WO2014103781A1 - Mold release film and method for producing same - Google Patents

Mold release film and method for producing same Download PDF

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Publication number
WO2014103781A1
WO2014103781A1 PCT/JP2013/083664 JP2013083664W WO2014103781A1 WO 2014103781 A1 WO2014103781 A1 WO 2014103781A1 JP 2013083664 W JP2013083664 W JP 2013083664W WO 2014103781 A1 WO2014103781 A1 WO 2014103781A1
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WO
WIPO (PCT)
Prior art keywords
ethylene
random copolymer
release film
release
adhesive
Prior art date
Application number
PCT/JP2013/083664
Other languages
French (fr)
Japanese (ja)
Inventor
季和 伊藤
Original Assignee
三井化学東セロ株式会社
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Filing date
Publication date
Application filed by 三井化学東セロ株式会社 filed Critical 三井化学東セロ株式会社
Priority to JP2014554333A priority Critical patent/JP6076375B2/en
Publication of WO2014103781A1 publication Critical patent/WO2014103781A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/68—Release sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C39/10—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. casting around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment

Definitions

  • the present invention relates to a release film excellent in releasability (peelability) from adhesives / adhesives such as acrylic resin adhesives / epoxy adhesives, and a method for producing the same.
  • the adhesive tape wound up in a coil shape is subjected to a release treatment on the back surface of the base material so that the adhesive layer can be easily peeled off from the back surface of the base material, or a pressure-sensitive adhesive sheet used for joining various articles.
  • a release liner laminated on the surface of the adhesive layer for the purpose of protecting the adhesive layer until use.
  • a release film is used when a copper-clad laminate or a copper foil is hot-pressed through a prepreg or a heat-resistant film. .
  • a release film is used in the manufacturing process of the flexible printed circuit board.
  • Silicone mold release agents are generally used as mold release agents used for mold release treatments on the back side of such base materials and release liners on the surface of adhesive layers, or release films used in the manufacturing process of printed wiring boards. Has been used.
  • a silicone-based mold release agent such as dimethylpolysiloxane is applied to the surface of the substrate (the surface that does not have an adhesive layer) and crosslinked by irradiation with temperature, light, electron beam, etc.
  • a method for improving the releasability of an adhesive layer in contact with a film is known.
  • a silicone compound such as a low molecular weight silicone resin, siloxane, or silicone oil contained in a silicone-based release agent applied to the surface of the substrate (the surface that does not have an adhesive layer)
  • a silicone-based release agent contained in a silicone-based release agent applied to the surface of the substrate (the surface that does not have an adhesive layer)
  • the adhesive performance is deteriorated by moving to the adjacent adhesive layer.
  • the silicone compound that has migrated to the adhesive layer when used for fixing electronic device components, the silicone compound that has migrated to the adhesive layer generates siloxane gas, which causes a problem of corrosion or malfunction of the electronic device.
  • Patent Document 1 Japanese Patent Laid-Open No. 55-65281
  • a release sheet supporting substrate is separated by an ethylene- ⁇ / olefin copolymer resin having a crystallinity of 40% or less through a polyolefin resin layer.
  • Patent Document 2 Japanese Patent Laid-Open No. 6-99551
  • Patent Document 3 Japanese Patent No. 4531911
  • Patent Document 3 Japanese Patent No. 4531911
  • an ethylene / ⁇ -olefin random copolymer having a density of 0.80 to 0.90 g / cm 3 described in Patent Document 1 or Patent Document 2, or a crystallinity of 40% or less (density When an ethylene / ⁇ -olefin random copolymer of 0.8 to 0.95 g / cm 3 ) is used, the releasability from the acrylic resin-based adhesive / adhesive layer may still be inferior.
  • the problems of the present invention are excellent in releasability (peelability) from adhesives / adhesives such as acrylic resin-based adhesives and epoxy resin adhesives, and the release layer is not sticky,
  • the object is to obtain a release film having contamination.
  • a release layer obtained from an ethylene / ⁇ -olefin random copolymer (A) having a density of 850 to 880 kg / m 3 and a melting point (Tm) of 63 ° C. or less is laminated on one surface of a base material layer.
  • the release layer has a release strength of 0.1 to 1 N / 50 mm with respect to the acrylic resin-based adhesive / adhesive.
  • the present invention also provides a release layer obtained from an ethylene / ⁇ -olefin random copolymer (A) having a density of 850 to 880 kg / m 3 and a melting point (Tm) of 63 ° C. or less on one side of the base material layer.
  • A ethylene / ⁇ -olefin random copolymer
  • Tm melting point
  • the release film of the present invention has a very low peel strength of 0.1 to 0.7 N / 50 mm from an adhesive / adhesive such as an acrylic resin-based adhesive / epoxy adhesive or an epoxy resin-based adhesive, and has excellent releasability
  • an adhesive / adhesive such as an acrylic resin-based adhesive / epoxy adhesive or an epoxy resin-based adhesive
  • the release layer is not sticky and has a non-silicone release layer, there is no contamination with silicon compounds, and the residual adhesion rate indicating non-contamination is good at about 90%.
  • the release film of the present invention has good writing properties of the release layer.
  • the base material layer constituting the release film of the present invention includes various known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, poly-1-butene, etc.), polyester (polyethylene terephthalate, Polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, A film made of polyacrylonitrile, polycarbonate, polystyrene, ionomer, or a mixture thereof.
  • thermoplastic resins preferred are thermoplastic resins having good stretchability and transparency, such as polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyamide, and polypropylene.
  • the base material layer according to the present invention may be an unstretched film or a uniaxially or biaxially stretched film.
  • the base material layer according to the present invention may be a single layer or a multilayer of two or more layers.
