WO2011099252A1 - Laminated film - Google Patents

Laminated film Download PDF

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Publication number
WO2011099252A1
WO2011099252A1 PCT/JP2011/000548 JP2011000548W WO2011099252A1 WO 2011099252 A1 WO2011099252 A1 WO 2011099252A1 JP 2011000548 W JP2011000548 W JP 2011000548W WO 2011099252 A1 WO2011099252 A1 WO 2011099252A1
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WO
WIPO (PCT)
Prior art keywords
laminated film
resin
film
weight
release layer
Prior art date
Application number
PCT/JP2011/000548
Other languages
French (fr)
Japanese (ja)
Inventor
八束太一
Original Assignee
住友ベークライト株式会社
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
Priority claimed from JP2010026146A external-priority patent/JP5557152B2/en
Priority claimed from JP2010026147A external-priority patent/JP5488809B2/en
Priority claimed from JP2010026148A external-priority patent/JP5581717B2/en
Application filed by 住友ベークライト株式会社 filed Critical 住友ベークライト株式会社
Priority to SG2012059630A priority Critical patent/SG183280A1/en
Priority to KR1020127017581A priority patent/KR101745038B1/en
Priority to CN201180008916.6A priority patent/CN102762376B/en
Publication of WO2011099252A1 publication Critical patent/WO2011099252A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered 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
    • B32B27/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/06Interconnection of layers permitting easy separation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869Acids or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions 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
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10Homopolymers or copolymers of methacrylic acid esters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/24All layers being polymeric
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00Resin or rubber layer containing a blend of at least two different polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/704Crystalline
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00Decorative or ornamental articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/08PCBs, i.e. printed circuit boards
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00Labels, badges

Definitions

  • the present invention relates to a laminated film.
  • Japanese Patent Application Laid-Open No. 2001-315273 discloses “a release layer composed of a resin mainly composed of syndiotactic polystyrene resin, and an elastomer resin alone, an olefin resin alone or a mixture thereof in 30 to 30 syndiotactic polystyrene resins.
  • a laminated film comprising an intermediate layer composed of a mixed resin containing 60% by weight has been proposed.
  • Such a laminated film is obtained by, for example, bonding a cover lay film (hereinafter referred to as “CL film”) to a flexible film (hereinafter referred to as “circuit exposed film”) having an exposed circuit through an adhesive with a hot press. It is used as a release film for producing a flexible printed circuit board (hereinafter referred to as “FPC”).
  • the “laminated film containing a relatively large amount of syndiotactic polystyrene resin in the intermediate layer” as disclosed in JP-A-2001-315273 has a high elastic modulus. It was found that it was easy to break during pressing because of too much. If the laminated film breaks during pressing, the FPC may be damaged by the broken laminated film, and there is a risk that the defective product rate of the FPC will increase.
  • An object of the present invention is to provide a laminated film that can improve the workability of a press set and can increase the rate of non-defective products such as FPC.
  • the laminated film according to one aspect of the present invention includes a first release layer and a cushion layer (corresponding to an intermediate layer).
  • the first release layer is formed from a resin whose main component is a polystyrene resin having a syndiotactic structure.
  • the polystyrene resin having a syndiotactic structure is at least 70 parts by weight, preferably 85 parts by weight of the resin forming the first release layer, when the resin forming the first release layer is 100 parts by weight. It is preferable to occupy more than part.
  • the cushion layer contains more than 60 parts by weight and less than 98 parts by weight of a polyolefin resin and 2 parts by weight or more and less than 40 parts by weight of a polystyrene resin having a syndiotactic structure.
  • the cushion layer preferably contains 65 to 95 parts by weight of a polyolefin resin and 5 to 35 parts by weight of a polystyrene resin having a syndiotactic structure.
  • the cushion layer is provided on one side of the first release layer.
  • this cushion layer may be formed only from the polyolefin-type resin and the polystyrene-type resin which has a syndiotactic structure.
  • the cushion layer may contain a resin other than the polyolefin resin and the polystyrene resin having a syndiotactic structure as long as the gist of the present invention is not impaired.
  • the composition of the cushion layer is as described above, (i) workability of the press set is improved, and (ii) the elastic modulus of the laminated film is moderate. It becomes clear that the laminated film becomes difficult to break during pressing, and (iii) it becomes possible to uniformly press the CL film on the circuit exposed film during the manufacture of the FPC, and voids are formed in the adhesive. It became clear that (small cavity defects) were less likely to occur, and the non-defective rate of FPC was increased. For this reason, this laminated film can improve the workability of the press set and can increase the rate of non-defective products such as FPC.
  • the polyolefin resin comprises 3 parts by weight or more and 40 parts by weight or less of a polypropylene resin and 20 parts by weight or more and 95 parts by weight or less of an ethylene-methyl methacrylate copolymer resin. It is preferable to contain.
  • the polyolefin resin preferably contains 5 to 35 parts by weight of a polypropylene resin and 30 to 90 parts by weight of an ethylene-methyl methacrylate copolymer resin.
  • the composition of the polyolefin resin in the cushion layer is as described above, the adhesion between the cushion layer and the first release layer can be improved without using a primer. It has become clear that the elastic modulus of the cushion layer can be further within an appropriate range. For this reason, in this laminated film, a cushion layer and a 1st mold release layer can be adhere
  • the ethylene-methyl methacrylate copolymer resin preferably contains 5% by weight to 14% by weight of units derived from methyl methacrylate.
  • the ethylene-methyl methacrylate copolymer resin may contain units derived from monomers other than ethylene and methyl methacrylate as long as the gist of the present invention is not impaired.
  • this laminated film the cushion layer and the first release layer can be favorably bonded without using a primer. Moreover, this laminated film can reduce the amount of stains on the end face of the cushion layer during pressing.
  • the resin forming the first release layer preferably has a crystallinity measured by a differential scanning calorimetry of 14.0% or more and less than 30.0%. .
  • the first release layer may be integrated with the cushion layer via a primer, or may be directly integrated with the cushion layer without using a primer.
  • this laminated film is used as a release film, the adhesion of the first release layer to the circuit exposed film and the CL film is prevented while adhering the CL film to the circuit exposed film. Also, good embedding property can be obtained.
  • the crystallinity of the resin forming the first release layer is set sufficiently low at the initial stage of the adhesion of the CL film to the circuit exposed film, and the first release layer is the cushion layer during the adhesion process. It is easy to follow the deformation of (Ii) During the process of bonding the CL film to the circuit exposed film, the resin forming the first release layer is heated to crystallize, and the adhesion of the first release layer to the circuit exposed film and the CL film is improved. It is inferred that this is due to a sufficient decrease.
  • the laminated film according to one aspect of the present invention preferably further includes a second release layer.
  • the second release layer is formed on the opposite side of the cushion layer from the first release layer forming side.
  • the second release layer may be formed from a polymethylpentene resin, may be formed from a resin containing polymethylpentene resin as a main component, or a polystyrene-based resin having a syndiotactic structure. You may form from resin which has a main component, and you may form from other mold release resin.
  • the second release layer is formed of “polymethylpentene resin”, “resin mainly composed of polymethylpentene resin”, and “other release resin”, the second release layer includes a primer layer ( It may be bonded to the cushion layer via an adhesive layer.
  • the second release layer is formed from “resin mainly composed of a polystyrene resin having a syndiotactic structure”, the second release layer adheres to the cushion layer without using a primer (adhesive). can do.
  • the cushion layer is prevented from adhering to the press hot platen when the CL film is adhered to the circuit exposed film. Can do. For this reason, the time spent for the adhesion process etc. of CL film to a circuit exposure film can be shortened.
  • the second release layer is preferably formed from a resin whose main component is a polystyrene resin having a syndiotactic structure.
  • the second release layer is formed from a resin whose main component is a polystyrene resin having a syndiotactic structure, it can be adhered to the cushion layer without using a primer (adhesive). For this reason, this laminated film can be manufactured while keeping material cost and process cost low.
  • the resin forming the second release layer preferably has a crystallinity measured by a differential scanning calorimetry of 14.0% or more and less than 30.0%. .
  • a 2nd mold release layer is a 1st mold release. It will have the same function as the layer. For this reason, in using this laminated film, the user does not need to specify the first release layer and the second release layer. For this reason, if this laminated film is used, it is possible to save the user from recognizing the first release layer and the second release layer, and to adhere the first release layer and the second release layer due to a specific mistake. Defects can be prevented.
  • the laminated film 100 mainly includes a release layer 110 and a cushion layer 120.
  • the thickness of the laminated film 100 is preferably 25 to 300 ⁇ m.
  • each of these layers will be described in detail.
  • the release layer 110 is formed of a resin (hereinafter referred to as “release layer forming resin”) whose main component is a polystyrene resin having a syndiotactic structure (hereinafter referred to as “SPS resin”). .
  • release layer forming resin a resin
  • SPS resin polystyrene resin having a syndiotactic structure
  • Such a release layer-forming resin is commercially available from Idemitsu Kosan Co., Ltd. under the trade name Zalek (registered trademark) (XAREC (registered trademark)).
  • the content of the SPS resin in the release layer forming resin is 70% by weight or more and 90% by weight or less, but preferably 85% by weight or more and 90% by weight or less.
  • the thickness of the release layer 110 is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more.
  • the crystallinity of the release layer forming resin is preferably 14.0% or more and less than 30.0% as measured by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • SPS resin SPS resin has a syndiotactic structure, that is, a stereoregulation in which phenyl groups and substituted phenyl groups which are side chains are alternately located in opposite directions with respect to the main chain formed from carbon-carbon sigma bonds. It is a resin having a structure.
  • racemic dyad is 75% or more, preferably 85% or more, or racemic pentad, 30% or more, preferably Polystyrene, poly (alkyl styrene), poly (aryl styrene), poly (halogenated styrene), poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (vinyl benzoic acid) having a syndiotacticity of 50% or more Esters), hydrogenated polymers thereof and mixtures thereof, or copolymers based on these.
  • poly (alkyl styrene) examples include poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (t-butyl styrene), and the like.
  • poly (aryl styrene) examples include poly (phenyl styrene), poly (vinyl naphthalene), and poly (vinyl styrene).
  • poly (halogenated styrene) examples include poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like.
  • poly (halogenated alkylstyrene) examples include poly (chloromethylstyrene).
  • poly (alkoxystyrene) examples include poly (methoxystyrene) and poly (ethoxystyrene).
  • polystyrene poly (p-methylstyrene), poly (m-methylstyrene), poly (pt-ptylstyrene), poly (p-chlorostyrene), poly (m-chlorostyrene), Poly (p-fluorostyrene), hydrogenated polystyrene, and copolymers containing these structural units are particularly preferred.
  • Resins other than SPS resin examples include, for example, elastomer resins, polyolefin resins, polystyrene resins, polyester resins, polyamide resins, polyphenylene ether resins, Polyphenylene sulfide resin (PPS) etc. are mentioned. In addition, these resin can be used individually or in combination of 2 or more types.
  • elastomer resin examples include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR).
  • natural rubber polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR).
  • SBR styrene-butadiene block copolymer
  • polyolefin resins examples include linear high density polyethylene, linear low density polyethylene, high pressure low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, block polypropylene, random polypropylene, polybutene, 1,2- Examples thereof include polybutadiene, poly (4-methylpentene), cyclic polyolefin, and copolymers thereof (for example, ethylene-methyl methacrylate copolymer).
  • polystyrene resins examples include atactic polystyrene, isotactic polystyrene, high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), and styrene-meta.
  • HIPS high impact polystyrene
  • ABS acrylonitrile-butadiene-styrene copolymer
  • AS acrylonitrile-styrene copolymer
  • styrene-meta examples include atactic polystyrene, isotactic polystyrene, high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), and styrene-meta.
  • Acrylic acid copolymer styrene-methacrylic acid / alkyl ester copolymer, styrene-methacrylic acid / glycidyl ester copolymer, styrene-acrylic acid copolymer, styrene-acrylic acid / alkyl ester copolymer, styrene -Maleic acid copolymer, styrene-fumaric acid copolymer and the like.
  • polyester resin examples include polycarbonate, polyethylene terephthalate, and polybutylene terephthalate.
  • polyamide-based resin examples include nylon (registered trademark) 6, nylon (registered trademark) 6, 6, and the like.
  • examples of the antiblocking agent include the following inorganic particles or organic particles.
  • Inorganic particles include Group IA, Group IIA, Group IVA, Group VIA, Group VIIA, Group VIIIA, Group IB, Group IIB, Group IIIB, Group IVB oxides, hydroxides, sulfides, nitrides, halogens , Carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, borates and their water-containing compounds, and composite compounds and natural mineral particles centered on them Is mentioned.
  • inorganic particles include group IA element compounds such as lithium fluoride and borax (sodium borate hydrate); magnesium carbonate, magnesium phosphate, magnesium oxide (magnesia), magnesium chloride, acetic acid Magnesium, magnesium fluoride, magnesium titanate, magnesium silicate, magnesium silicate hydrate (talc), calcium carbonate, calcium phosphate, calcium phosphite, calcium sulfate (gypsum), calcium acetate, calcium terephthalate, calcium hydroxide, silicic acid
  • Group IIA element compounds such as calcium, calcium fluoride, calcium titanate, strontium titanate, barium carbonate, barium phosphate, barium sulfate, barium sulfite; titanium dioxide (titania), titanium monoxide, titanium nitride, two Group IVA element compounds such as zirconium fluoride (zirconia) and zirconium monoxide;
  • Group VIA element compounds such as molybdenum dioxide, molybdenum tri
  • organic particles examples include fluororesins, melamine resins, styrene-divinylbenzene copolymers, acrylic resin silicones, and cross-linked products thereof.
  • the average particle diameter of the above-mentioned inorganic particles and organic particles is preferably 0.1 to 10 ⁇ m, and the addition amount is preferably 0.01 to 15% by weight.
  • antiblocking agents can be used individually or in combination of 2 or more types.
  • Antioxidants include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, 2-[(1-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6- And di-t-pentylphenyl acrylate. These antioxidants can be used alone or in combination of two or more.
  • Nucleating agents include metal salts of carboxylic acids such as aluminum di (pt-butylbenzoate), metal salts of phosphoric acid such as methylenebis (2,4-di-t-butylphenol) acid phosphate, talc, phthalocyanine derivatives Etc. In addition, these nucleating agents can be used individually or in combination of 2 or more types.
  • plasticizer examples include polyethylene glycol, polyamide oligomer, ethylene bisstearamide, phthalate ester, polystyrene oligomer, polyethylene wax, silicone oil, and the like.
  • plasticizers can be used individually or in combination of 2 or more types.
  • release agent examples include polyethylene wax, silicone oil, long chain carboxylic acid, and long chain carboxylic acid metal salt.
  • these mold release agents can be used individually or in combination of 2 or more types.
