set at a temperature of 250 ° C. or 260 ° C. for 40 seconds or 100 seconds to have a thickness of about 40 ⁇ m. A biaxially stretched film was obtained.
  • peeling strength was measured about each film of the Example produced by the said method and a comparative example.
  • a prepreg prepreg FR-4 for epoxy multilayer printed wiring board (product number: EI-6765) manufactured by Sumitomo Bakelite Co., Ltd.) are sandwiched between the films of Examples or Comparative Examples, and a press machine is used. After being held at 30 ° C. for 30 minutes to be semi-cured, the prepreg was cured by applying pressure for 45 minutes under the conditions of 175 ° C. and 2.2 MPa (22.5 kgf / cm 2 ).
  • a strip-shaped test piece having a width of 15 mm was cut out from the laminate of the film and the prepreg. And in the state which has arrange
  • TENSILON RTC-1210A manufactured by A & D Corporation was used as the tensile tester, the test speed was 50 mm / min, and the test environment was 23 ° C. and 50% RH. Moreover, the measurement of peeling strength was performed about nine test pieces, and the average was taken.
  • each film of an Example and a comparative example it analyzed about the kind of element of the depth of about several nanometers from the surface, the abundance ratio, and a chemical state by XPS (Quantack SX by ULVAC-PHI Co., Ltd.). The C / S ratio was determined. At that time, a monochromated Al line (1486.6 eV) was used as the X-ray source. The detection region was 100 ⁇ m ⁇ , and the detection depth was about 4 to 5 nm (extraction angle 45 °). The above results are summarized in Table 2 below. Table 2 below also shows the measurement conditions (theoretical values) of the production conditions of each film and the C / S ratio at the center of the film.
  • Example No. 1 having a C / S ratio of 7.5 or more on the film surface.
  • Nos. 11 to 18 are films having a C / S ratio of less than 7.5.
  • Comparative Example No. containing no s-PS was used. The film No.

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Abstract

L'invention concerne un film de résine de poly(sulfure de phénylène) qui présente non seulement une excellente tenue à la chaleur, une excellente tenue aux produits chimiques et une bonne adhérence sur un matériau de substrat, mais également une bonne aptitude au détachement par rapport au matériau de substrat après un traitement. L'invention propose également un stratifié. Une composition de résine de poly(sulfure de phénylène) qui contient de 0,1 à 30 % en volume de polystyrène syndiotactique est étirée biaxialement pour former un film antiadhésif en résine de poly(sulfure de phénylène) d'une épaisseur de 20 à 100 µm. Le film est utilisé comme film antiadhésif, par exemple dans une étape de production d'un substrat rigide.
PCT/JP2009/059182 2008-05-28 2009-05-19 Film antiadhésif comprenant une résine de poly(sulfure de phénylène) et stratifié WO2009145083A1 (fr)

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CN2009801197921A CN102046349B (zh) 2008-05-28 2009-05-19 聚苯硫醚树脂制离型膜和叠层体
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WO2011111826A1 (fr) * 2010-03-12 2011-09-15 積水化学工業株式会社 Film de libération de moule et procédé pour fabriquer un film de libération de moule
WO2013021816A1 (fr) * 2011-08-11 2013-02-14 東レ株式会社 Film de poly(sulfure d'arylène) de démoulage et procédé de fabrication pour un corps formé de résine durcie thermiquement l'utilisant
WO2013089075A1 (fr) * 2011-12-13 2013-06-20 東レ株式会社 Stratifié et procédé de fabrication d'une diode électroluminescente munie d'une couche de conversion de longueur d'onde
WO2014157440A1 (fr) * 2013-03-27 2014-10-02 富士フイルム株式会社 Stratifié pour collage temporaire dans la fabrication de dispositif semi-conducteur, et procédé de fabrication de dispositif semi-conducteur

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JP2000038461A (ja) * 1998-07-24 2000-02-08 Idemitsu Petrochem Co Ltd 離型フィルム
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JP2005007745A (ja) * 2003-06-19 2005-01-13 Toray Ind Inc 離型用ポリフェニレンサルファイドフィルム
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JPH02175228A (ja) * 1988-12-28 1990-07-06 Idemitsu Kosan Co Ltd ポリアリーレンスルフィド系配向成形品
JP2000038461A (ja) * 1998-07-24 2000-02-08 Idemitsu Petrochem Co Ltd 離型フィルム
JP2004051688A (ja) * 2002-07-17 2004-02-19 Idemitsu Petrochem Co Ltd 接着用樹脂組成物及び積層体
JP2005007745A (ja) * 2003-06-19 2005-01-13 Toray Ind Inc 離型用ポリフェニレンサルファイドフィルム
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Publication number Priority date Publication date Assignee Title
WO2011111826A1 (fr) * 2010-03-12 2011-09-15 積水化学工業株式会社 Film de libération de moule et procédé pour fabriquer un film de libération de moule
JPWO2011111826A1 (ja) * 2010-03-12 2013-06-27 積水化学工業株式会社 離型フィルム及び離型フィルムの製造方法
JP5719290B2 (ja) * 2010-03-12 2015-05-13 積水化学工業株式会社 離型フィルム及び離型フィルムの製造方法
WO2013021816A1 (fr) * 2011-08-11 2013-02-14 東レ株式会社 Film de poly(sulfure d'arylène) de démoulage et procédé de fabrication pour un corps formé de résine durcie thermiquement l'utilisant
JPWO2013021816A1 (ja) * 2011-08-11 2015-03-05 東レ株式会社 離型用ポリアリーレンスルフィドフィルムおよびこれを用いた熱硬化性樹脂成形体の製造方法
WO2013089075A1 (fr) * 2011-12-13 2013-06-20 東レ株式会社 Stratifié et procédé de fabrication d'une diode électroluminescente munie d'une couche de conversion de longueur d'onde
JP5488761B2 (ja) * 2011-12-13 2014-05-14 東レ株式会社 積層体および波長変換層付き発光ダイオードの製造方法
CN104010813A (zh) * 2011-12-13 2014-08-27 东丽株式会社 层叠体及带波长转换层的发光二极管的制造方法
CN104010813B (zh) * 2011-12-13 2016-08-24 东丽株式会社 层叠体及带波长转换层的发光二极管的制造方法
WO2014157440A1 (fr) * 2013-03-27 2014-10-02 富士フイルム株式会社 Stratifié pour collage temporaire dans la fabrication de dispositif semi-conducteur, et procédé de fabrication de dispositif semi-conducteur
JP2014192350A (ja) * 2013-03-27 2014-10-06 Fujifilm Corp 半導体装置製造用仮接合用積層体、および、半導体装置の製造方法

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