  • biaxially stretched films made of polyester such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate are particularly preferable because they are excellent in solvent resistance and heat resistance.
  • the surface of the substrate layer according to the present invention is subjected to surface activation treatment such as corona treatment, plasma treatment, undercoat treatment, primer coat treatment, frame treatment, etc. You may keep going.
  • surface activation treatment such as corona treatment, plasma treatment, undercoat treatment, primer coat treatment, frame treatment, etc. You may keep going.
  • Ethylene ⁇ alpha-olefin random copolymer constituting the release layer constituting the release film of the present invention has a density of 850 ⁇ 880kg / m 3, preferably 855 ⁇ 875kg / m 3, a melting point (Tm ) Is 63 ° C. or lower, preferably 58 ° C. or lower, and carbon number of 3 or more, preferably propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc. Random copolymers with 3 to 10 ⁇ -olefins.
  • the copolymer having a melting point (Tm) of 63 ° C. or lower includes an ethylene / ⁇ -olefin random copolymer that does not clearly show the melting point (Tm), that is, has no melting point (Tm). .
  • An ethylene / ⁇ -olefin random copolymer having a density exceeding 880 kg / m 3 or an ethylene / ⁇ -olefin random copolymer having a melting point (Tm) exceeding 63 ° C. may be used for the release layer of the release film. It is inferior in peelability from the adhesive / adhesive, and even when irradiated with energy rays, the releasability from the adhesive / adhesive is not improved.
  • An ethylene / ⁇ -olefin random copolymer having a density exceeding 880 kg / m 3 or an ethylene / ⁇ -olefin random copolymer having a melting point (Tm) exceeding 63 ° C. is soluble in an organic solvent such as toluene or hexane. Even if it is difficult to form a release layer with a uniform thickness because it is difficult, or even if it is dissolved in an organic solvent, it can be used as a release layer for a release film as described above. In addition, the releasability from the adhesive / adhesive agent is not improved by irradiation with energy rays.
  • the ethylene content is not particularly limited as long as the density and the melting point (Tm) are in the above ranges, but usually in the range of 70 to 92 mol%. It is in.
  • the ethylene / ⁇ -olefin random copolymer (A) according to the present invention usually has an MFR (load: 2160 g, temperature: 190 ° C.) of 0.1 to 50 g / 10 minutes, preferably 0.2 to 20 g / It is in the range of 10 minutes.
  • MFR load: 2160 g, temperature: 190 ° C.
  • the ethylene / ⁇ -olefin random copolymer (A) according to the present invention is a random copolymerization of ethylene and ⁇ -olefin using various known production methods, specifically, vanadium catalysts or metallocene catalysts. Can be manufactured.
  • the ethylene / ⁇ -olefin random copolymer (A) according to the present invention is available from Mitsui Chemicals, Inc. as Toughmer P-0275, P-0375, P-0180, P- They are manufactured and sold under trade names such as 0280, P-0480, P-0680, and as ethylene / 1-butene random copolymers under trade names such as Toughmer A4070S and A1050S.
  • the release film of the present invention is a release film obtained from an ethylene / ⁇ -olefin random copolymer (A) having a density of 850 to 880 kg / m 3 and a melting point (Tm) of 63 ° C. or less on one surface of a base material layer.
  • the release film is a release film characterized in that the release layer has a peel strength of 0.1 to 1 N / 50 mm with respect to the acrylic resin-based adhesive / adhesive.
  • release film of the present invention is obtained from an ethylene / ⁇ -olefin random copolymer (A) having a density of 850 to 880 kg / m 3 and a melting point (Tm) of 63 ° C. or less on one side of the base material layer.
  • the release layer is a release film characterized by being irradiated with energy rays.
  • the thickness of the substrate layer of the release film of the present invention is usually in the range of 10 to 200 ⁇ m, preferably 15 to 100 ⁇ m, more preferably 25 to 50 ⁇ m.
  • the thickness of the release layer of the release film of the present invention is usually in the range of 0.025 to 0.20 ⁇ m, preferably 0.050 to 0.15 ⁇ m, and more preferably 0.075 to 0.125 ⁇ m.
  • the peel strength with an adhesive / adhesive such as an acrylic resin adhesive / epoxy adhesive may exceed 1 N / 50 mm.
  • the thickness of the release layer is increased, the peel strength is further reduced, but the surface state of the release layer is deteriorated, the slipping property is lowered, and the handling property may be lowered.
  • the release film of the present invention is also characterized in that the release layer is as thin as 0.050 to 0.15 ⁇ m.
  • the release film of the present invention usually has a peel strength from an adhesive / adhesive such as an acrylic resin-based adhesive / epoxy resin-based adhesive of 0.1-1 N / 50 mm, preferably 0.1-0. Within the range of 7 N / 50 mm.
  • the release layer obtained from the ethylene / ⁇ -olefin random copolymer (A) according to the present invention With energy rays, acrylic resin-based adhesives, epoxy resin-based adhesives, etc.
  • the reason why the peel strength with the agent is in the range of 0.1 to 1 N / 50 mm, preferably 0.1 to 0.7 N / 50 mm is not clear, but by applying energy rays, the adhesive / adhesive The release strength is reduced, and a release film having excellent peelability can be obtained.
  • the release film of the present invention is obtained by applying and drying a solution of the ethylene / ⁇ -olefin random copolymer (A) according to the present invention on one surface of a previously obtained base material layer, and then ethylene / ⁇ -olefin random It can be produced by irradiating the surface of the copolymer (A) with energy rays.
  • the peel strength from an adhesive / adhesive such as an acrylic resin-based adhesive / epoxy adhesive is 0.1-1 N / 50 mm, preferably 0.1-0.7 N / 50 mm. It is possible to produce a release film having excellent release properties within the range.