  • Process oils include paraffinic oil, naphthenic oil, and aroma oil. Of these, paraffinic oils having a percentage of the total number of carbon atoms related to paraffin (straight chain) calculated by the ndM method of 60% Cp or more are preferable.
  • the viscosity of the process oil is preferably 15 to 600 cs at 40 ° C., more preferably 15 to 500 cs.
  • the amount of process oil added is preferably from 0.01 to 1.5 parts by weight, more preferably from 0.05 to 1.4 parts by weight, based on 100 parts by weight of the release forming resin. More preferably, the content is 0.1 to 1.3 parts by weight.
  • these process oil can be used individually or in combination of 2 or more types.
  • the cushion layer 120 is mainly formed from a resin blend of a polyolefin-based resin of more than 60 parts by weight and 98 parts by weight or less and an SPS resin of 2 parts by weight or more and less than 40 parts by weight. Yes.
  • this resin blend can be prepared by the dry blend method without pre-kneading, you may pre-process with a biaxial kneader.
  • the thickness of the cushion layer 120 is preferably at least 3 times the thickness of the release layer 110, more preferably at least 5 times, and even more preferably at least 8 times.
  • polyolefin resins include linear high-density polyethylene, linear low-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, block polypropylene, random polypropylene, polybutene, 1, Examples thereof include 2-polybutadiene, poly (4-methylpentene), cyclic polyolefin, and copolymers thereof (for example, ethylene-methyl methacrylate copolymer).
  • the SPS resin is the same as the SPS resin described above.
  • the cushion layer 120 includes 2 parts by weight or more and less than 40 parts by weight of an SPS resin, 3 parts by weight or more and 40 parts by weight or less of a polypropylene resin, and more than 20 parts by weight of 95 parts by weight or less of an ethylene-methyl methacrylate copolymer. More preferably, it is formed from a resin blend with resin. In such a case, the ethylene-methyl methacrylate copolymer resin preferably contains 5% by weight to 14% by weight of units derived from methyl methacrylate.
  • the composition of the cushion layer 120 and the composition of the ethylene-methyl methacrylate copolymer resin are as described above, (i) good adhesion between the cushion layer 120 and the release layer 110 without using a primer. This is because (ii) it is possible to reduce the amount of smearing of the end face of the cushion layer 120 to the hot platen during pressing.
  • the above-mentioned elastomer resin and additives may be blended with the resin blend as necessary, as long as the gist of the present invention is not impaired.
  • the laminated film 100 according to the present embodiment can be manufactured by a method such as a coextrusion method or an extrusion lamination method.
  • the laminated film 100 is manufactured by simultaneously extruding the release layer 110 and the cushion layer 120 using a feed block and a multi-manifold die.
  • the melt M that has passed through the die 210 is guided between the first roll 230 and the touch roll 220 as shown in FIG.
  • the laminated film 100 is cooled by the touch roll 220 and the first roll 230.
  • the laminated film 100 is sent to the downstream side in the film feeding direction (see the arrow in FIG. 3) by the second roll 240 and is finally taken up by a take-up roll (not shown).
  • the temperature of the first roll 230 is preferably 30 to 100 ° C.
  • the temperature of the touch roll 220 is preferably 50 to 120 ° C.
  • the peripheral speed of the second roll 240 with respect to the first roll 230 is preferably from 0.990 to 0.998.
  • the temperature of the extruder cylinder is set to 270 to 300 ° C.
  • the release layer 110 is extruded
  • the release layer 110 and the cushion layer 120 are joined together to form the release layer 110 and the cushion layer 120.
  • the laminated film 100 is manufactured by laminating.
  • the release layer forming resin melt M that has passed through the die 210 is guided between the first roll 230 and the touch roll 220 as shown in FIG. Until it is detached, it is cooled by the touch roll 220 and the first roll 230 to form the release layer film F. Thereafter, the release layer film F is sent downstream by the second roll 240 in the film feeding direction (see the arrow in FIG. 3).
  • the melt (not shown) of the resin blend that forms the cushion layer 120 is merged with the release layer film F sent to the downstream side in the film feed direction and integrated with the release layer film F,
  • the laminated film 100 is manufactured.
  • multilayer film 100 manufactured in this way is wound up by the winding roll (not shown) further provided in the film feed direction downstream.
  • the temperature of the first roll 230 is preferably 30 to 100 ° C.
  • the temperature of the touch roll 220 is preferably 50 to 120 ° C.
  • the circumference of the second roll 240 with respect to the first roll 230 is preferred.
  • the speed ratio is preferably 0.990 to 0.998.
  • the crystallinity of the SPS resin in the release layer 110 of the laminated film 100 obtained as described above may be adjusted by a known heat treatment apparatus.
  • heat treatment may be performed in the vicinity of 50 to 220 ° C. using a method of heat-setting the laminated film 100 in a dryer using a tenter device or a heat treatment roll.
  • the laminated film 100 is disposed so as to wrap the CL film so that the CL film adheres to the concavo-convex portion of the circuit pattern when the CL film is adhered to the circuit exposed film, and together with the circuit exposed film and the CL film. Pressurized by a press device. Specifically, as shown in FIG. 4, the laminated film 100 is obtained by sandwiching a circuit-exposed film and a CL film temporarily fixed with an adhesive 340 so that the release layer 110 faces each other.
  • the sheet is sequentially sandwiched between a Teflon (registered trademark) sheet 330, a rubber cushion 320, and a stainless steel plate 310, and pressed by a hot platen 300 (see white arrows in FIG. 4).
  • the heating method using the hot platen 300 is as shown in FIG. That is, the hot platen 300 is rapidly heated from room temperature to 185 ° C. in 10 seconds after the start of pressurization, and then maintained at that temperature for 60 seconds. Note that pressurization by the hot platen 300 is started at the time of 0 seconds and released at the time of 70 seconds. The pressing pressure at this time is appropriately adjusted to 5 to 15 MPa.
  • the laminated film 100 in which the release layer 110 is provided only on one side of the cushion layer 120 was introduced.
  • the release layers 110a and 110b on both sides of the cushion layer 120 were also included in one embodiment of the present invention.
  • the release layer denoted by reference numeral 110a is referred to as a “first release layer”
  • the release layer denoted by reference numeral 110b is referred to as a “second release layer”.
  • the first release layer 110a has the same structure as the release layer 110 according to the previous embodiment.
  • the second release layer 110b may have the same structure as the first release layer 110a, or may have a different structure from the first release layer 110a.
  • the second release layer 110b is formed of, for example, a resin mainly composed of polymethylpentene resin or methylpentene- ⁇ olefin copolymer.
  • a resin is commercially available from Mitsui Chemicals, Inc. under the trade name TPX (registered trademark).
  • TPX registered trademark
  • an anchor layer or a primer layer is interposed between the second release layer 110b and the cushion layer 120. (Adhesive layer) may be interposed.
  • the Teflon (registered trademark) sheet 330, the rubber cushion 320, and the stainless steel plate 310 are sequentially sandwiched between the laminated film 100 and the heating platen 300.
  • the (registered trademark) sheet 330, the rubber cushion 320, and the stainless steel plate 310 may be omitted.
  • the cushion layer raw material is 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 75 parts by weight of ethylene-methyl methacrylate copolymer. Combined (methyl methacrylate derived unit content: 5% by weight) (Aclift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 5 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) What was dry blended (hereinafter referred to as “cushion layer forming blend resin”) was used.
  • SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.), cushion layer forming blend resin and SPS resin (Idemitsu Kosan Co., Ltd.) using a feed block and a multi-manifold die.
  • Zalek (registered trademark) S104 manufactured by the company was simultaneously extruded to produce a laminated film.
  • the apparatus shown in FIG. 3 was used, but the temperature of the first roll 230 was 30 ° C., the temperature of the touch roll 220 was 70 ° C., and the circumference of the second roll 240 with respect to the first roll 230 was changed.
  • the speed ratio was 0.990.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • a cushion layer forming blend resin 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 70 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 5% by weight) (Acrylift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used.
  • a laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated.
  • cushion layer forming blend resin 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 60 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) (Unit content: 5% by weight) (Akulift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 20 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used.
  • a laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • a cushion layer forming blend resin 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 50 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) (Unit content: 5% by weight) (Aclift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 30 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used.
  • a laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • a cushion layer forming blend resin 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 70 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 10% by weight) (Acrylift (registered trademark) WD201 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used.
  • a laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • a cushion layer forming blend resin 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 70 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 14% by weight) (Acrylift (registered trademark) CM8033 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used.
  • a laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • a cushion layer-forming blend resin 39 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 21 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 14% by weight) (Acrylift (registered trademark) CM8033 manufactured by Sumitomo Chemical Co., Ltd.) and 40 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used.
  • a laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • a cushion layer-forming blend resin As a cushion layer-forming blend resin, 5 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 90 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 14% by weight) (Acrylift (registered trademark) CM8033 manufactured by Sumitomo Chemical Co., Ltd.) and 5 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used.
  • a laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • a cushion layer forming blend resin 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 80 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived)
  • SPS resin Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.
  • ethylene-methyl methacrylate copolymer methyl methacrylate derived
  • a laminated film was prepared in the same manner as in Example 1 except that a dry blend of (unit content: 5% by weight) (Aclift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) was used. Was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • a cushion layer forming blend resin 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 70 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 20% by weight) (Acrylift (registered trademark) WH206 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used.
  • a laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • a cushion layer forming blend resin 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 70 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 17.5% by weight (Akulift (registered trademark) CM8014 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.)
  • a laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • the cushion layer raw material is 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 70 parts by weight of ethylene-methyl methacrylate copolymer. Combined (Methyl methacrylate derived unit content: 5% by weight) (Akulift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) What was dry blended (hereinafter referred to as “cushion layer forming blend resin”) was used.
  • a multi-manifold die was used to simultaneously extrude SPS resin, cushion layer forming blend resin, and SPS resin to produce a laminated film.
  • the temperature of the first roll 230 was 35 ° C.
  • the temperature of the touch roll 220 was 70 ° C.
  • the circumference of the second roll 240 with respect to the first roll 230 was changed.
  • the speed ratio was 0.998.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • Example 12 is the same as Example 12 except that the temperature of the first roll 230 is set to 98 ° C., the temperature of the touch roll 220 is set to 120 ° C., and the peripheral speed ratio of the second roll 240 to the first roll 230 is set to 0.998.
  • a laminated film was produced and the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • the temperature of the first roll 230 was set to 35 ° C.
  • the temperature of the touch roll 220 was set to 70 ° C.
  • the peripheral speed ratio of the second roll 240 to the first roll 230 was set to 0.998, as in Example 12.
  • a laminated film was prepared, and the laminated film was further annealed by being sandwiched between stainless plates with a surface temperature of 120 ° C. and held at a pressure of 10 MPa for 10 minutes, and then the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • the temperature of the first roll 230 was set to 35 ° C.
  • the temperature of the touch roll 220 was set to 70 ° C.
  • the peripheral speed ratio of the second roll 240 to the first roll 230 was set to 0.998, as in Example 12.
  • a laminated film was prepared, and the laminated film was further annealed by being sandwiched between stainless plates having a surface temperature of 125 ° C. and held at a pressure of 10 MPa for 10 minutes, and then the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • the temperature of the first roll 230 was set to 35 ° C.
  • the temperature of the touch roll 220 was set to 70 ° C.
  • the peripheral speed ratio of the second roll 240 to the first roll 230 was set to 0.998, as in Example 12.
  • a laminated film was prepared, and the laminated film was further annealed by being sandwiched between stainless plates having a surface temperature of 130 ° C. and held at a pressure of 10 MPa for 10 minutes, and then the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • a cushion layer forming blend resin 80 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived unit content: 5% by weight) (Aclift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.)
  • a laminated film was produced in the same manner as in Example 1 except that a dry blend of 20 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) was used, and the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • a cushion layer forming blend resin 40 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 50 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 5% by weight) (Acrylift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used.
  • a laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • a cushion layer forming blend resin 70 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 20 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 5% by weight) (Acrylift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used.
  • a laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated.
  • the thickness of the release layer of this laminated film was 25 ⁇ m on both sides, and the thickness of the cushion layer was 70 ⁇ m.
  • the laminated film according to the present invention is characterized in that the workability of the press set can be improved, and the rate of non-defective products such as FPC can be increased, and the CL film is adhered to the circuit exposed film by a pressure press. It is particularly useful as a release film that is sometimes used to wrap a coverlay film in order to bring the CL film into close contact with the uneven portion of the circuit pattern.
  • release films include (1) those used in the production of laminates, (2) those used in the production of advanced composite materials, and (3) those used in the production of sports and leisure goods.
  • the laminated film according to the present invention is also useful as these release films.
  • the release film used in the production of the laminated board is a press-molding process for producing a multilayer printed board, in order to prevent adhesion between the printed board and the separator plate or other printed boards. It is an intervening film.
  • the release film used when manufacturing the advanced composite material product is, for example, a film used when manufacturing various products by curing a prepreg made of glass cloth, carbon fiber or aramid fiber and an epoxy resin.
  • the release film used in the manufacture of sports / leisure goods is, for example, the production of fishing rods, golf club shafts, windsurfing poles, etc. It is a film wound around.
  • This laminated film is also useful as a release film for adhesive tapes, double-sided tapes, masking tapes, labels, seals, stickers, poultices for skin application, and the like.
  • This laminated film is also useful as a process film used in the production of printed circuit boards, ceramic electronic parts, thermosetting resin products, decorative boards and the like.
  • the process film here refers to a metal in the molding process so that metal plates and resins do not adhere to each other when manufacturing printed circuit boards, ceramic electronic parts, thermosetting resin products, decorative boards, etc. It refers to a film that is sandwiched between boards or between resins, and is particularly suitable for use in the production of laminated boards, the production of flexible printed boards, the production of advanced composite materials, and the production of sports and leisure goods.
  • This laminated film is also useful as a packaging film.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

Disclosed is a laminated film which can be subjected to press bonding with good workability and enables the production of FPCs in improved yield. Specifically disclosed is a laminate film (100, 100A) which comprises a first mold release layer (110, 110a) and a cushion layer (120). The first mold release layer comprises a resin mainly composed of a polystyrene resin having a syndiotactic structure. The cushion layer comprises more than 60 parts by weight and not more than 98 parts by weight of a polyolefin resin and not less than 2 parts by weight and less than 40 parts by weight of a polystyrene resin having a syndiotactic structure. The cushion layer is arranged on one surface of the first mold release layer.

Description

積層フィルムLaminated film
 本発明は、積層フィルムに関する。 The present invention relates to a laminated film.
 特開2001-315273号公報には、「シンジオタクチックポリスチレン樹脂を主成分とする樹脂からなる離型層と、シンジオタクチックポリスチレン樹脂にエラストマー樹脂単体、オレフィン系樹脂単体又はこれらの混合物を30~60重量%含有する混合樹脂から構成された中間層とを備える積層フィルム」が提案されている。このような積層フィルムは、例えば、回路が露出したフレキシブルフィルム(以下「回路露出フィルム」と称する)に接着剤を介してカバーレイフィルム(以下「CLフィルム」と称する)を加熱プレスにより接着してフレキシブルプリント回路基板(以下「FPC」と称する)を作製する際の離型フィルムとして用いられる。 Japanese Patent Application Laid-Open No. 2001-315273 discloses “a release layer composed of a resin mainly composed of syndiotactic polystyrene resin, and an elastomer resin alone, an olefin resin alone or a mixture thereof in 30 to 30 syndiotactic polystyrene resins. A laminated film comprising an intermediate layer composed of a mixed resin containing 60% by weight has been proposed. Such a laminated film is obtained by, for example, bonding a cover lay film (hereinafter referred to as “CL film”) to a flexible film (hereinafter referred to as “circuit exposed film”) having an exposed circuit through an adhesive with a hot press. It is used as a release film for producing a flexible printed circuit board (hereinafter referred to as “FPC”).
特開2001-315273号公報JP 2001-315273 A
 しかし、本願発明者の検討の結果、特開2001-315273号公報に開示されるような「比較的多量のシンジオタクチックポリスチレン樹脂が中間層に含まれている積層フィルム」は、弾性率が高すぎるため、プレス中に割れやすいことが判明した。そして、プレス中に積層フィルムが割れてしまうと、その割れた積層フィルムによりFPCに傷がつく場合があり得、延いては、FPCの不良品率が高くなってしまうおそれがある。 However, as a result of the study by the inventors of the present application, the “laminated film containing a relatively large amount of syndiotactic polystyrene resin in the intermediate layer” as disclosed in JP-A-2001-315273 has a high elastic modulus. It was found that it was easy to break during pressing because of too much. If the laminated film breaks during pressing, the FPC may be damaged by the broken laminated film, and there is a risk that the defective product rate of the FPC will increase.
 また、このような積層フィルムは、先と同様の理由から、FPCの製造時においてCLフィルムを回路露出フィルムに均一にプレスすることが難しくなり、接着剤中にボイド(微小な空洞欠陥)が生じやすく、延いてはFPCの不良品率が高くなってしまうことが本願発明者により明らかとされている。 In addition, for such a laminated film, it becomes difficult to press the CL film uniformly on the circuit exposed film during the manufacture of FPC for the same reason as described above, and voids (minute void defects) are generated in the adhesive. It has been made clear by the inventor of the present application that the rate of defective FPCs tends to increase.
 また、このような積層フィルムは、プレスセットの作業性が非常に悪い。 Also, such a laminated film has a very poor workability of the press set.
 本発明の課題は、プレスセットの作業性を良好にすることができると共にFPC等の良品率を高めることができる積層フィルムを提供することにある。 An object of the present invention is to provide a laminated film that can improve the workability of a press set and can increase the rate of non-defective products such as FPC.
 (1)
 本発明の一局面に係る積層フィルムは、第1離型層およびクッション層(中間層に相当する)を備える。第1離型層は、シンジオタクチック構造を有するポリスチレン系樹脂を主成分とする樹脂から形成される。なお、シンジオタクチック構造を有するポリスチレン系樹脂は、第1離型層を形成する樹脂を100重量部とした場合、第1離型層を形成する樹脂の少なくとも70重量部以上、好ましくは85重量部以上を占めるのが好ましい。クッション層は、60重量部超98重量部以下のポリオレフィン系樹脂と、2重量部以上40重量部未満のシンジオタクチック構造を有するポリスチレン系樹脂とを含有する。なお、クッション層は、65重量部以上95重量部以下のポリオレフィン系樹脂と、5重量部以上35重量部以下のシンジオタクチック構造を有するポリスチレン系樹脂とを含有するのがより好ましい。そして、このクッション層は、第1離型層の片側に設けられている。なお、このクッション層は、ポリオレフィン系樹脂およびシンジオタクチック構造を有するポリスチレン系樹脂のみから形成されていてもよい。また、このクッション層は、本発明の趣旨を損なわない範囲でポリオレフィン系樹脂およびシンジオタクチック構造を有するポリスチレン系樹脂以外の樹脂を含有していてもかまわない。
(1)
The laminated film according to one aspect of the present invention includes a first release layer and a cushion layer (corresponding to an intermediate layer). The first release layer is formed from a resin whose main component is a polystyrene resin having a syndiotactic structure. The polystyrene resin having a syndiotactic structure is at least 70 parts by weight, preferably 85 parts by weight of the resin forming the first release layer, when the resin forming the first release layer is 100 parts by weight. It is preferable to occupy more than part. The cushion layer contains more than 60 parts by weight and less than 98 parts by weight of a polyolefin resin and 2 parts by weight or more and less than 40 parts by weight of a polystyrene resin having a syndiotactic structure. The cushion layer preferably contains 65 to 95 parts by weight of a polyolefin resin and 5 to 35 parts by weight of a polystyrene resin having a syndiotactic structure. The cushion layer is provided on one side of the first release layer. In addition, this cushion layer may be formed only from the polyolefin-type resin and the polystyrene-type resin which has a syndiotactic structure. Further, the cushion layer may contain a resin other than the polyolefin resin and the polystyrene resin having a syndiotactic structure as long as the gist of the present invention is not impaired.
 本願発明者の鋭意検討の結果、クッション層の組成が上記の通りであると、(i)プレスセットの作業性が良好となることが明らかとなると共に、(ii)積層フィルムの弾性率が適度になって積層フィルムがプレス中に割れにくくなることも明らかとなり、さらに、(iii)FPCの製造時においてCLフィルムを回路露出フィルムに均一にプレスすることが可能となって、接着剤中にボイド(微小な空洞欠陥)が生じにくくなり、FPCの良品率が高まることが明らかとなった。
 このため、この積層フィルムは、プレスセットの作業性を良好にすることができると共に、FPC等の良品率を高めることができる。
As a result of intensive studies by the inventor of the present application, it becomes clear that the composition of the cushion layer is as described above, (i) workability of the press set is improved, and (ii) the elastic modulus of the laminated film is moderate. It becomes clear that the laminated film becomes difficult to break during pressing, and (iii) it becomes possible to uniformly press the CL film on the circuit exposed film during the manufacture of the FPC, and voids are formed in the adhesive. It became clear that (small cavity defects) were less likely to occur, and the non-defective rate of FPC was increased.
For this reason, this laminated film can improve the workability of the press set and can increase the rate of non-defective products such as FPC.
 (2)
 本発明の一局面に係る積層フィルムにおいて、ポリオレフィン系樹脂は、3重量部以上40重量部以下のポリプロピレン樹脂と、20重量部超95重量部以下のエチレン-メタアクリル酸メチル共重合体樹脂とを含有するのが好ましい。また、ポリオレフィン系樹脂は、5重量部以上35重量部以下のポリプロピレン樹脂と、30重量部以上90重量部以下のエチレン-メタアクリル酸メチル共重合体樹脂とを含有するのがより好ましい。
(2)
In the laminated film according to one aspect of the present invention, the polyolefin resin comprises 3 parts by weight or more and 40 parts by weight or less of a polypropylene resin and 20 parts by weight or more and 95 parts by weight or less of an ethylene-methyl methacrylate copolymer resin. It is preferable to contain. The polyolefin resin preferably contains 5 to 35 parts by weight of a polypropylene resin and 30 to 90 parts by weight of an ethylene-methyl methacrylate copolymer resin.
 本願発明者の鋭意検討の結果、クッション層中のポリオレフィン系樹脂の組成が上記の通りであると、プライマーを使用することなくクッション層と第1離型層との接着性を良好とすることができると共に、クッション層の弾性率をさらに適度な範囲内とすることができることが明らかとなった。
 このため、この積層フィルムでは、クッション層と第1離型層とを良好に接着することができ、また、クッション層の弾性率をさらに適度に保つことができる。
As a result of intensive studies by the present inventors, when the composition of the polyolefin resin in the cushion layer is as described above, the adhesion between the cushion layer and the first release layer can be improved without using a primer. It has become clear that the elastic modulus of the cushion layer can be further within an appropriate range.
For this reason, in this laminated film, a cushion layer and a 1st mold release layer can be adhere | attached favorably, and the elasticity modulus of a cushion layer can be kept further moderately.
 (3)
 本発明の一局面に係る積層フィルムにおいて、エチレン-メタアクリル酸メチル共重合体樹脂には、メタアクリル酸メチルから誘導される単位が5重量%以上14重量%以下含有されているのが好ましい。なお、エチレン-メタアクリル酸メチル共重合体樹脂は、本発明の趣旨を損なわない範囲でエチレンおよびメタアクリル酸メチル以外のモノマーから誘導される単位を含有していてもかまわない。
(3)
In the laminated film according to one aspect of the present invention, the ethylene-methyl methacrylate copolymer resin preferably contains 5% by weight to 14% by weight of units derived from methyl methacrylate. The ethylene-methyl methacrylate copolymer resin may contain units derived from monomers other than ethylene and methyl methacrylate as long as the gist of the present invention is not impaired.
 本願発明者の鋭意検討の結果、メタアクリル酸メチルから誘導される単位の含有率が上記の通りであると、プライマーを使用することなくクッション層と第1離型層との接着性を良好とすることができることが明らかとなり、さらにプレス中にクッション層端面の熱盤へのシミ出し量を低減することができることが明らかとなった。 As a result of intensive studies by the inventor of the present application, when the content of units derived from methyl methacrylate is as described above, the adhesiveness between the cushion layer and the first release layer is good without using a primer. It became clear that it was possible to reduce the amount of stains on the hot platen of the end face of the cushion layer during pressing.
 このため、この積層フィルムでは、プライマーを使用することなくクッション層と第1離型層とが良好に接着することができる。また、この積層フィルムは、プレス中のクッション層端面のシミ出し量を低減することができる。 For this reason, in this laminated film, the cushion layer and the first release layer can be favorably bonded without using a primer. Moreover, this laminated film can reduce the amount of stains on the end face of the cushion layer during pressing.
 (4)
 本発明の一局面に係る積層フィルムにおいて、第1離型層を形成する樹脂は、示差走査熱量測定法により測定される結晶化度が14.0%以上30.0%未満であるのが好ましい。なお、かかる場合、第1離型層は、プライマーを介してクッション層と一体化されてもよいし、プライマーを介さずに直接的にクッション層と一体化されてもよい。
(4)
In the laminated film according to one aspect of the present invention, the resin forming the first release layer preferably has a crystallinity measured by a differential scanning calorimetry of 14.0% or more and less than 30.0%. . In such a case, the first release layer may be integrated with the cushion layer via a primer, or may be directly integrated with the cushion layer without using a primer.
 本願発明者の鋭意検討の結果、第1離型層を形成する樹脂の結晶化度が上述の通りであると、回路露出フィルムへのCLフィルムの接着時に、第1離型層の回路露出フィルム及びCLフィルムへの密着を防ぎつつ従来の離型フィルムよりも良好な埋め込み性を得ることができることが明らかとなった。 As a result of intensive studies by the inventors of the present application, when the crystallinity of the resin forming the first release layer is as described above, the circuit exposure film of the first release layer is bonded to the circuit exposure film when the CL film is adhered. And it became clear that better embedding property than the conventional release film can be obtained while preventing adhesion to the CL film.
 このため、この積層フィルムを離型フィルムとして利用すれば、回路露出フィルムへのCLフィルムの接着時に、第1離型層の回路露出フィルム及びCLフィルムへの密着を防ぎつつ従来の離型フィルムよりも良好な埋め込み性を得ることができる。 For this reason, if this laminated film is used as a release film, the adhesion of the first release layer to the circuit exposed film and the CL film is prevented while adhering the CL film to the circuit exposed film. Also, good embedding property can be obtained.
 なお、この効果は、
(i)第1離型層を形成する樹脂の結晶化度が回路露出フィルムへのCLフィルムの接着初期時において十分に低く設定されており、その接着工程中において第1離型層がクッション層の変形に追従しやすくなっていること、
(ii)回路露出フィルムへのCLフィルムの接着工程中に、第1離型層を形成する樹脂が加熱されることにより結晶化して回路露出フィルム及びCLフィルムに対する第1離型層の密着性が十分に低下すること
に起因するものと推察される。
This effect is
(I) The crystallinity of the resin forming the first release layer is set sufficiently low at the initial stage of the adhesion of the CL film to the circuit exposed film, and the first release layer is the cushion layer during the adhesion process. It is easy to follow the deformation of
(Ii) During the process of bonding the CL film to the circuit exposed film, the resin forming the first release layer is heated to crystallize, and the adhesion of the first release layer to the circuit exposed film and the CL film is improved. It is inferred that this is due to a sufficient decrease.
 (5)
 本発明の一局面に係る積層フィルムは、第2離型層をさらに備えるのが好ましい。この第2離型層は、クッション層の第1離型層形成側の反対側に形成される。なお、この第2離型層は、ポリメチルペンテン樹脂から形成されてもよいし、ポリメチルペンテン樹脂を主成分とする樹脂から形成されてもよいし、シンジオタクチック構造を有するポリスチレン系樹脂を主成分とする樹脂から形成されてもよいし、その他の離型性樹脂から形成されてもよい。第2離型層が「ポリメチルペンテン樹脂」、「ポリメチルペンテン樹脂を主成分とする樹脂」および「その他の離型性樹脂」から形成される場合、第2離型層は、プライマー層(接着層)を介してクッション層に接着されてもよい。第2離型層が「シンジオタクチック構造を有するポリスチレン系樹脂を主成分とする樹脂」から形成される場合、第2離型層は、プライマー(接着剤)を使用することなくクッション層に接着することができる。
(5)
The laminated film according to one aspect of the present invention preferably further includes a second release layer. The second release layer is formed on the opposite side of the cushion layer from the first release layer forming side. The second release layer may be formed from a polymethylpentene resin, may be formed from a resin containing polymethylpentene resin as a main component, or a polystyrene-based resin having a syndiotactic structure. You may form from resin which has a main component, and you may form from other mold release resin. When the second release layer is formed of “polymethylpentene resin”, “resin mainly composed of polymethylpentene resin”, and “other release resin”, the second release layer includes a primer layer ( It may be bonded to the cushion layer via an adhesive layer. When the second release layer is formed from “resin mainly composed of a polystyrene resin having a syndiotactic structure”, the second release layer adheres to the cushion layer without using a primer (adhesive). can do.
 このようにクッション層の第1離型層形成側の反対側に第2離型層を形成すると、回路露出フィルムへのCLフィルムの接着時にクッション層がプレス熱盤に付着することを防止することができる。このため、回路露出フィルムへのCLフィルムの接着工程等に費やされる時間を短くすることができる。 Thus, when the second release layer is formed on the opposite side of the cushion layer to the first release layer forming side, the cushion layer is prevented from adhering to the press hot platen when the CL film is adhered to the circuit exposed film. Can do. For this reason, the time spent for the adhesion process etc. of CL film to a circuit exposure film can be shortened.