  • the thickness of the release layer is 0.025 to 0.20 ⁇ m, preferably 0.8. This is preferable because it can be as thin as 050 to 0.15 ⁇ m.
  • Solvents used for preparing the ethylene / ⁇ -olefin random copolymer (A) solution include aliphatic hydrocarbons such as n-decane, n-heptane, and n-hexane, and aromatics such as toluene and xylene. Examples include hydrocarbons, alicyclic hydrocarbons such as decalin and tetralin, organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, and mixed solvents thereof, and toluene / isobutyl ketone mixed solvent (9/1) is most preferable.
  • a method of applying a solution of the ethylene / ⁇ -olefin random copolymer (A) to the base material layer a method of applying the solution to the surface of the base material layer, a method of immersing the base material layer in the solution, the solution
  • Various known coating methods such as a method of spraying the surface of the substrate layer can be employed.
  • Examples of the method for applying the ethylene / ⁇ -olefin random copolymer (A) solution to the base material layer include an air knife coater, a direct gravure coater, a gravure offset, an arc gravure coater, a gravure reverse and a jet nozzle method.
  • the ethylene / ⁇ -olefin random copolymer (A) in the solution (solid content) may be applied in an amount of 0.05 to 10 g / m 2 , preferably 0.1 to 5 g / m 2 .
  • the application temperature of the solution can be usually carried out at room temperature, for example, a temperature range of 10 to 40 ° C., preferably 15 to 30 ° C.
  • the ethylene / ⁇ -olefin random copolymer (A) If it is difficult to dissolve, it may be heated to a temperature below the boiling point depending on the solvent used.
  • the applied solution is usually dried at a temperature of 70 to 120 ° C., preferably 90 to 100 ° C.
  • the energy ray that irradiates the surface of the ethylene / ⁇ -olefin random copolymer (A) according to the present invention is usually an energy ray having a wavelength range of 0.0001 to 800 nm. Examples thereof include rays, ⁇ rays, ⁇ rays, X rays, visible rays, ultraviolet rays, and electron beams. Among these ionizing radiations, visible light in the wavelength range of 400 to 800 nm, ultraviolet light in the range of 50 to 400 nm, and electron beam in the range of 0.01 to 0.002 nm are easy to handle and equipment is widespread. Therefore, it is preferable.
  • the peel strength from the adhesive / adhesive such as acrylic resin-based adhesive / epoxy resin-based adhesive can be increased.
  • the reason why it is in the range of 0.1 to 1 N / 50 mm, preferably 0.1 to 0.7 N / 50 mm is not clear, but by irradiation with energy rays, an ethylene / ⁇ -olefin random copolymer ( It is inferred that A) aggregates and the peel strength changes.
  • the melting point (Tm) of the ethylene / ⁇ -olefin random copolymer (A) is changed. Absent.
  • the toluene solubility of the copolymer was expressed as follows: ⁇ : dissolved when stirred at room temperature (15-30 ° C.), ⁇ : dissolved when stirred at 40 ° C., x: not dissolved even when stirred at 40 ° C. (3) Peeling force [N / 50mm]
  • the release films obtained in Examples and Comparative Examples were placed on a horizontal table with the release layer facing up, and the polyester adhesive tape having an acrylic adhesive layer on the release layer surface [manufactured by Nitto Denko Corporation, Part No. 31B] was pasted and cut into a size of 200 mm ⁇ 50 mm, and a load was placed on the polyester pressure-sensitive adhesive tape so as to be 20 g / cm 2 , followed by aging at 70 ° C. for 20 hours.
  • the release film is peeled off, and the polyester adhesive tape is pressure-bonded 3 times with a 2 kg rubber roller to a stainless steel plate and heat-treated at 70 ° C. for 2 hours.
  • the adhesive force F is measured according to the method of JIS-C-2107 (adhesive strength to stainless steel plate, 180 ° peeling method). The percentage of F (F / F0 ⁇ 100) relative to the adhesive force F0 when the polyester adhesive tape was directly adhered to and peeled from the stainless steel plate was determined as the residual adhesion rate.
  • Example 1 Ethylene prepared by the above-described method as a release layer on one side of a biaxially stretched polyethylene terephthalate film (trade name Lumirror R58 manufactured by Toray Industries, Inc.) having a thickness of 31 ⁇ m and a stretching ratio of 3 ⁇ 3 as a base film.
  • a solution of the propylene random copolymer (A1) was added to the Mayer bar No. 4 was applied and dried in an oven at 95 ° C. for 20 seconds to obtain a release film precursor.
  • the release layer surface of the precursor was irradiated with ultraviolet rays (UV) (200 mW / cm 2 , 100 mJ / cm 2 ) to obtain a release film.
  • UV ultraviolet rays
  • Example 2 A release film was obtained in the same manner as in Example 1 except that instead of the ethylene / propylene random copolymer (A1) used in Example 1, an ethylene / propylene random copolymer (A2) was used. Table 1 shows the results of the obtained precursor and the release film.
  • Example 3 A release film was obtained in the same manner as in Example 1 except that the ethylene / propylene random copolymer (A1) used in Example 1 was used instead of the ethylene / propylene random copolymer (A1). Table 1 shows the results of the obtained precursor and the release film.
  • Example 4 A release film was obtained in the same manner as in Example 1 except that instead of the ethylene / propylene random copolymer (A1) used in Example 1, an ethylene / propylene random copolymer (A4) was used. Table 1 shows the results of the obtained precursor and the release film.
  • Example 5 A release film was obtained in the same manner as in Example 1, except that the ethylene / propylene random copolymer (A1) used in Example 1 was used instead of the ethylene / propylene random copolymer (A5). Table 1 shows the results of the obtained precursor and the release film.