 (6)
 本発明の一局面に係る積層フィルムにおいて、第2離型層は、シンジオタクチック構造を有するポリスチレン系樹脂を主成分とする樹脂から形成されるのが好ましい。
(6)
In the laminated film according to one aspect of the present invention, the second release layer is preferably formed from a resin whose main component is a polystyrene resin having a syndiotactic structure.
 このようにシンジオタクチック構造を有するポリスチレン系樹脂を主成分とする樹脂から第2離型層を形成すると、プライマー(接着剤)を使用することなくクッション層に接着することができる。このため、この積層フィルムは、材料コストや工程コストを低く維持しつつ製造することができる。 Thus, when the second release layer is formed from a resin whose main component is a polystyrene resin having a syndiotactic structure, it can be adhered to the cushion layer without using a primer (adhesive). For this reason, this laminated film can be manufactured while keeping material cost and process cost low.
 (7)
 本発明の一局面に係る積層フィルムにおいて、第2離型層を形成する樹脂は、示差走査熱量測定法により測定される結晶化度が14.0%以上30.0%未満であるのが好ましい。
(7)
In the laminated film according to one aspect of the present invention, the resin forming the second release layer preferably has a crystallinity measured by a differential scanning calorimetry of 14.0% or more and less than 30.0%. .
 本発明の一局面に係る積層フィルムが上記(4)の通りである場合、第2離型層を形成する樹脂の結晶化度を上述の通りとすると、第2離型層が第1離型層と同一の機能を有することになる。このため、本積層フィルムの使用にあたり、ユーザは第1離型層、第2離型層を特定する必要がない。このため、この積層フィルムを利用すれば、ユーザが第1離型層、第2離型層を認識する手間を省くことができると共に第1離型層、第2離型層の特定ミスによる接着不良を防止することができる。 When the laminated film which concerns on 1 aspect of this invention is as above-mentioned (4), when the crystallinity degree of resin which forms a 2nd mold release layer is as above-mentioned, a 2nd mold release layer is a 1st mold release. It will have the same function as the layer. For this reason, in using this laminated film, the user does not need to specify the first release layer and the second release layer. For this reason, if this laminated film is used, it is possible to save the user from recognizing the first release layer and the second release layer, and to adhere the first release layer and the second release layer due to a specific mistake. Defects can be prevented.
本発明の実施の形態に係る積層フィルムの縦断面図である。It is a longitudinal cross-sectional view of the laminated film which concerns on embodiment of this invention. 変形例(A)に係る積層フィルムの縦断面図である。It is a longitudinal cross-sectional view of the laminated film which concerns on a modification (A). 本発明の実施の形態に係る積層フィルムの製造装置の一例を示す図である。It is a figure which shows an example of the manufacturing apparatus of the laminated film which concerns on embodiment of this invention. 本発明の実施の形態に係る積層フィルムの使用方法の一例を示す図である。It is a figure which shows an example of the usage method of the laminated | multilayer film based on embodiment of this invention. 本発明の実施の形態に係る積層フィルムを使用してCLフィルムを回路パターンの凹凸部に密着させるときの加熱プレスの加熱パターンを示す図である。It is a figure which shows the heating pattern of a heating press when using the laminated | multilayer film which concerns on embodiment of this invention, and making CL film adhere to the uneven | corrugated | grooved part of a circuit pattern. 本発明の実施の形態に係る積層フィルムの離型層の貯蔵弾性率の温度依存性を示すグラフ図である。It is a graph which shows the temperature dependence of the storage elastic modulus of the mold release layer of the laminated film which concerns on embodiment of this invention.
100,100A   積層フィルム
110   離型層(第1離型層)
110a  第1離型層
110b  第2離型層
120   クッション層
100, 100A laminated film 110 release layer (first release layer)
110a First release layer 110b Second release layer 120 Cushion layer
 本発明の実施の形態に係る積層フィルム100は、図1に示されるように、主に、離型層110およびクッション層120から構成される。なお、本実施の形態において、積層フィルム100の厚みは25~300μmであるのが好ましい。
 以下、これらの層それぞれについて詳述する。
As shown in FIG. 1, the laminated film 100 according to the embodiment of the present invention mainly includes a release layer 110 and a cushion layer 120. In the present embodiment, the thickness of the laminated film 100 is preferably 25 to 300 μm.
Hereinafter, each of these layers will be described in detail.
 <積層フィルムの構成層の詳細> <Details of constituent layers of laminated film>
 1.離型層
 離型層110は、シンジオタクチック構造を有するポリスチレン系樹脂(以下「SPS樹脂」と称する)を主成分とする樹脂(以下、「離型層形成樹脂」と称する)から形成される。なお、このような離型層形成樹脂は、出光興産(株)から商品名ザレック(登録商標)(XAREC(登録商標))として市販されている。離型層形成樹脂におけるSPS樹脂の含有率は、70重量%以上90重量%以下であるが、85重量%以上90重量%以下であるのが好ましい。本実施の形態において、離型層110の厚みは5μm以上であるのが好ましく、10μm以上であるのがより好ましい。本実施の形態において、離型層形成樹脂の結晶化度は、示差走査熱量計(DSC)による測定値が14.0%以上30.0%未満であるのが好ましい。離型層形成樹脂の結晶化度が上述の通りであると、回路露出フィルムへのCLフィルムの接着時に、離型層110の回路露出フィルム及びCLフィルムへの密着を防ぎつつ従来の離型フィルムよりも良好な埋め込み性を得ることができるからである。なお、このとき、離型層110の貯蔵弾性率の温度依存性は、図6に示されるようになる。
 以下、離型層形成樹脂の構成成分について詳述する。
1. Release Layer The release layer 110 is formed of a resin (hereinafter referred to as “release layer forming resin”) whose main component is a polystyrene resin having a syndiotactic structure (hereinafter referred to as “SPS resin”). . Such a release layer-forming resin is commercially available from Idemitsu Kosan Co., Ltd. under the trade name Zalek (registered trademark) (XAREC (registered trademark)). The content of the SPS resin in the release layer forming resin is 70% by weight or more and 90% by weight or less, but preferably 85% by weight or more and 90% by weight or less. In the present embodiment, the thickness of the release layer 110 is preferably 5 μm or more, and more preferably 10 μm or more. In the present embodiment, the crystallinity of the release layer forming resin is preferably 14.0% or more and less than 30.0% as measured by a differential scanning calorimeter (DSC). When the crystallinity of the release layer forming resin is as described above, the conventional release film while preventing adhesion of the release layer 110 to the circuit exposed film and the CL film when the CL film is adhered to the circuit exposed film This is because better embedding properties can be obtained. At this time, the temperature dependence of the storage elastic modulus of the release layer 110 is as shown in FIG.
Hereinafter, the components of the release layer forming resin will be described in detail.
 (1)SPS樹脂
 SPS樹脂とは、シンジオタクチック構造、すなわち炭素-炭素シグマ結合から形成される主鎖に対して側鎖であるフェニル基や置換フェニル基が交互に反対方向に位置する立体規則構造を有する樹脂である。
(1) SPS resin SPS resin has a syndiotactic structure, that is, a stereoregulation in which phenyl groups and substituted phenyl groups which are side chains are alternately located in opposite directions with respect to the main chain formed from carbon-carbon sigma bonds. It is a resin having a structure.
 なお、このようなSPS樹脂としては、例えば、特開2000-038461号公報に示されるように、ラセミダイアッドで75%以上、好ましくは85%以上、若しくはラセミペンタッドで30%以上、好ましくは50%以上のシンジオタクティシティーを有するポリスチレン、ポリ(アルキルスチレン)、ポリ(アリールスチレン)、ポリ(ハロゲン化スチレン)、ポリ(ハロゲン化アルキルスチレン)、ポリ(アルコキシスチレン)、ポリ(ビニル安息香酸エステル)、これらの水素化重合体およびこれらの混合物、あるいはこれらを主成分とする共重合体などが挙げられる。 As such an SPS resin, for example, as disclosed in JP-A-2000-038461, racemic dyad is 75% or more, preferably 85% or more, or racemic pentad, 30% or more, preferably Polystyrene, poly (alkyl styrene), poly (aryl styrene), poly (halogenated styrene), poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (vinyl benzoic acid) having a syndiotacticity of 50% or more Esters), hydrogenated polymers thereof and mixtures thereof, or copolymers based on these.
 ポリ(アルキルスチレン)としては、例えば、ポリ(メチルスチレン)、ポリ(エチルスチレン)、ポリ(イソプロピルスチレン)、ポリ(t-ブチルスチレン)等が挙げられる。 Examples of poly (alkyl styrene) include poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (t-butyl styrene), and the like.
 ポリ(アリールスチレン)としては、例えば、ポリ(フェニルスチレン)、ポリ(ビニルナフタレン)、ポリ(ビニルスチレン)等が挙げられる。 Examples of poly (aryl styrene) include poly (phenyl styrene), poly (vinyl naphthalene), and poly (vinyl styrene).
 ポリ(ハロゲン化スチレン)としては、例えば、ポリ(クロロスチレン)、ポリ(ブロモスチレン)、ポリ(フルオロスチレン)等が挙げられる。 Examples of poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like.
 ポリ(ハロゲン化アルキルスチレン)としては、例えば、ポリ(クロロメチルスチレン)等が挙げられる。 Examples of poly (halogenated alkylstyrene) include poly (chloromethylstyrene).
 ポリ(アルコキシスチレン)としては、ポリ(メトキシスチレン)、ポリ(エトキシスチレン)等が挙げられる。 Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).
 なお、上述のうち、ポリスチレン、ポリ(p-メチルスチレン)、ポリ(m-メチルスチレン)、ポリ(p-t-プチルスチレン)、ポリ(p-クロロスチレン)、ポリ(m-クロロスチレン)、ポリ(p-フルオロスチレン)、水素化ポリスチレン及びこれらの構造単位を含む共重合体が特に好ましい。 Of the above, polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (pt-ptylstyrene), poly (p-chlorostyrene), poly (m-chlorostyrene), Poly (p-fluorostyrene), hydrogenated polystyrene, and copolymers containing these structural units are particularly preferred.
 (2)SPS樹脂以外の樹脂
 離型層形成樹脂を構成するSPS樹脂以外の樹脂としては、例えば、エラストマー樹脂や、ポリオレフィン系樹脂、ポリスチレン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンサルファイド樹脂(PPS)等が挙げられる。なお、これらの樹脂は単独で、または、二種以上を組み合わせて用いることができる。
(2) Resins other than SPS resin Examples of the resin other than the SPS resin constituting the release layer forming resin include, for example, elastomer resins, polyolefin resins, polystyrene resins, polyester resins, polyamide resins, polyphenylene ether resins, Polyphenylene sulfide resin (PPS) etc. are mentioned. In addition, these resin can be used individually or in combination of 2 or more types.
 なお、エラストマー樹脂としては、例えば、天然ゴム、ポリブタジエン、ポリイソプレン、ポリイソブチレン、ネオプレン、ポリスルフィドゴム、チオコールゴム、アクリルゴム、ウレタンゴム、シリコーンゴム、エピクロロヒドリンゴム、スチレン-ブタジエンブロック共重合体(SBR)、水素添加スチレン-ブタジエンブロック共重合体(SEB)、スチレン-ブタジエン-スチレンブロック共重合体(SBS)、水素添加スチレン-ブタジエン-スチレンブロック共重合体(SEBS)、スチレン-イソプレンブロック共重合体(SIR)、水素添加スチレン-イソプレンブロック共重合体(SEP)、スチレン-イソプレン-スチレンブロック共重合体(SIS)、水素添加スチレン-イソプレン-スチレンブロック共重合体(SEPS)、またはエチレンプロピレンゴム(EPM)、エチレンプロピレンジエンゴム(EPDM)、直鎖状低密度ポリエチレン系エラストマー等のオレフィン系ゴム、もしくはブタジエン-アクリロニトリル-スチレン-コアシェルゴム(ABS)、メチルメタアクリレート-ブタジエン-スチレン-コアシェルゴム(MBS)、メチルメタアクリレート-ブチルアクリレート-スチレン-コアシェルゴム(MAS)、オクチルアクリレート-ブタジエン-スチレン-コアシェルゴム(MABS)、アルキルアクリレート-ブタジエン-アクリロニトリル-スチレン-コアシェルゴム(AABS)、ブタジエン-スチレン-コアシェルゴム(SBR)、メチルメタアクリレート-ブチルアクリレート-シロキサン等のシロキサン含有コアシェルゴム等のコアシェルタイプの粒子状弾性体、またはこれらを変性したゴム等が挙げられる。 Examples of the elastomer resin include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR). ), Hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer ( EPS), or olefin rubbers such as ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), linear low density polyethylene elastomer, or 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 ( Silica-containing cores such as AABS), butadiene-styrene-core shell rubber (SBR), methyl methacrylate-butyl acrylate-siloxane Particulate elastic material of the core-shell type, such as Erugomu, or they were modified rubber, and the like.
 ポリオレフィン系樹脂としては、例えば、直鎖状高密度ポリエチレン、直鎖状低密度ポリエチレン、高圧法低密度ポリエチレン、アイソタクチックポリプロピレン、シンジオタクチックポリプロピレン、ブロックポリプロピレン、ランダムポリプロピレン、ポリブテン、1,2-ポリブタジエン、ポリ(4-メチルペンテン)、環状ポリオレフィン及びこれらの共重合体(例えば、エチレン-メタアクリル酸メチル共重合体等)等が挙げられる。 Examples of polyolefin resins include linear high density polyethylene, linear low density polyethylene, high pressure low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, block polypropylene, random polypropylene, polybutene, 1,2- Examples thereof include polybutadiene, poly (4-methylpentene), cyclic polyolefin, and copolymers thereof (for example, ethylene-methyl methacrylate copolymer).
 ポリスチレン系樹脂としては、例えば、アタクチックポリスチレン、アイソタクチックポリスチレン、高耐衝撃ポリスチレン(HIPS)、アクリロニトリル-ブタジエン-スチレン共重合体(ABS)、アクリロニトリル-スチレン共重合体(AS)、スチレン-メタアクリル酸共重合体、スチレン-メタアクリル酸・アルキルエステル共重合体、スチレン-メタアクリル酸・グリシジルエステル共重合体、スチレン-アクリル酸共重合体、スチレン-アクリル酸・アルキルエステル共重合体、スチレン-マレイン酸共重合体、スチレン-フマル酸共重合体等が挙げられる。 Examples of polystyrene resins include atactic polystyrene, isotactic polystyrene, high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), and styrene-meta. Acrylic acid copolymer, styrene-methacrylic acid / alkyl ester copolymer, styrene-methacrylic acid / glycidyl ester copolymer, styrene-acrylic acid copolymer, styrene-acrylic acid / alkyl ester copolymer, styrene -Maleic acid copolymer, styrene-fumaric acid copolymer and the like.