  • Example 6 A release film was obtained in the same manner as in Example 1 except that the ethylene / propylene random copolymer (A1) used in Example 1 was used instead of the ethylene / propylene random copolymer (A6). Table 1 shows the results of the obtained precursor and the release film.
  • Example 7 A release film was obtained in the same manner as in Example 1 except that the ethylene / 1-butene random copolymer (A7) was used instead of the ethylene / propylene random copolymer (A1) used in Example 1. .
  • Table 1 shows the results of the obtained precursor and the release film.
  • Example 8 A release film was obtained in the same manner as in Example 1 except that the ethylene / 1-butene random copolymer (A8) was used instead of the ethylene / propylene random copolymer (A1) used in Example 1. . Table 1 shows the results of the obtained precursor and the release film.
  • Example 2 A release film was obtained in the same manner as in Example 1 except that the propylene / ethylene random copolymer (C2) was used instead of the ethylene / propylene random copolymer (A1) used in Example 1. Table 1 shows the results of the obtained precursor and the release film.
  • Example 3 A release film was obtained in the same manner as in Example 1 except that the propylene / ethylene random copolymer (C3) was used instead of the ethylene / propylene random copolymer (A1) used in Example 1. Table 1 shows the results of the obtained precursor and the release film.
  • the precursor film before UV irradiation has a release layer peel strength of 4.8 to 13.9 N / 15 mm, whereas the release layer is irradiated with UV.
  • (Release film) shows that the release layer has a release strength as low as 0.18 to 0.60 N / 50 mm, and a release film having excellent release properties can be obtained.
  • the ethylene / ⁇ -olefin random copolymer having a density and melting point (Tm) exceeding the upper limit used in Comparative Example 1 was insoluble in a solvent such as toluene and could not be applied. Further, as shown in Comparative Examples 2 and 3, when a propylene / ethylene random copolymer having a melting point (Tm) exceeding 63 ° C. was used, the peel strength did not change even when irradiated with UV, and the releasability was improved. It was not possible to obtain a release film excellent in.
  • the release film of the present invention is excellent in releasability, and can be used as a release film for acrylic adhesives and epoxy adhesives. It is used for a release film for a process such as a substrate, a flexible printed circuit board, a multilayer printed circuit board.

Abstract

[Problem] The problem addressed by the present invention is to obtain a mold release film having superior mold release characteristics (peeling characteristics) from an adhesive agent such as an acrylic resin-based adhesive agent, an epoxy resin-based adhesive agent, or the like, has no stickiness of a mold release layer, and has non-staining properties. [Solution] The present invention pertains to: a mold release film characterized by resulting from laminating, to one surface of a substrate layer, a mold release layer obtained from an ethylene/α-olefin random copolymer (A) having a density of 850-880 kg/m3 and a melting point (Tm) of no greater than 63°C, the peel strength of the mold release layer with respect to an acrylic resin-based adhesive agent being 0.1-1 N/50 mm; and a method for producing the mold release film.

Description

離型フィルム、及びその製造方法Release film and method for producing the same
　本発明は、アクリル樹脂系粘・接着剤、エポキシ樹脂系接着剤などの粘・接着剤との離型性（剥離性）に優れる離型フィルム、及びその製造方法に関する。 The present invention relates to a release film excellent in releasability (peelability) from adhesives / adhesives such as acrylic resin adhesives / epoxy adhesives, and a method for producing the same.
　コイル状に巻き上げた粘着テープには、基材の背面から粘着層を剥離しやすくなるように基材の背面に離型処理が施されたり、各種物品の接合に使用される感圧性接着シートには使用時まで粘着層を保護する目的で粘着層の表面に離型ライナーが積層されている。 The adhesive tape wound up in a coil shape is subjected to a release treatment on the back surface of the base material so that the adhesive layer can be easily peeled off from the back surface of the base material, or a pressure-sensitive adhesive sheet used for joining various articles. Has a release liner laminated on the surface of the adhesive layer for the purpose of protecting the adhesive layer until use.
　また、プリント配線基板、フレキシブルプリント配線基板、多層プリント配線基板などの製造工程において、プリプレグ又は耐熱フィルムを介して銅張り積層板又は銅箔を熱プレスする際には離型フィルムが使用されている。また、フレキシブルプリント基板の製造工程において、電気回路を形成したフレキシブルプリント基板本体に、エポキシ樹脂系熱硬化型接着剤又は熱硬化性接着シートによってカバーレイフィルム又は補強板を熱プレス接着する際に、カバーレイフィルムとプレス熱板とが接着するのを防止するために、離型フィルムが用いられている。 Moreover, in the manufacturing process of a printed wiring board, a flexible printed wiring board, a multilayer printed wiring board, etc., a release film is used when a copper-clad laminate or a copper foil is hot-pressed through a prepreg or a heat-resistant film. . Moreover, in the manufacturing process of the flexible printed circuit board, when the cover lay film or the reinforcing plate is hot press bonded to the flexible printed circuit board body on which the electric circuit is formed by the epoxy resin thermosetting adhesive or the thermosetting adhesive sheet, In order to prevent the cover lay film and the press hot plate from adhering to each other, a release film is used.