 ポリエステル系樹脂としては、例えば、ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート等が挙げられる。 Examples of the polyester resin include polycarbonate, polyethylene terephthalate, and polybutylene terephthalate.
 ポリアミド系樹脂としては、例えば、ナイロン(登録商標)6、ナイロン(登録商標)6,6等が挙げられる。 Examples of the polyamide-based resin include nylon (registered trademark) 6, nylon (registered trademark) 6, 6, and the like.
 (3)その他
 離型性形成樹脂には、各種の添加剤、例えば、アンチブロッキング剤、酸化防止剤、核剤、帯電防止剤、プロセスオイル、可塑剤、離型剤、難燃剤、難燃助剤、顔料等が配合されてもかまわない。
(3) Others For the mold release forming resin, various additives such as anti-blocking agent, antioxidant, nucleating agent, antistatic agent, process oil, plasticizer, mold release agent, flame retardant, flame retardant aid Agents, pigments, etc. may be blended.
 なお、アンチブロッキング剤としては、以下のような無機粒子または有機粒子が挙げられる。無機粒子としては、IA族、IIA族、IVA族、VIA族、VIIA族、VIIIA族、IB族、IIB族、IIIB族、IVB族元素の酸化物、水酸化物、硫化物、窒素化物、ハロゲン化物、炭酸塩、硫酸塩、酢酸塩、燐酸塩、亜燐酸塩、有機カルボン酸塩、珪酸塩、チタン酸塩、硼酸塩及びそれらの含水化合物、並びにそれらを中心とする複合化合物及び天然鉱物粒子が挙げられる。 In addition, examples of the antiblocking agent include the following inorganic particles or organic particles. Inorganic particles include Group IA, Group IIA, Group IVA, Group VIA, Group VIIA, Group VIIIA, Group IB, Group IIB, Group IIIB, Group IVB oxides, hydroxides, sulfides, nitrides, halogens , Carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, borates and their water-containing compounds, and composite compounds and natural mineral particles centered on them Is mentioned.
 このような無機粒子の具体的な例としては、フッ化リチウム、ホウ砂(ホウ酸ナトリウム含水塩)等のIA族元素化合物;炭酸マグネシウム、リン酸マグネシウム、酸化マグネシウム(マグネシア)、塩化マグネシウム、酢酸マグネシウム、フッ化マグネシウム、チタン酸マグネシウム、ケイ酸マグネシウム、ケイ酸マグネシウム含水塩(タルク)、炭酸カルシウム、リン酸カルシウム、亜リン酸カルシウム、硫酸カルシウム(石膏)、酢酸カルシウム、テレフタル酸カルシウム、水酸化カルシウム、ケイ酸カルシウム、フッ化カルシウム、チタン酸カルシウム、チタン酸ストロンチウム、炭酸バリウム、リン酸バリウム、硫酸バリウム、亜硫酸バリウム等のIIA族元素化合物;二酸化チタン(チタニア)、一酸化チタン、窒化チタン、二酸化ジルコニウム(ジルコニア)、一酸化ジルコニウム等のIVA族元素化合物;二酸化モリブデン、三酸化モリブデン、硫化モリブデン等のVIA族元素化合物;塩化マンガン、酢酸マンガン等のVIIA族元素化合物;塩化コバルト、酢酸コバルト等のVIII族元素化合物;ヨウ化第一銅等のIB族元素化合物;酸化亜鉛、酢酸亜鉛等のIIB族元素化合物;酸化アルミニウム(アルミナ)、水酸化アルミニウム、フッ化アルミニウム、アルミナシリケート(ケイ酸アルミナ、カオリン、カオリナイト)等のIIIB族元素化合物;酸化ケイ素(シリカ、シリカゲル)、石墨、カーボン、グラファイト、ガラス等のIVB族元素化合物;カーナル石、カイナイト、雲母(マイカ、キンウンモ)、バイロース鉱等の天然鉱物の粒子が挙げられる。 Specific examples of such inorganic particles include group IA element compounds such as lithium fluoride and borax (sodium borate hydrate); magnesium carbonate, magnesium phosphate, magnesium oxide (magnesia), magnesium chloride, acetic acid Magnesium, magnesium fluoride, magnesium titanate, magnesium silicate, magnesium silicate hydrate (talc), calcium carbonate, calcium phosphate, calcium phosphite, calcium sulfate (gypsum), calcium acetate, calcium terephthalate, calcium hydroxide, silicic acid Group IIA element compounds such as calcium, calcium fluoride, calcium titanate, strontium titanate, barium carbonate, barium phosphate, barium sulfate, barium sulfite; titanium dioxide (titania), titanium monoxide, titanium nitride, two Group IVA element compounds such as zirconium fluoride (zirconia) and zirconium monoxide; Group VIA element compounds such as molybdenum dioxide, molybdenum trioxide and molybdenum sulfide; Group VIIA element compounds such as manganese chloride and manganese acetate; Cobalt chloride and cobalt acetate Group VIII element compounds; Group IB element compounds such as cuprous iodide; Group IIB element compounds such as zinc oxide and zinc acetate; Aluminum oxide (alumina), aluminum hydroxide, aluminum fluoride, alumina silicate (alumina silicate) Group IIIB element compounds such as silicon oxide (silica, silica gel), graphite, carbon, graphite, glass, etc .; Carnal stone, kainite, mica (mica, quinumo), villose ore, etc. And natural mineral particles.
 有機粒子としては、フッ素樹脂、メラミン系樹脂、スチレン-ジビニルベンゼン共重合体、アクリル系レジンシリコーン及びそれらの架橋体が挙げられる。 Examples of the organic particles include fluororesins, melamine resins, styrene-divinylbenzene copolymers, acrylic resin silicones, and cross-linked products thereof.
 上述の無機粒子や有機粒子の平均粒径は0.1~10μmであるのが好ましく、添加量は0.01~15重量%であるのが好ましい。 The average particle diameter of the above-mentioned inorganic particles and organic particles is preferably 0.1 to 10 μm, and the addition amount is preferably 0.01 to 15% by weight.
 なお、これらのアンチブロッキング剤は単独で又は二種以上を組み合わせて用いることができる。 In addition, these antiblocking agents can be used individually or in combination of 2 or more types.
 酸化防止剤としては、リン系酸化防止剤、フェノール系酸化防止剤、イオウ系酸化防止剤、2-[(1-ヒドロキシ-3,5-ジ-t-ペンチルフェニル)エチル]-4,6-ジ-t-ペンチルフェニルアクリレートなどが挙げられる。なお、これらの酸化防止剤は単独で、または、二種以上を組み合わせて用いることができる。 Antioxidants include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, 2-[(1-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6- And di-t-pentylphenyl acrylate. These antioxidants can be used alone or in combination of two or more.
 核剤としては、アルミニウムジ(p-t-ブチルベンゾエート)等のカルボン酸の金属塩、メチレンビス(2,4-ジ-t-ブチルフェノール)アシッドホスフェートナトリウム等のリン酸の金属塩、タルク、フタロシアニン誘導体等が挙げられる。なお、これらの核剤は単独で、または、二種以上を組み合わせて用いることができる。 Nucleating agents include metal salts of carboxylic acids such as aluminum di (pt-butylbenzoate), metal salts of phosphoric acid such as methylenebis (2,4-di-t-butylphenol) acid phosphate, talc, phthalocyanine derivatives Etc. In addition, these nucleating agents can be used individually or in combination of 2 or more types.
 可塑剤としては、ポリエチレングリコール、ポリアミドオリゴマー、エチレンビスステアロアマイド、フタル酸エステル、ポリスチレンオリゴマー、ポリエチレンワックス、シリコーンオイル等が挙げられる。なお、これらの可塑剤は、単独で、または、二種以上を組み合わせて用いることができる。 Examples of the plasticizer include polyethylene glycol, polyamide oligomer, ethylene bisstearamide, phthalate ester, polystyrene oligomer, polyethylene wax, silicone oil, and the like. In addition, these plasticizers can be used individually or in combination of 2 or more types.
 離型剤としては、ポリエチレンワックス、シリコーンオイル、長鎖カルボン酸、長鎖カルボン酸金属塩等が挙げられる。なお、これらの離型剤は単独で、または、二種以上を組み合わせて用いることができる。 Examples of the release agent include polyethylene wax, silicone oil, long chain carboxylic acid, and long chain carboxylic acid metal salt. In addition, these mold release agents can be used individually or in combination of 2 or more types.
 プロセスオイルとしては、パラフィン系オイル、ナフテン系オイル、アロマ系オイルが挙げられる。なお、これらの中でもn-d-M法で算出されるパラフィン(直鎖)に関わる炭素数の全炭素数に対する百分率が60%Cp以上のパラフィン系オイルが好ましい。 Process oils include paraffinic oil, naphthenic oil, and aroma oil. Of these, paraffinic oils having a percentage of the total number of carbon atoms related to paraffin (straight chain) calculated by the ndM method of 60% Cp or more are preferable.
 プロセスオイルの粘度は、40℃での動粘度が15~600csであるのが好ましく、15~500csであるのがさらに好ましい。また、プロセスオイルの添加量は、離型性形成樹脂100重量部に対して0.01~1.5重量部であるのが好ましく、0.05~1.4重量部であるのがより好ましく、0.1~1.3重量部であるのがさらに好ましい。なお、これらのプロセスオイルは、単独で、または、二種以上を組み合わせて用いることができる。 The viscosity of the process oil is preferably 15 to 600 cs at 40 ° C., more preferably 15 to 500 cs. The amount of process oil added is preferably from 0.01 to 1.5 parts by weight, more preferably from 0.05 to 1.4 parts by weight, based on 100 parts by weight of the release forming resin. More preferably, the content is 0.1 to 1.3 parts by weight. In addition, these process oil can be used individually or in combination of 2 or more types.
 2.クッション層
 クッション層120は、本実施の形態において、主に、60重量部超98重量部以下のポリオレフィン系樹脂と、2重量部以上40重量部未満のSPS樹脂との樹脂ブレンド物から形成されている。なお、この樹脂ブレンド物は、前練りなしのドライブレンド法により調製することができるが、2軸混練機による前処理を行ってもかまわない。また、本実施の形態において、クッション層120の厚みは離型層110の厚みの3倍以上であるのが好ましく、5倍以上であるのがより好ましく、8倍以上であるのがさらに好ましい。
2. Cushion layer In the present embodiment, the cushion layer 120 is mainly formed from a resin blend of a polyolefin-based resin of more than 60 parts by weight and 98 parts by weight or less and an SPS resin of 2 parts by weight or more and less than 40 parts by weight. Yes. In addition, although this resin blend can be prepared by the dry blend method without pre-kneading, you may pre-process with a biaxial kneader. In the present embodiment, the thickness of the cushion layer 120 is preferably at least 3 times the thickness of the release layer 110, more preferably at least 5 times, and even more preferably at least 8 times.
 なお、ポリオレフィン系樹脂としては、例えば、直鎖状高密度ポリエチレン、直鎖状低密度ポリエチレン、高圧法低密度ポリエチレン、アイソタクチックポリプロピレン、シンジオタクチックポリプロピレン、ブロックポリプロピレン、ランダムポリプロピレン、ポリブテン、1,2-ポリブタジエン、ポリ(4-メチルペンテン)、環状ポリオレフィン及びこれらの共重合体(例えば、エチレン-メタアクリル酸メチル共重合体等)等が挙げられる。 Examples of polyolefin resins include linear high-density polyethylene, linear low-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, block polypropylene, random polypropylene, polybutene, 1, Examples thereof include 2-polybutadiene, poly (4-methylpentene), cyclic polyolefin, and copolymers thereof (for example, ethylene-methyl methacrylate copolymer).
 SPS樹脂は、上述のSPS樹脂と同様である。 The SPS resin is the same as the SPS resin described above.
 このクッション層120は、2重量部以上40重量部未満のSPS樹脂と、3重量部以上40重量部以下のポリプロピレン樹脂と、20重量部超95重量部以下のエチレン-メタアクリル酸メチル共重合体樹脂との樹脂ブレンド物から形成されるのがより好ましい。かかる場合、エチレン-メタアクリル酸メチル共重合体樹脂は、メタアクリル酸メチルから誘導される単位を5重量%以上14重量%以下含有するのが好ましい。クッション層120の組成およびエチレン-メタアクリル酸メチル共重合体樹脂の組成が上記の通りであると、(i)プライマーを使用することなくクッション層120と離型層110との接着性を良好とすることができると共に(ii)プレス中にクッション層120端面の熱盤へのシミ出し量を低減することができるからである。 The cushion layer 120 includes 2 parts by weight or more and less than 40 parts by weight of an SPS resin, 3 parts by weight or more and 40 parts by weight or less of a polypropylene resin, and more than 20 parts by weight of 95 parts by weight or less of an ethylene-methyl methacrylate copolymer. More preferably, it is formed from a resin blend with resin. In such a case, the ethylene-methyl methacrylate copolymer resin preferably contains 5% by weight to 14% by weight of units derived from methyl methacrylate. When the composition of the cushion layer 120 and the composition of the ethylene-methyl methacrylate copolymer resin are as described above, (i) good adhesion between the cushion layer 120 and the release layer 110 without using a primer. This is because (ii) it is possible to reduce the amount of smearing of the end face of the cushion layer 120 to the hot platen during pressing.
 なお、この樹脂ブレンド物には、必要に応じて、本発明の趣旨を損ねない範囲で、その他、上述のエラストマー樹脂や添加剤が配合されてもかまわない。 In addition, the above-mentioned elastomer resin and additives may be blended with the resin blend as necessary, as long as the gist of the present invention is not impaired.
 <積層フィルムの製造方法>
 本実施の形態に係る積層フィルム100は、共押出法や押出ラミネート法等の方法で製造することができる。
<Method for producing laminated film>
The laminated film 100 according to the present embodiment can be manufactured by a method such as a coextrusion method or an extrusion lamination method.
 共押出法では、フィードブロック、マルチマニホールドダイを使用して離型層110とクッション層120とを同時に押し出すことにより積層フィルム100を製造する。なお、共押出法では、ダイス210を通過した融解物Mは、図3に示されるように、第1ロール230とタッチロール220との間に誘導され、第1ロール230から脱離するまでの間にタッチロール220及び第1ロール230により冷却され、積層フィルム100となる。その後、その積層フィルム100は、第2ロール240によりフィルム送り方向(図3の矢印参照)下流側に送られ、最終的に巻取ロール(図示せず)に巻き取られる。なお、このとき、第1ロール230の温度は30~100℃であるのが好ましく、タッチロール220の温度は50~120℃であるのが好ましく、第1ロール230に対する第2ロール240の周速比は0.990~0.998であるのが好ましい。 In the coextrusion method, the laminated film 100 is manufactured by simultaneously extruding the release layer 110 and the cushion layer 120 using a feed block and a multi-manifold die. In the coextrusion method, the melt M that has passed through the die 210 is guided between the first roll 230 and the touch roll 220 as shown in FIG. The laminated film 100 is cooled by the touch roll 220 and the first roll 230. Thereafter, the laminated film 100 is sent to the downstream side in the film feeding direction (see the arrow in FIG. 3) by the second roll 240 and is finally taken up by a take-up roll (not shown). At this time, the temperature of the first roll 230 is preferably 30 to 100 ° C., the temperature of the touch roll 220 is preferably 50 to 120 ° C., and the peripheral speed of the second roll 240 with respect to the first roll 230. The ratio is preferably from 0.990 to 0.998.
 押出しラミネート法では、押出機シリンダーの温度を270~300℃に設定して離型層110を押出し、その離型層110をクッション層120と合流させることにより離型層110とクッション層120とを積層して積層フィルム100を製造する。なお、押出しラミネート法では、ダイス210を通過した離型層形成樹脂の融解物Mは、図3に示されるように、第1ロール230とタッチロール220との間に誘導され、第1ロール230から脱離するまでの間にタッチロール220及び第1ロール230により冷却されて離型層フィルムFとなる。その後、その離型層フィルムFは、第2ロール240によりフィルム送り方向(図3の矢印参照)下流側に送られる。そして、フィルム送り方向下流側に送られた離型層フィルムFに、クッション層120を形成する樹脂ブレンド物の溶融物(図示せず)が合流させられて離型層フィルムFと一体化され、積層フィルム100が製造される。なお、このようにして製造された積層フィルム100は、さらにフィルム送り方向下流側に設けられる巻取ロール(図示せず)に巻き取られる。なお、このときも、第1ロール230の温度は30~100℃であるのが好ましく、タッチロール220の温度は50~120℃であるのが好ましく、第1ロール230に対する第2ロール240の周速比は0.990~0.998であるのが好ましい。 In the extrusion laminating method, the temperature of the extruder cylinder is set to 270 to 300 ° C., the release layer 110 is extruded, and the release layer 110 and the cushion layer 120 are joined together to form the release layer 110 and the cushion layer 120. The laminated film 100 is manufactured by laminating. In the extrusion laminating method, the release layer forming resin melt M that has passed through the die 210 is guided between the first roll 230 and the touch roll 220 as shown in FIG. Until it is detached, it is cooled by the touch roll 220 and the first roll 230 to form the release layer film F. Thereafter, the release layer film F is sent downstream by the second roll 240 in the film feeding direction (see the arrow in FIG. 3). And the melt (not shown) of the resin blend that forms the cushion layer 120 is merged with the release layer film F sent to the downstream side in the film feed direction and integrated with the release layer film F, The laminated film 100 is manufactured. In addition, the laminated | multilayer film 100 manufactured in this way is wound up by the winding roll (not shown) further provided in the film feed direction downstream. Also at this time, the temperature of the first roll 230 is preferably 30 to 100 ° C., the temperature of the touch roll 220 is preferably 50 to 120 ° C., and the circumference of the second roll 240 with respect to the first roll 230 is preferred. The speed ratio is preferably 0.990 to 0.998.
 なお、必要に応じて、上述のようにして得られた積層フィルム100の離型層110中のSPS樹脂の結晶化度を公知の熱処理装置により調節してもかまわない。例えば、テンター装置を使用し乾燥機の中にて積層フィルム100を熱固定する方法や熱処理ロールを使用して50~220℃近辺で熱処理を行えばよい。 If necessary, the crystallinity of the SPS resin in the release layer 110 of the laminated film 100 obtained as described above may be adjusted by a known heat treatment apparatus. For example, heat treatment may be performed in the vicinity of 50 to 220 ° C. using a method of heat-setting the laminated film 100 in a dryer using a tenter device or a heat treatment roll.
 <積層フィルムの使用の一例>
 本発明の実施の形態に係る積層フィルム100は、回路露出フィルムへのCLフィルム接着時にCLフィルムを回路パターンの凹凸部に密着させるためにCLフィルムを包むように配置され、回路露出フィルム及びCLフィルムと共にプレス装置により加圧される。具体的には、積層フィルム100は、図4に示されるように、回路露出フィルムとCLフィルムとが接着剤により仮止めされたもの340を、離型層110が対向するように挟み込んだ後、テフロン(登録商標)シート330、ゴムクッション320及びステンレス板310で順次挟み込まれ、熱盤300でプレスされる(図4の白抜矢印参照)。なお、その熱盤300による加熱方法としては、図5に示される通りである。つまり、熱盤300は、加圧を開始してから10秒で常温から185℃まで急速昇温された後、その温度に60秒間維持される。なお、熱盤300による加圧は、0秒の時点で開始され、70秒の時点で開放される。なお、このときのプレス圧力は、5~15MPaで適宜調節される。
<Example of use of laminated film>
The laminated film 100 according to the embodiment of the present invention is disposed so as to wrap the CL film so that the CL film adheres to the concavo-convex portion of the circuit pattern when the CL film is adhered to the circuit exposed film, and together with the circuit exposed film and the CL film. Pressurized by a press device. Specifically, as shown in FIG. 4, the laminated film 100 is obtained by sandwiching a circuit-exposed film and a CL film temporarily fixed with an adhesive 340 so that the release layer 110 faces each other. The sheet is sequentially sandwiched between a Teflon (registered trademark) sheet 330, a rubber cushion 320, and a stainless steel plate 310, and pressed by a hot platen 300 (see white arrows in FIG. 4). The heating method using the hot platen 300 is as shown in FIG. That is, the hot platen 300 is rapidly heated from room temperature to 185 ° C. in 10 seconds after the start of pressurization, and then maintained at that temperature for 60 seconds. Note that pressurization by the hot platen 300 is started at the time of 0 seconds and released at the time of 70 seconds. The pressing pressure at this time is appropriately adjusted to 5 to 15 MPa.
 <変形例> <Modification>
 (A)
 先の実施の形態では、クッション層120の片側にのみ離型層110が設けられる積層フィルム100が紹介されたが、図2に示されるように、クッション層120の両側に離型層110a,110bが設けられる積層フィルム110Aも本発明の一実施の形態に含まれる。なお、以下、符号110aの離型層を「第1離型層」と称し、符号110bの離型層を「第2離型層」と称する。
(A)
In the previous embodiment, the laminated film 100 in which the release layer 110 is provided only on one side of the cushion layer 120 was introduced. However, as shown in FIG. 2, the release layers 110a and 110b on both sides of the cushion layer 120. A laminated film 110 </ b> A provided with is also included in one embodiment of the present invention. Hereinafter, the release layer denoted by reference numeral 110a is referred to as a “first release layer”, and the release layer denoted by reference numeral 110b is referred to as a “second release layer”.
 第1離型層110aは、先の実施の形態に係る離型層110と同一の構造を有する。その一方、第2離型層110bは、第1離型層110aと同一の構造を有していてもよいし、第1離型層110aと異なる構造を有していてもよい。後者の場合、第2離型層110bは、例えば、ポリメチルペンテン樹脂やメチルペンテン-αオレフィン共重合体を主成分とする樹脂から形成される。なお、このような樹脂は、三井化学(株)から商品名TPX(登録商標)として市販されている。かかる場合、第2離型層110bとクッション層120と接着力が低下するおそれがあるが、そのような場合には、第2離型層110bとクッション層120との間にアンカー層やプライマー層(接着層)を介在させてもよい。 The first release layer 110a has the same structure as the release layer 110 according to the previous embodiment. On the other hand, the second release layer 110b may have the same structure as the first release layer 110a, or may have a different structure from the first release layer 110a. In the latter case, the second release layer 110b is formed of, for example, a resin mainly composed of polymethylpentene resin or methylpentene-α olefin copolymer. Such a resin is commercially available from Mitsui Chemicals, Inc. under the trade name TPX (registered trademark). In such a case, the adhesive force between the second release layer 110b and the cushion layer 120 may be reduced. In such a case, an anchor layer or a primer layer is interposed between the second release layer 110b and the cushion layer 120. (Adhesive layer) may be interposed.
 (B)
 先の実施の形態に係る積層フィルムの使用の一例では、積層フィルム100と熱盤300との間にテフロン(登録商標)シート330、ゴムクッション320及びステンレス板310で順次挟み込まれていたが、テフロン(登録商標)シート330、ゴムクッション320及びステンレス板310は省かれてもかまわない。
(B)
In the example of use of the laminated film according to the previous embodiment, the Teflon (registered trademark) sheet 330, the rubber cushion 320, and the stainless steel plate 310 are sequentially sandwiched between the laminated film 100 and the heating platen 300. The (registered trademark) sheet 330, the rubber cushion 320, and the stainless steel plate 310 may be omitted.
 <実施例>
 以下、実施例を示して本発明をより詳細に説明する。
<Example>
Hereinafter, the present invention will be described in more detail with reference to examples.
 1.積層フィルムの製造 1. Production of laminated film
 (1)離型層の原料
 離型層の原料として、SPS樹脂(出光興産(株)社製のザレック(登録商標)S104)を用いた。
(1) Release Layer Raw Material As a release layer raw material, SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) was used.
 (2)クッション層の原料
 クッション層の原料としては、20重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、75重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:5重量%)(住友化学(株)製のアクリフト(登録商標)WD106)と、5重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたもの(以下「クッション層形成ブレンド樹脂」と称する)を用いた。
(2) Cushion Layer Raw Material The cushion layer raw material is 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 75 parts by weight of ethylene-methyl methacrylate copolymer. Combined (methyl methacrylate derived unit content: 5% by weight) (Aclift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 5 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) What was dry blended (hereinafter referred to as “cushion layer forming blend resin”) was used.
 (3)積層フィルムの作製
 共押出法を利用して、クッション層の表裏に同一の離型層を有する積層フィルム(図2参照)を作製した。
(3) Production of Laminated Film A laminated film (see FIG. 2) having the same release layer on the front and back of the cushion layer was produced using a coextrusion method.
 なお、具体的には、フィードブロック、マルチマニホールドダイを使用してSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)、クッション層形成ブレンド樹脂およびSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)を同時に押し出して積層フィルムを作製した。なお、この際、図3に示される装置を用いたが、第1ロール230の温度は30℃であり、タッチロール220の温度は70℃であり、第1ロール230に対する第2ロール240の周速比は0.990であった。 Specifically, SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.), cushion layer forming blend resin and SPS resin (Idemitsu Kosan Co., Ltd.) using a feed block and a multi-manifold die. Zalek (registered trademark) S104 manufactured by the company was simultaneously extruded to produce a laminated film. At this time, the apparatus shown in FIG. 3 was used, but the temperature of the first roll 230 was 30 ° C., the temperature of the touch roll 220 was 70 ° C., and the circumference of the second roll 240 with respect to the first roll 230 was changed. The speed ratio was 0.990.
 この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 The thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 2.積層フィルムの評価 2. Evaluation of laminated film
 (1)プレスセットの作業性
 作業者による官能試験を行った。その結果、上述の積層フィルムのプレスセットの作業性は良好であった(表1参照)。
(1) Workability of press set A sensory test was conducted by an operator. As a result, the workability of the above-described laminated film press set was good (see Table 1).
 (2)ボイド観察
 プレス後のFPCを光学顕微鏡で観察したところ、そのFPC中にボイドは発見されなかった(表1参照)。
(2) Void Observation When the FPC after pressing was observed with an optical microscope, no void was found in the FPC (see Table 1).
 (3)CLフィルム接着試験
 実際に、CLフィルムが接着剤を介して仮止めされた回路露出フィルムを、上記積層フィルムで両側から包み込み、熱盤プレスにより図5に示される加熱パターンで加熱プレスした。その結果、積層フィルムには、割れが発生しなかった(表1参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm未満であり、許容範囲内であった(表1参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表1参照)。
(3) CL film adhesion test Actually, the circuit-exposed film in which the CL film was temporarily fixed via an adhesive was wrapped from both sides with the laminated film, and was hot-pressed with a heating pattern shown in FIG. . As a result, no crack occurred in the laminated film (see Table 1). The amount of the adhesive between the circuit-exposed film and the CL film spilled into the circuit pattern was less than 100 μm and was within an allowable range (see Table 1). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within an allowable range (see Table 1).
 クッション層形成ブレンド樹脂として、20重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、70重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:5重量%)(住友化学(株)製のアクリフト(登録商標)WD106)と、10重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。 As a cushion layer forming blend resin, 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 70 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 5% by weight) (Acrylift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used. A laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表1参照)。プレス後のFPC中には、ボイドは発見されなかった(表1参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表1参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm未満であり、許容範囲内であった(表1参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表1参照)。 As a result of the evaluation, the workability of this laminated film press set was good (see Table 1). No voids were found in the FPC after pressing (see Table 1). This laminated film was not cracked even after hot pressing (see Table 1). The amount of the adhesive between the circuit-exposed film and the CL film spilled into the circuit pattern was less than 100 μm and was within an allowable range (see Table 1). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within an allowable range (see Table 1).
 クッション層形成ブレンド樹脂として、20重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、60重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:5重量%)(住友化学(株)製のアクリフト(登録商標)WD106)と、20重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 As cushion layer forming blend resin, 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 60 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) (Unit content: 5% by weight) (Akulift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 20 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used. A laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表1参照)。プレス後のFPC中には、ボイドは発見されなかった(表1参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表1参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm未満であり、許容範囲内であった(表1参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表1参照)。 As a result of the evaluation, the workability of this laminated film press set was good (see Table 1). No voids were found in the FPC after pressing (see Table 1). This laminated film was not cracked even after hot pressing (see Table 1). The amount of the adhesive between the circuit-exposed film and the CL film spilled into the circuit pattern was less than 100 μm and was within an allowable range (see Table 1). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within an allowable range (see Table 1).
 クッション層形成ブレンド樹脂として、20重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、50重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:5重量%)(住友化学(株)製のアクリフト(登録商標)WD106)と、30重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 As a cushion layer forming blend resin, 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 50 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) (Unit content: 5% by weight) (Aclift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 30 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used. A laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表1参照)。プレス後のFPC中には、ボイドは発見されなかった(表1参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表1参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm未満であり、許容範囲内であった(表1参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表1参照)。 As a result of the evaluation, the workability of this laminated film press set was good (see Table 1). No voids were found in the FPC after pressing (see Table 1). This laminated film was not cracked even after hot pressing (see Table 1). The amount of the adhesive between the circuit-exposed film and the CL film spilled into the circuit pattern was less than 100 μm and was within an allowable range (see Table 1). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within an allowable range (see Table 1).