　このような基材の背面の離型処理や粘着層の表面の離型ライナー等に用いる離型剤、あるいはプリント配線基板の製造工程に用いられる離型フィルムとしては、シリコーン系離型剤が一般的に使用されている。例えば、ジメチルポリシロキサン等のシリコーン系離型剤を基材の表面（粘着層を有しない面）に塗布し、温度、光、電子線等を照射して架橋させ、基材の表面と離型フィルムと接する粘着層との離型性を改良する方法が知られている。 Silicone mold release agents are generally used as mold release agents used for mold release treatments on the back side of such base materials and release liners on the surface of adhesive layers, or release films used in the manufacturing process of printed wiring boards. Has been used. For example, a silicone-based mold release agent such as dimethylpolysiloxane is applied to the surface of the substrate (the surface that does not have an adhesive layer) and crosslinked by irradiation with temperature, light, electron beam, etc. A method for improving the releasability of an adhesive layer in contact with a film is known.
　しかしながら、コイル状に巻き上げた粘着テープの場合、基材の表面（粘着層を有しない面）に塗布されたシリコーン系離型剤に含まれる低分子量のシリコーン樹脂、シロキサン、シリコーンオイル等のシリコーン化合物が隣接する粘着層に移行して粘着性能を低下させる問題がある。また、感圧性接着シートの場合、電子機器部品の固定等に用いると、粘着層に移行したシリコーン化合物がシロキサンガスを発生し、電子機器の腐食または誤動作の原因となる問題がある。 However, in the case of a pressure-sensitive adhesive tape wound up in a coil shape, a silicone compound such as a low molecular weight silicone resin, siloxane, or silicone oil contained in a silicone-based release agent applied to the surface of the substrate (the surface that does not have an adhesive layer) However, there is a problem that the adhesive performance is deteriorated by moving to the adjacent adhesive layer. In the case of a pressure-sensitive adhesive sheet, when used for fixing electronic device components, the silicone compound that has migrated to the adhesive layer generates siloxane gas, which causes a problem of corrosion or malfunction of the electronic device.
　かかる問題点を解決する方法として、シリコーン系離型剤に替えて、密度が０．８０～０．９０ｇ／ｃｍ3、融点が８０℃以下のエチレン・α‐オレフィンランダム共重合体を用いる方法（特許文献１：特開昭５５－６５２８１号公報）、離型シート用支持基材に対して、ポリオレフィン樹脂層を介して、結晶化度４０％以下のエチレン－α・オレフィン共重合体樹脂による離型剤層が形成されていることを特徴とする離型シートとする方法（特許文献２：特開平６－９９５５１号公報）が提案されている。更に、エチレン・α‐オレフィンランダム共重合体の押出加工性を改良する方法として、離型剤層に、密度が０．８０～０．９０ｇ／ｃｍ3のエチレン・α‐オレフィンランダム共重合体とメタロセン触媒を用いて合成された密度が０．９０２～０．９１２ｇ／ｃｍ3であるポリエチレン樹脂との組成物を用いる方法（特許文献３：特許第４５３１９１１号公報）が提案されている。 As a method for solving such a problem, a method of using an ethylene / α-olefin random copolymer having a density of 0.80 to 0.90 g / cm 3 and a melting point of 80 ° C. or less in place of the silicone mold release agent ( (Patent Document 1: Japanese Patent Laid-Open No. 55-65281), a release sheet supporting substrate is separated by an ethylene-α / olefin copolymer resin having a crystallinity of 40% or less through a polyolefin resin layer. A method for forming a release sheet (Patent Document 2: Japanese Patent Laid-Open No. 6-99551) has been proposed in which a mold agent layer is formed. Further, as a method for improving the extrusion processability of the ethylene / α-olefin random copolymer, an ethylene / α-olefin random copolymer having a density of 0.80 to 0.90 g / cm 3 and There has been proposed a method (Patent Document 3: Japanese Patent No. 4531911) using a composition with a polyethylene resin synthesized using a metallocene catalyst and having a density of 0.902 to 0.912 g / cm 3 .
　しかしながら、離型層として、特許文献１あるいは特許文献２に記載された密度が０．８０～０．９０ｇ／ｃｍ3のエチレン・α‐オレフィンランダム共重合体、あるいは結晶化度４０％以下（密度０．８～０．９５ｇ／ｃｍ3）のエチレン・α‐オレフィンランダム共重合体を用いた場合は、未だ、アクリル樹脂系粘・接着剤層との離型性に劣る虞がある。 However, as a release layer, an ethylene / α-olefin random copolymer having a density of 0.80 to 0.90 g / cm 3 described in Patent Document 1 or Patent Document 2, or a crystallinity of 40% or less (density When an ethylene / α-olefin random copolymer of 0.8 to 0.95 g / cm 3 ) is used, the releasability from the acrylic resin-based adhesive / adhesive layer may still be inferior.
特開昭５５－６５２８１号公報JP-A-55-65281 特開平６－９９５５１号公報JP-A-6-99551 特許第４５３１９１１号公報Japanese Patent No. 4531911
　本発明の課題は、アクリル樹脂系粘・接着剤、エポキシ樹脂系接着剤などの粘・接着剤との離型性（剥離性）に優れ、且つ、離型層のべとつきもなく、また、非汚染性を有する離型フィルム得ることにある。 The problems of the present invention are excellent in releasability (peelability) from adhesives / adhesives such as acrylic resin-based adhesives and epoxy resin adhesives, and the release layer is not sticky, The object is to obtain a release film having contamination.
　本発明は、基材層の片面に、密度が８５０～８８０ｋｇ／ｍ3、融点（Ｔｍ）が６３℃以下のエチレン・α‐オレフィンランダム共重合体（Ａ）から得られる離型層が積層されてなり、当該離型層が、アクリル樹脂系粘・接着剤との剥離強度が０．１～１Ｎ／５０ｍｍであることを特徴とする離型フィルムに係る。 In the present invention, a release layer obtained from an ethylene / α-olefin random copolymer (A) having a density of 850 to 880 kg / m 3 and a melting point (Tm) of 63 ° C. or less is laminated on one surface of a base material layer. The release layer has a release strength of 0.1 to 1 N / 50 mm with respect to the acrylic resin-based adhesive / adhesive.
　また、本発明は、基材層の片面に、密度が８５０～８８０ｋｇ／ｍ3、融点（Ｔｍ）が６３℃以下のエチレン・α‐オレフィンランダム共重合体（Ａ）から得られる離型層が、エネルギー線が照射されてなることを特徴とする離型フィルム及び、その製造方法に係る。 The present invention also provides a release layer obtained from an ethylene / α-olefin random copolymer (A) having a density of 850 to 880 kg / m 3 and a melting point (Tm) of 63 ° C. or less on one side of the base material layer. The present invention relates to a release film that is irradiated with energy rays and a method for producing the same.
　本発明の離型フィルムは、アクリル樹脂系粘・接着剤、エポキシ樹脂系接着剤などの粘・接着剤との剥離強度が、０．１～０．７Ｎ／５０ｍｍと極めて低く、剥離性に優れると共に、且つ、離型層のべとつきもなく、また、非シリコーン系の離型層を有するので、珪素化合物による汚染性がなく、非汚染性を示す残留接着率も約９０％と良好である。また、本発明の離型フィルムは、離型層の加筆性も良好である。 The release film of the present invention has a very low peel strength of 0.1 to 0.7 N / 50 mm from an adhesive / adhesive such as an acrylic resin-based adhesive / epoxy adhesive or an epoxy resin-based adhesive, and has excellent releasability In addition, since the release layer is not sticky and has a non-silicone release layer, there is no contamination with silicon compounds, and the residual adhesion rate indicating non-contamination is good at about 90%. Further, the release film of the present invention has good writing properties of the release layer.
　＜基材層＞
　本発明の離型フィルムを構成する基材層は、種々公知の熱可塑性樹脂、例えば、ポリオレフィン（ポリエチレン、ポリプロピレン、ポリ４－メチル・１－ペンテン、ポリ１－ブテン等）、ポリエステル（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、ポリエチレンナフタレート等）、ポリアミド（ナイロン－６、ナイロン－６６、ポリメタキシレンアジパミド等）、ポリ塩化ビニル、ポリイミド、エチレン・酢酸ビニル共重合体もしくはその鹸化物、ポリビニルアルコール、ポリアクリロニトリル、ポリカーボネート、ポリスチレン、アイオノマー、あるいはこれらの混合物等からなるフィルムである。これら熱可塑性樹脂の中でも、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、ポリエチレンナフタレートなどのポリエステル、ポリアミド、ポリプロピレン等、延伸性、透明性が良好な熱可塑性樹脂が好ましい。 <Base material layer>
The base material layer constituting the release film of the present invention includes various known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, poly-1-butene, etc.), polyester (polyethylene terephthalate, Polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, A film made of polyacrylonitrile, polycarbonate, polystyrene, ionomer, or a mixture thereof. Among these thermoplastic resins, preferred are thermoplastic resins having good stretchability and transparency, such as polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyamide, and polypropylene.
　本発明に係る基材層は、無延伸フィルムであっても、一軸あるいは二軸延伸フィルムであってもよい。
　また、本発明に係る基材層は一層でも二層以上の多層であってもよい。 The base material layer according to the present invention may be an unstretched film or a uniaxially or biaxially stretched film.
The base material layer according to the present invention may be a single layer or a multilayer of two or more layers.
　これら基材層の中でも、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、ポリエチレンナフタレートなどのポリエステルからなる二軸延伸フィルムが、耐溶剤性、耐熱性に優れるので、特に好ましい。 Among these base material layers, biaxially stretched films made of polyester such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate are particularly preferable because they are excellent in solvent resistance and heat resistance.
　本発明に係る基材層は、離型層との接着性を改良するために、その表面を、例えば、コロナ処理、プラズマ処理、アンダーコート処理、プライマーコート処理、フレーム処理等の表面活性化処理を行っておいてもよい。 In order to improve the adhesion with the release layer, the surface of the substrate layer according to the present invention is subjected to surface activation treatment such as corona treatment, plasma treatment, undercoat treatment, primer coat treatment, frame treatment, etc. You may keep going.
　＜エチレン・α‐オレフィンランダム共重合体（Ａ）＞
　本発明の離型フィルムを構成する離型層を構成するエチレン・α‐オレフィンランダム共重合体（Ａ）は、密度が８５０～８８０ｋｇ／ｍ3、好ましくは８５５～８７５ｋｇ／ｍ3、融点（Ｔｍ）が６３℃以下、好ましくは５８℃以下のエチレンと炭素数３以上、好ましくはプロピレン、１－ブテン、１－ヘキセン、４－メチル－１－ペンテン、１－オクテン、１－デセンなどの炭素数３～１０のα－オレフィンとのランダム共重合体である。 <Ethylene / α-olefin random copolymer (A)>
Ethylene · alpha-olefin random copolymer constituting the release layer constituting the release film of the present invention (A) has a density of 850 ~ 880kg / m 3, preferably 855 ~ 875kg / m 3, a melting point (Tm ) Is 63 ° C. or lower, preferably 58 ° C. or lower, and carbon number of 3 or more, preferably propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc. Random copolymers with 3 to 10 α-olefins.
　本発明において、融点（Ｔｍ）が６３℃以下である共重合体とは、融点（Ｔｍ）を明確に示さない、すなわち、融点（Ｔｍ）を有しないエチレン・α－オレフィンランダム共重合体を含む。 In the present invention, the copolymer having a melting point (Tm) of 63 ° C. or lower includes an ethylene / α-olefin random copolymer that does not clearly show the melting point (Tm), that is, has no melting point (Tm). .