 クッション層形成ブレンド樹脂として、20重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、70重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:10重量%)(住友化学(株)製のアクリフト(登録商標)WD201)と、10重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 As a cushion layer forming blend resin, 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 70 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 10% by weight) (Acrylift (registered trademark) WD201 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used. A laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表2参照)。プレス後のFPC中には、ボイドは発見されなかった(表2参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表2参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm未満であり、許容範囲内であった(表2参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表2参照)。 As a result of evaluation, the workability of the press set of this laminated film was good (see Table 2). No voids were found in the FPC after pressing (see Table 2). This laminated film did not crack even after hot pressing (see Table 2). The amount of the adhesive between the circuit-exposed film and the CL film spilled into the circuit pattern was less than 100 μm and was within an allowable range (see Table 2). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within the allowable range (see Table 2).
 クッション層形成ブレンド樹脂として、20重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、70重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:14重量%)(住友化学(株)製のアクリフト(登録商標)CM8033)と、10重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 As a cushion layer forming blend resin, 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 70 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 14% by weight) (Acrylift (registered trademark) CM8033 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used. A laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表2参照)。プレス後のFPC中には、ボイドは発見されなかった(表2参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表2参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm未満であり、許容範囲内であった(表2参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表2参照)。 As a result of evaluation, the workability of the press set of this laminated film was good (see Table 2). No voids were found in the FPC after pressing (see Table 2). This laminated film did not crack even after hot pressing (see Table 2). The amount of the adhesive between the circuit-exposed film and the CL film spilled into the circuit pattern was less than 100 μm and was within an allowable range (see Table 2). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within the allowable range (see Table 2).
 クッション層形成ブレンド樹脂として、39重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、21重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:14重量%)(住友化学(株)製のアクリフト(登録商標)CM8033)と、40重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 As a cushion layer-forming blend resin, 39 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 21 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 14% by weight) (Acrylift (registered trademark) CM8033 manufactured by Sumitomo Chemical Co., Ltd.) and 40 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used. A laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表2参照)。プレス後のFPC中には、ボイドは発見されなかった(表2参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表2参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm未満であり、許容範囲内であった(表2参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表2参照)。 As a result of evaluation, the workability of the press set of this laminated film was good (see Table 2). No voids were found in the FPC after pressing (see Table 2). This laminated film did not crack even after hot pressing (see Table 2). The amount of the adhesive between the circuit-exposed film and the CL film spilled into the circuit pattern was less than 100 μm and was within an allowable range (see Table 2). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within the allowable range (see Table 2).
 クッション層形成ブレンド樹脂として、5重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、90重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:14重量%)(住友化学(株)製のアクリフト(登録商標)CM8033)と、5重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 As a cushion layer-forming blend resin, 5 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 90 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 14% by weight) (Acrylift (registered trademark) CM8033 manufactured by Sumitomo Chemical Co., Ltd.) and 5 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used. A laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表2参照)。プレス後のFPC中には、ボイドは発見されなかった(表2参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表2参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm未満であり、許容範囲内であった(表2参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表2参照)。 As a result of evaluation, the workability of the press set of this laminated film was good (see Table 2). No voids were found in the FPC after pressing (see Table 2). This laminated film did not crack even after hot pressing (see Table 2). The amount of the adhesive between the circuit-exposed film and the CL film spilled into the circuit pattern was less than 100 μm and was within an allowable range (see Table 2). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within the allowable range (see Table 2).
 クッション層形成ブレンド樹脂として、20重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、80重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:5重量%)(住友化学(株)製のアクリフト(登録商標)WD106)とをドライブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 As a cushion layer forming blend resin, 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 80 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) A laminated film was prepared in the same manner as in Example 1 except that a dry blend of (unit content: 5% by weight) (Aclift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) was used. Was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表3参照)。プレス後のFPC中には、ボイドは発見されなかった(表3参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表3参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm未満であり、許容範囲内であった(表3参照)。しかし、クッション層端面のシミ出し量は、5mm以上であり、許容範囲外であった(表3参照)。 As a result of the evaluation, the workability of this laminated film press set was good (see Table 3). No voids were found in the FPC after pressing (see Table 3). This laminated film did not crack even after hot pressing (see Table 3). The amount of the adhesive between the circuit-exposed film and the CL film oozed out into the circuit pattern was less than 100 μm, and was within an allowable range (see Table 3). However, the amount of the stain on the end face of the cushion layer was 5 mm or more, which was outside the allowable range (see Table 3).
 クッション層形成ブレンド樹脂として、20重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、70重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:20重量%)(住友化学(株)製のアクリフト(登録商標)WH206)と、10重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 As a cushion layer forming blend resin, 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 70 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 20% by weight) (Acrylift (registered trademark) WH206 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used. A laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表3参照)。プレス後のFPC中には、ボイドは発見されなかった(表3参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表3参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm未満であり、許容範囲内であった(表3参照)。しかし、クッション層端面のシミ出し量は、5mm以上であり、許容範囲外であった(表3参照)。 As a result of the evaluation, the workability of this laminated film press set was good (see Table 3). No voids were found in the FPC after pressing (see Table 3). This laminated film did not crack even after hot pressing (see Table 3). The amount of the adhesive between the circuit-exposed film and the CL film oozed out into the circuit pattern was less than 100 μm, and was within an allowable range (see Table 3). However, the amount of the stain on the end face of the cushion layer was 5 mm or more, which was outside the allowable range (see Table 3).
 クッション層形成ブレンド樹脂として、20重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、70重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:17.5重量%)(住友化学(株)製のアクリフト(登録商標)CM8014)と、10重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 As a cushion layer forming blend resin, 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 70 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 17.5% by weight (Akulift (registered trademark) CM8014 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) A laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表3参照)。プレス後のFPC中には、ボイドは発見されなかった(表3参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表3参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm未満であり、許容範囲内であった(表3参照)。しかし、クッション層端面のシミ出し量は、5mm以上であり、許容範囲外であった(表3参照)。 As a result of the evaluation, the workability of this laminated film press set was good (see Table 3). No voids were found in the FPC after pressing (see Table 3). This laminated film did not crack even after hot pressing (see Table 3). The amount of the adhesive between the circuit-exposed film and the CL film oozed out into the circuit pattern was less than 100 μm, and was within an allowable range (see Table 3). However, the amount of the stain on the end face of the cushion layer was 5 mm or more, which was outside the allowable range (see Table 3).
 1.積層フィルムの製造 1. Production of laminated film
 (1)離型層の原料
 離型層の原料として、SPS樹脂(出光興産(株)社製のザレック(登録商標)S104)を用いた。
(1) Release Layer Raw Material As a release layer raw material, SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) was used.
 (2)クッション層の原料
 クッション層の原料としては、20重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、70重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:5重量%)(住友化学(株)製のアクリフト(登録商標)WD106)と、10重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたもの(以下「クッション層形成ブレンド樹脂」と称する)を用いた。
(2) Cushion Layer Raw Material The cushion layer raw material is 20 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 70 parts by weight of ethylene-methyl methacrylate copolymer. Combined (Methyl methacrylate derived unit content: 5% by weight) (Akulift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) What was dry blended (hereinafter referred to as “cushion layer forming blend resin”) was used.
 (3)積層フィルムの作製
 共押出法を利用して、クッション層の表裏に同一の離型層を有する積層フィルム(図2参照)を作製した。
(3) Production of Laminated Film A laminated film (see FIG. 2) having the same release layer on the front and back of the cushion layer was produced using a coextrusion method.
 なお、具体的には、マルチマニホールドダイを使用してSPS樹脂、クッション層形成ブレンド樹脂およびSPS樹脂を同時に押し出して積層フィルムを作製した。なお、この際、図3に示される装置を用いたが、第1ロール230の温度は35℃であり、タッチロール220の温度は70℃であり、第1ロール230に対する第2ロール240の周速比は0.998であった。 Specifically, a multi-manifold die was used to simultaneously extrude SPS resin, cushion layer forming blend resin, and SPS resin to produce a laminated film. In this case, although the apparatus shown in FIG. 3 was used, the temperature of the first roll 230 was 35 ° C., the temperature of the touch roll 220 was 70 ° C., and the circumference of the second roll 240 with respect to the first roll 230 was changed. The speed ratio was 0.998.
 この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 The thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 2.積層フィルムの評価 2. Evaluation of laminated film
 (1)プレスセットの作業性
 作業者による官能試験を行った。その結果、上述の積層フィルムのプレスセットの作業性は良好であった(表4参照)。
(1) Workability of press set A sensory test was conducted by an operator. As a result, the workability of the above-described laminated film press set was good (see Table 4).
 (2)ボイド観察
 プレス後のFPCを光学顕微鏡で観察したところ、そのFPC中にボイドは発見されなかった(表4参照)。
(2) Void Observation When the FPC after pressing was observed with an optical microscope, no void was found in the FPC (see Table 4).
 (3)CLフィルム接着試験
 実際に、CLフィルムが接着剤を介して仮止めされた回路露出フィルムを、上記積層フィルムで両側から包み込み、熱盤プレスにより図5に示される加熱パターンで加熱プレスした。その後、上記積層フィルムは、回路露出フィルム及びCLフィルムから容易に剥離することができた(表4参照)。また、積層フィルムには、割れが発生しなかった(表4参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、80μm未満であり、従来の離型フィルムよりも優れていた(表4参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表4参照)。
 (4)離型層の結晶化度測定
 上述の積層フィルムから離型層を剥ぎ取り、その離型層片を示差走査熱量計にて20℃/分の速度で昇温し、融解エンタルピー(ΔHf)及び冷結晶化のエンタルピー(ΔHTcc )を測定した。そして、この融解エンタルピー(ΔHf)及び冷結晶化のエンタルピー(ΔHTcc )の値を下式に代入して離型層の結晶化度を算出したところ、その値は15.8%であった(表4参照)
   結晶化度(%)=100×(ΔH-ΔHTcc)/53(J/g)
(3) CL film adhesion test Actually, the circuit-exposed film in which the CL film was temporarily fixed via an adhesive was wrapped from both sides with the laminated film, and was hot-pressed with a heating pattern shown in FIG. . Thereafter, the laminated film could be easily peeled from the circuit exposed film and the CL film (see Table 4). Further, no cracks occurred in the laminated film (see Table 4). The amount of the adhesive between the circuit-exposed film and the CL film oozed out into the circuit pattern was less than 80 μm, which was superior to the conventional release film (see Table 4). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within an allowable range (see Table 4).
(4) Measurement of crystallinity of release layer The release layer was peeled off from the above laminated film, and the release layer piece was heated at a rate of 20 ° C / min with a differential scanning calorimeter, and the melting enthalpy (ΔHf ) And cold crystallization enthalpy (ΔH Tcc ). Then, the crystallinity of the release layer was calculated by substituting the melting enthalpy (ΔHf) and the cold crystallization enthalpy (ΔH Tcc ) into the following equation, and the value was 15.8% ( (See Table 4)
Crystallinity (%) = 100 × (ΔH f −ΔH Tcc ) / 53 (J / g)
 第1ロール230の温度を98℃とし、タッチロール220の温度を120℃とし、第1ロール230に対する第2ロール240の周速比を0.998と設定した以外は実施例12と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 Example 12 is the same as Example 12 except that the temperature of the first roll 230 is set to 98 ° C., the temperature of the touch roll 220 is set to 120 ° C., and the peripheral speed ratio of the second roll 240 to the first roll 230 is set to 0.998. A laminated film was produced and the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表4参照)。プレス後のFPC中には、ボイドは発見されなかった(表4参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表4参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、80μm未満であり、従来の離型フィルムよりも優れていた(表4参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表4参照)。この積層フィルムの離型層の結晶化度は17.3%であった(表4参照)。積層フィルムは、回路露出フィルム及びCLフィルムから容易に剥離することができた(表4参照)。 As a result of the evaluation, the workability of this laminated film press set was good (see Table 4). No voids were found in the FPC after pressing (see Table 4). This laminated film was not cracked even after hot pressing (see Table 4). The amount of the adhesive between the circuit-exposed film and the CL film oozed out into the circuit pattern was less than 80 μm, which was superior to the conventional release film (see Table 4). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within an allowable range (see Table 4). The crystallinity of the release layer of this laminated film was 17.3% (see Table 4). The laminated film could be easily peeled from the circuit exposed film and the CL film (see Table 4).
 第1ロール230の温度を35℃とし、タッチロール220の温度を70℃とし、第1ロール230に対する第2ロール240の周速比を0.998と設定した以外は実施例12と同様にして積層フィルムを作製し、さらに、その積層フィルムを、表面温度120℃のステンレス板で挟み込んで圧力10MPaで10分間保持することによりアニール処理した後、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 The temperature of the first roll 230 was set to 35 ° C., the temperature of the touch roll 220 was set to 70 ° C., and the peripheral speed ratio of the second roll 240 to the first roll 230 was set to 0.998, as in Example 12. A laminated film was prepared, and the laminated film was further annealed by being sandwiched between stainless plates with a surface temperature of 120 ° C. and held at a pressure of 10 MPa for 10 minutes, and then the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表4参照)。プレス後のFPC中には、ボイドは発見されなかった(表4参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表4参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、80μm未満であり、従来の離型フィルムよりも優れていた(表4参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表4参照)。この積層フィルムの離型層の結晶化度は20.5%であった(表4参照)。積層フィルムは、回路露出フィルム及びCLフィルムから容易に剥離することができた(表4参照)。 As a result of the evaluation, the workability of this laminated film press set was good (see Table 4). No voids were found in the FPC after pressing (see Table 4). This laminated film was not cracked even after hot pressing (see Table 4). The amount of the adhesive between the circuit-exposed film and the CL film oozed out into the circuit pattern was less than 80 μm, which was superior to the conventional release film (see Table 4). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within an allowable range (see Table 4). The crystallinity of the release layer of this laminated film was 20.5% (see Table 4). The laminated film could be easily peeled from the circuit exposed film and the CL film (see Table 4).
 第1ロール230の温度を35℃とし、タッチロール220の温度を70℃とし、第1ロール230に対する第2ロール240の周速比を0.998と設定した以外は実施例12と同様にして積層フィルムを作製し、さらに、その積層フィルムを、表面温度125℃のステンレス板で挟み込んで圧力10MPaで10分間保持することによりアニール処理した後、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 The temperature of the first roll 230 was set to 35 ° C., the temperature of the touch roll 220 was set to 70 ° C., and the peripheral speed ratio of the second roll 240 to the first roll 230 was set to 0.998, as in Example 12. A laminated film was prepared, and the laminated film was further annealed by being sandwiched between stainless plates having a surface temperature of 125 ° C. and held at a pressure of 10 MPa for 10 minutes, and then the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表4参照)。プレス後のFPC中には、ボイドは発見されなかった(表4参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表4参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、80μm未満であり、従来の離型フィルムよりも優れていた(表4参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表4参照)。この積層フィルムの離型層の結晶化度は23.4%であった(表4参照)。積層フィルムは、回路露出フィルム及びCLフィルムから容易に剥離することができた(表4参照)。 As a result of the evaluation, the workability of this laminated film press set was good (see Table 4). No voids were found in the FPC after pressing (see Table 4). This laminated film was not cracked even after hot pressing (see Table 4). The amount of the adhesive between the circuit-exposed film and the CL film oozed out into the circuit pattern was less than 80 μm, which was superior to the conventional release film (see Table 4). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within an allowable range (see Table 4). The crystallinity of the release layer of this laminated film was 23.4% (see Table 4). The laminated film could be easily peeled from the circuit exposed film and the CL film (see Table 4).