　密度が８８０ｋｇ／ｍ3を超えるエチレン・α－オレフィンランダム共重合体、あるいは融点（Ｔｍ）が６３℃を超えるエチレン・α－オレフィンランダム共重合体は、離型フィルムの離型層に用いても粘・接着剤との剥離性に劣り、また、エネルギー線を照射しても、粘・接着剤との離型性は改良されない。 An ethylene / α-olefin random copolymer having a density exceeding 880 kg / m 3 or an ethylene / α-olefin random copolymer having a melting point (Tm) exceeding 63 ° C. may be used for the release layer of the release film. It is inferior in peelability from the adhesive / adhesive, and even when irradiated with energy rays, the releasability from the adhesive / adhesive is not improved.
　また、密度が８８０ｋｇ／ｍ3を超えるエチレン・α－オレフィンランダム共重合体、あるいは融点（Ｔｍ）が６３℃を超えるエチレン・α－オレフィンランダム共重合体は、トルエン、ヘキサンなどの有機溶剤に溶け難いので、均一な厚さの離型層を形成することが困難であったり、仮に有機溶剤に溶けたとしても、上記のように、離型フィルムの離型層に用いても粘・接着剤との剥離性に劣り、また、エネルギー線を照射しても、粘・接着剤との離型性は改良されない。 An ethylene / α-olefin random copolymer having a density exceeding 880 kg / m 3 or an ethylene / α-olefin random copolymer having a melting point (Tm) exceeding 63 ° C. is soluble in an organic solvent such as toluene or hexane. Even if it is difficult to form a release layer with a uniform thickness because it is difficult, or even if it is dissolved in an organic solvent, it can be used as a release layer for a release film as described above. In addition, the releasability from the adhesive / adhesive agent is not improved by irradiation with energy rays.
　本発明に係るエチレン・α‐オレフィンランダム共重合体（Ａ）は、密度及び融点（Ｔｍ）が上記範囲にある限り、エチレン含有量は特に限定はされないが、通常、７０～９２モル％の範囲にある。 In the ethylene / α-olefin random copolymer (A) according to the present invention, the ethylene content is not particularly limited as long as the density and the melting point (Tm) are in the above ranges, but usually in the range of 70 to 92 mol%. It is in.
　本発明に係るエチレン・α‐オレフィンランダム共重合体（Ａ）は、通常、ＭＦＲ（荷重：２１６０ｇ、温度：１９０℃）が、０．１～５０ｇ／１０分、好ましくは０．２～２０ｇ／１０分の範囲にある。 The ethylene / α-olefin random copolymer (A) according to the present invention usually has an MFR (load: 2160 g, temperature: 190 ° C.) of 0.1 to 50 g / 10 minutes, preferably 0.2 to 20 g / It is in the range of 10 minutes.
　本発明に係るエチレン・α‐オレフィンランダム共重合体（Ａ）は、種々公知の製造方法、具体的には、バナジウム触媒、あるいはメタロセン触媒を用いて、エチレンとα－オレフィンとをランダム共重合させることにより製造し得る。 The ethylene / α-olefin random copolymer (A) according to the present invention is a random copolymerization of ethylene and α-olefin using various known production methods, specifically, vanadium catalysts or metallocene catalysts. Can be manufactured.
　また、本発明に係るエチレン・α‐オレフィンランダム共重合体（Ａ）は、三井化学株式会社から、エチレン・プロピレンランダム共重合体として、タフマーＰ－０２７５、Ｐ－０３７５、Ｐ－０１８０、Ｐ－０２８０、Ｐ－０４８０、Ｐ－０６８０などの商品名で、及び、エチレン・１－ブテンランダム共重合体として、タフマーＡ４０７０Ｓ、Ａ１０５０Ｓなどの商品名で製造・販売されている。 Further, the ethylene / α-olefin random copolymer (A) according to the present invention is available from Mitsui Chemicals, Inc. as Toughmer P-0275, P-0375, P-0180, P- They are manufactured and sold under trade names such as 0280, P-0480, P-0680, and as ethylene / 1-butene random copolymers under trade names such as Toughmer A4070S and A1050S.
　＜離型フィルム＞
　本発明の離型フィルムは、基材層の片面に、密度が８５０～８８０ｋｇ／ｍ3、融点（Ｔｍ）が６３℃以下のエチレン・α‐オレフィンランダム共重合体（Ａ）から得られる離型層が積層されてなり、当該離型層が、アクリル樹脂系粘・接着剤との剥離強度が０．１～１Ｎ／５０ｍｍであることを特徴とする離型フィルムである。 <Release film>
The release film of the present invention is a release film obtained from an ethylene / α-olefin random copolymer (A) having a density of 850 to 880 kg / m 3 and a melting point (Tm) of 63 ° C. or less on one surface of a base material layer. The release film is a release film characterized in that the release layer has a peel strength of 0.1 to 1 N / 50 mm with respect to the acrylic resin-based adhesive / adhesive.
　本発明の離型フィルムの他の態様は、基材層の片面に、密度が８５０～８８０ｋｇ／ｍ3、融点（Ｔｍ）が６３℃以下エチレン・α‐オレフィンランダム共重合体（Ａ）から得られる離型層が、エネルギー線が照射されてなることを特徴とする離型フィルムである。 Another embodiment of the release film of the present invention is obtained from an ethylene / α-olefin random copolymer (A) having a density of 850 to 880 kg / m 3 and a melting point (Tm) of 63 ° C. or less on one side of the base material layer. The release layer is a release film characterized by being irradiated with energy rays.