 第1ロール230の温度を35℃とし、タッチロール220の温度を70℃とし、第1ロール230に対する第2ロール240の周速比を0.998と設定した以外は実施例12と同様にして積層フィルムを作製し、さらに、その積層フィルムを、表面温度130℃のステンレス板で挟み込んで圧力10MPaで10分間保持することによりアニール処理した後、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 The temperature of the first roll 230 was set to 35 ° C., the temperature of the touch roll 220 was set to 70 ° C., and the peripheral speed ratio of the second roll 240 to the first roll 230 was set to 0.998, as in Example 12. A laminated film was prepared, and the laminated film was further annealed by being sandwiched between stainless plates having a surface temperature of 130 ° C. and held at a pressure of 10 MPa for 10 minutes, and then the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表4参照)。プレス後のFPC中には、ボイドは発見されなかった(表4参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表4参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、80μm未満であり、従来の離型フィルムよりも優れていた(表4参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表4参照)。この積層フィルムの離型層の結晶化度は28.7%であった(表4参照)。積層フィルムは、回路露出フィルム及びCLフィルムから容易に剥離することができた(表4参照)。
(比較例1)
As a result of the evaluation, the workability of the press set of this laminated film was good (see Table 4). No voids were found in the FPC after pressing (see Table 4). This laminated film was not cracked even after hot pressing (see Table 4). The amount of the adhesive between the circuit-exposed film and the CL film oozed out into the circuit pattern was less than 80 μm, which was superior to the conventional release film (see Table 4). The amount of the stain on the end face of the cushion layer was less than 5 mm and was within an allowable range (see Table 4). The crystallinity of the release layer of this laminated film was 28.7% (see Table 4). The laminated film could be easily peeled from the circuit exposed film and the CL film (see Table 4).
(Comparative Example 1)
 クッション層形成ブレンド樹脂として、80重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:5重量%)(住友化学(株)製のアクリフト(登録商標)WD106)と、20重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 As a cushion layer forming blend resin, 80 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived unit content: 5% by weight) (Aclift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) A laminated film was produced in the same manner as in Example 1 except that a dry blend of 20 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) was used, and the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好であった(表5参照)。プレス後のFPC中には、ボイドは発見されなかった(表5参照)。この積層フィルムは、加熱プレス後でも割れが生じることはなかった(表5参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm未満であり、許容範囲内であった(表5参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表5参照)。しかし、完成したFPCから積層フィルムを引き剥がすときに、回路露出フィルムおよびCLフィルムに接触している側の離型層からクッション層が剥離し、FPCを良好な状態で取り出すことができなかった。
(比較例2)
As a result of the evaluation, the workability of this laminated film press set was good (see Table 5). No voids were found in the FPC after pressing (see Table 5). This laminated film did not crack even after hot pressing (see Table 5). The amount of the adhesive between the circuit-exposed film and the CL film oozed out into the circuit pattern was less than 100 μm, and was within an allowable range (see Table 5). The amount of stain on the end face of the cushion layer was less than 5 mm, and was within an allowable range (see Table 5). However, when the laminated film was peeled from the completed FPC, the cushion layer was peeled from the release layer on the side in contact with the circuit exposed film and the CL film, and the FPC could not be taken out in a good state.
(Comparative Example 2)
 クッション層形成ブレンド樹脂として、40重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、50重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:5重量%)(住友化学(株)製のアクリフト(登録商標)WD106)と、10重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 As a cushion layer forming blend resin, 40 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 50 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 5% by weight) (Acrylift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used. A laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は良好とは言えなかった(表5参照)。プレス後のFPC中には、極めて少量であるがボイドが発見された(表5参照)。この積層フィルムは、加熱プレス後、微小な割れが生じていた(表5参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm以上であり、許容範囲外であった(表5参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表5参照)。
(比較例3)
As a result of the evaluation, the workability of the press set of this laminated film was not good (see Table 5). In the FPC after pressing, a very small amount of void was found (see Table 5). This laminated film had micro cracks after heat pressing (see Table 5). The amount of the adhesive between the circuit-exposed film and the CL film oozed out into the circuit pattern was 100 μm or more, which was outside the allowable range (see Table 5). The amount of stain on the end face of the cushion layer was less than 5 mm, and was within an allowable range (see Table 5).
(Comparative Example 3)
 クッション層形成ブレンド樹脂として、70重量部のSPS樹脂(出光興産(株)社製のザレック(登録商標)S104)と、20重量部のエチレン-メタアクリル酸メチル共重合体(メタアクリル酸メチル誘導単位含有量:5重量%)(住友化学(株)製のアクリフト(登録商標)WD106)と、10重量部のポリプロピレン(住友化学(株)製のノーブレンFH1016)とをドライブレンドしたものを用いた以外は実施例1と同様にして積層フィルムを作製し、その積層フィルムの評価を行った。なお、この積層フィルムの離型層の厚みは表裏共に25μmであり、クッション層の厚みは70μmであった。 As a cushion layer forming blend resin, 70 parts by weight of SPS resin (Zarek (registered trademark) S104 manufactured by Idemitsu Kosan Co., Ltd.) and 20 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate derived) Unit content: 5% by weight) (Acrylift (registered trademark) WD106 manufactured by Sumitomo Chemical Co., Ltd.) and 10 parts by weight of polypropylene (Nobrene FH1016 manufactured by Sumitomo Chemical Co., Ltd.) were used. A laminated film was produced in the same manner as in Example 1 except that the laminated film was evaluated. In addition, the thickness of the release layer of this laminated film was 25 μm on both sides, and the thickness of the cushion layer was 70 μm.
 評価の結果、この積層フィルムのプレスセットの作業性は不良であった(表5参照)。プレス後のFPC中には、かなりの数のボイドが発見された(表5参照)。この積層フィルムは、加熱プレス後、比較的大きな割れが生じていた(表5参照)。回路露出フィルムとCLフィルムとの間の接着剤が回路パターンへシミ出した量は、100μm以上であり、許容範囲外であった(表5参照)。クッション層端面のシミ出し量は、5mm未満であり、許容範囲内であった(表5参照)。 As a result of evaluation, the workability of this laminated film press set was poor (see Table 5). A considerable number of voids were found in the FPC after pressing (see Table 5). This laminated film had relatively large cracks after heat pressing (see Table 5). The amount of the adhesive between the circuit-exposed film and the CL film spilled into the circuit pattern was 100 μm or more, which was outside the allowable range (see Table 5). The amount of stain on the end face of the cushion layer was less than 5 mm, and was within an allowable range (see Table 5).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
 本発明に係る積層フィルムは、プレスセットの作業性を良好にすることができると共に、FPC等の良品率を高めることができるという特徴を有し、加圧プレスによる回路露出フィルムへのCLフィルム接着時にCLフィルムを回路パターンの凹凸部に密着させるためにカバーレイフィルムを包むように用いられる離型フィルムとして特に有用である。 The laminated film according to the present invention is characterized in that the workability of the press set can be improved, and the rate of non-defective products such as FPC can be increased, and the CL film is adhered to the circuit exposed film by a pressure press. It is particularly useful as a release film that is sometimes used to wrap a coverlay film in order to bring the CL film into close contact with the uneven portion of the circuit pattern.
 離型フィルムとしては他に(1)積層板製造時に用いられるもの、(2)先端複合材料製品製造時に用いられるもの、(3)スポーツ・レジャー用品製造時に用いられるものが知られているが、本発明に係る積層フィルムは、これらの離型フィルムとしても有用である。なお、積層板製造時に用いられる離型フィルムとは、多層プリント基板を製造する際のプレス成形において、プリント基板とセパレータープレート又は他のプリント基板との間の接着を防止するためにそれらの間に介在させるフィルムである。先端複合材料製品製造時に用いられる離型フィルムとは、例えば、ガラスクロス,炭素繊維又はアラミド繊維とエポキシ樹脂からなるプリプレグを硬化させて種々の製品を製造する際に用いられるフィルムである。スポーツ・レジャー用品製造時に用いられる離型フィルムとは、例えば、釣り竿、ゴルフクラブのシャフト、ウィンドサーフィンのポール等の製造において、プリプレグを円筒状に巻いてオートクレーブ中で硬化させる際にそのプリプレグの上に巻かれるフィルムである。 Other known release films include (1) those used in the production of laminates, (2) those used in the production of advanced composite materials, and (3) those used in the production of sports and leisure goods. The laminated film according to the present invention is also useful as these release films. Note that the release film used in the production of the laminated board is a press-molding process for producing a multilayer printed board, in order to prevent adhesion between the printed board and the separator plate or other printed boards. It is an intervening film. The release film used when manufacturing the advanced composite material product is, for example, a film used when manufacturing various products by curing a prepreg made of glass cloth, carbon fiber or aramid fiber and an epoxy resin. The release film used in the manufacture of sports / leisure goods is, for example, the production of fishing rods, golf club shafts, windsurfing poles, etc. It is a film wound around.
 この積層フィルムは、その他、粘着テープ、両面テープ、マスキングテープ、ラベル、シール、ステッカー、皮膚貼付用湿布剤等の剥離フィルムとしても有用である。 This laminated film is also useful as a release film for adhesive tapes, double-sided tapes, masking tapes, labels, seals, stickers, poultices for skin application, and the like.
 この積層フィルムは、プリント回路基板やセラミックス電子部品、熱硬化性樹脂製品、化粧板等の製造時に用いられる工程フィルムとしても有用である。なお、ここにいう工程フィルムとは、プリント基板やセラミックス電子部品、熱硬化性樹脂製品、化粧板等を製造する時、金属板同士や樹脂同士が接着してしまわないように、成形工程時に金属板同士の間や樹脂同士の間に挟み込まれるフィルムをいい、特に積層板製造時、フレキシブルプリント基板製造時、先端複合材料製品製造時、スポーツ・レジャー用品製造時に好適に用いられるものである。
 この積層フィルムは、包装フィルムしても有用である。
This laminated film is also useful as a process film used in the production of printed circuit boards, ceramic electronic parts, thermosetting resin products, decorative boards and the like. In addition, the process film here refers to a metal in the molding process so that metal plates and resins do not adhere to each other when manufacturing printed circuit boards, ceramic electronic parts, thermosetting resin products, decorative boards, etc. It refers to a film that is sandwiched between boards or between resins, and is particularly suitable for use in the production of laminated boards, the production of flexible printed boards, the production of advanced composite materials, and the production of sports and leisure goods.
This laminated film is also useful as a packaging film.

Claims (7)

  1.  シンジオタクチック構造を有するポリスチレン系樹脂を主成分とする樹脂から形成される第1離型層と、
     60重量部超98重量部以下のポリオレフィン系樹脂と、2重量部以上40重量部未満のシンジオタクチック構造を有するポリスチレン系樹脂とを含有し、前記第1離型層の片側に設けられるクッション層と
    を備える、積層フィルム。
    A first release layer formed from a resin mainly composed of a polystyrene-based resin having a syndiotactic structure;
    A cushion layer provided on one side of the first release layer, comprising a polyolefin resin of more than 60 parts by weight and 98 parts by weight or less and a polystyrene resin having a syndiotactic structure of 2 parts by weight or more and less than 40 parts by weight. A laminated film comprising:
  2.  前記ポリオレフィン系樹脂は、3重量部以上40重量部以下のポリプロピレン樹脂と、20重量部超95重量部以下のエチレン-メタアクリル酸メチル共重合体樹脂とを含有する
    請求項1に記載の積層フィルム。
    2. The laminated film according to claim 1, wherein the polyolefin-based resin contains 3 parts by weight or more and 40 parts by weight or less of a polypropylene resin and 20 parts by weight or more and 95 parts by weight or less of an ethylene-methyl methacrylate copolymer resin. .
  3.  前記エチレン-メタアクリル酸メチル共重合体樹脂には、メタアクリル酸メチルから誘導される単位が5重量%以上14重量%以下含有される
    請求項2に記載の積層フィルム。
    The laminated film according to claim 2, wherein the ethylene-methyl methacrylate copolymer resin contains 5 wt% to 14 wt% of units derived from methyl methacrylate.
  4.  第1離型層は、シンジオタクチック構造を有するポリスチレン系樹脂を主成分とし、示差走査熱量測定法により測定される結晶化度が14.0%以上30.0%未満である樹脂から形成される
    請求項1から3のいずれかに記載に積層フィルム。
    The first release layer is formed of a resin having a polystyrene resin having a syndiotactic structure as a main component and having a crystallinity measured by differential scanning calorimetry of 14.0% or more and less than 30.0%. The laminated film according to any one of claims 1 to 3.
  5.  前記クッション層の第1離型層形成側の反対側に形成される第2離型層をさらに備える
    請求項1から4のいずれかに記載の積層フィルム。
    The laminated film according to any one of claims 1 to 4, further comprising a second release layer formed on a side opposite to the first release layer forming side of the cushion layer.
  6.  前記第2離型層は、前記シンジオタクチック構造を有するポリスチレン系樹脂を主成分とする樹脂から形成される
    請求項5に記載の積層フィルム。
    The said 2nd mold release layer is a laminated film of Claim 5 formed from resin which has as a main component the polystyrene-type resin which has the said syndiotactic structure.
  7.  前記第2離型層を形成する樹脂は、示差走査熱量測定法により測定される結晶化度が14.0%以上30.0%未満である
    請求項6に記載の積層フィルム。
    The laminated film according to claim 6, wherein the resin forming the second release layer has a crystallinity measured by a differential scanning calorimetry of 14.0% or more and less than 30.0%.
PCT/JP2011/000548 2010-02-09 2011-02-01 Laminated film WO2011099252A1 (en)

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JP6062407B2 (en) * 2013-11-14 2017-01-18 株式会社ダイセル Release film, laminate, method for producing the same, and method for producing fuel cell
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JP2014019017A (en) * 2012-07-17 2014-02-03 Sumitomo Bakelite Co Ltd Release film
CN104507680A (en) * 2012-07-17 2015-04-08 住友电木株式会社 Mold release film
CN104584708A (en) * 2012-08-16 2015-04-29 住友电木株式会社 EM-shielding film and method for covering electronic component
KR101799630B1 (en) 2012-08-16 2017-11-20 스미또모 베이크라이트 가부시키가이샤 Em-shielding film and method for covering electronic component

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TWI532598B (en) 2016-05-11
KR20120125459A (en) 2012-11-15

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