　本発明の離型フィルムの基材層の厚さは、通常、１０～２００μｍ、好ましくは１５～１００μｍ、さらに好ましくは２５～５０μｍの範囲にある。
　本発明の離型フィルムの離型層の厚さは、通常、０．０２５～０．２０μｍ、好ましくは０．０５０～０．１５μｍ、さらに好ましくは０．０７５～０．１２５μｍの範囲にある。離型層の厚さが０．０２５μｍを下回る場合は、アクリル樹脂系粘・接着剤、エポキシ樹脂系接着剤などの粘・接着剤との剥離強度が、１Ｎ／５０ｍｍを超える場合がある。一方、離型層の厚さが増すとより剥離強度は低下するが、剥離層の表面の状態が悪くなり、滑り性が低下して、ハンドリング性が低下する虞がある。 The thickness of the substrate layer of the release film of the present invention is usually in the range of 10 to 200 μm, preferably 15 to 100 μm, more preferably 25 to 50 μm.
The thickness of the release layer of the release film of the present invention is usually in the range of 0.025 to 0.20 μm, preferably 0.050 to 0.15 μm, and more preferably 0.075 to 0.125 μm. When the thickness of the release layer is less than 0.025 μm, the peel strength with an adhesive / adhesive such as an acrylic resin adhesive / epoxy adhesive may exceed 1 N / 50 mm. On the other hand, when the thickness of the release layer is increased, the peel strength is further reduced, but the surface state of the release layer is deteriorated, the slipping property is lowered, and the handling property may be lowered.
　本発明の離型フィルムは、また、離型層の厚さを０．０５０～０．１５μｍと薄いことを特徴の一つとする。
　本発明の離型フィルムは、通常、アクリル樹脂系粘・接着剤、エポキシ樹脂系接着剤などの粘・接着剤との剥離強度が、０．１～１Ｎ／５０ｍｍ、好ましくは０．１～０．７Ｎ／５０ｍｍの範囲にある。 The release film of the present invention is also characterized in that the release layer is as thin as 0.050 to 0.15 μm.
The release film of the present invention usually has a peel strength from an adhesive / adhesive such as an acrylic resin-based adhesive / epoxy resin-based adhesive of 0.1-1 N / 50 mm, preferably 0.1-0. Within the range of 7 N / 50 mm.
　本発明に係る前記エチレン・α‐オレフィンランダム共重合体（Ａ）から得られる離型層にエネルギー線を照射することにより、アクリル樹脂系粘・接着剤、エポキシ樹脂系接着剤などの粘・接着剤との剥離強度が、０．１～１Ｎ／５０ｍｍ、好ましくは０．１～０．７Ｎ／５０ｍｍの範囲になる理由は定かではないが、エネルギー線が照射されることにより、粘・接着剤との剥離強度が低下し、剥離性に優れる離型フィルムとすることができる。 By irradiating the release layer obtained from the ethylene / α-olefin random copolymer (A) according to the present invention with energy rays, acrylic resin-based adhesives, epoxy resin-based adhesives, etc. The reason why the peel strength with the agent is in the range of 0.1 to 1 N / 50 mm, preferably 0.1 to 0.7 N / 50 mm is not clear, but by applying energy rays, the adhesive / adhesive The release strength is reduced, and a release film having excellent peelability can be obtained.
　＜離型フィルムの製造方法＞
　本発明の離型フィルムは、予め得られた基材層の片面に、本発明に係るエチレン・α－オレフィンランダム共重合体（Ａ）の溶液を塗布・乾燥した後、エチレン・α－オレフィンランダム共重合体（Ａ）の表面にエネルギー線を照射することにより製造し得る。 <Method for producing release film>
The release film of the present invention is obtained by applying and drying a solution of the ethylene / α-olefin random copolymer (A) according to the present invention on one surface of a previously obtained base material layer, and then ethylene / α-olefin random It can be produced by irradiating the surface of the copolymer (A) with energy rays.
　かかる製造方法により、アクリル樹脂系粘・接着剤、エポキシ樹脂系接着剤などの粘・接着剤との剥離強度が、０．１～１Ｎ／５０ｍｍ、好ましくは０．１～０．７Ｎ／５０ｍｍの範囲にある離型性に優れる離型フィルムを製造し得る。 By such a production method, the peel strength from an adhesive / adhesive such as an acrylic resin-based adhesive / epoxy adhesive is 0.1-1 N / 50 mm, preferably 0.1-0.7 N / 50 mm. It is possible to produce a release film having excellent release properties within the range.
　本発明の製造方法は、エチレン・α－オレフィンランダム共重合体（Ａ）の溶液を塗布・乾燥する方法であるので、離型層の厚さを０．０２５～０．２０μｍ、好ましくは０．０５０～０．１５μｍと薄くすることができるので好ましい。 Since the production method of the present invention is a method of applying and drying a solution of the ethylene / α-olefin random copolymer (A), the thickness of the release layer is 0.025 to 0.20 μm, preferably 0.8. This is preferable because it can be as thin as 050 to 0.15 μm.
　エチレン・α－オレフィンランダム共重合体（Ａ）の溶液を調整するために用いる溶媒は、ｎ－デカン、ｎ－ヘプタン、ｎ－ヘキサンなどの脂肪族炭化水素、トルエン、キシレンなどのなどの芳香族炭化水素、デカリン、テトラリンなどの脂環族炭化水素、メチルエチルケトン、メチルイソブチルケトンなどの有機溶媒あるいはそれらの混合溶媒が挙げられるが、トルエン・イソブチルケトン混合溶剤（９／１）が最も好ましい。 Solvents used for preparing the ethylene / α-olefin random copolymer (A) solution include aliphatic hydrocarbons such as n-decane, n-heptane, and n-hexane, and aromatics such as toluene and xylene. Examples include hydrocarbons, alicyclic hydrocarbons such as decalin and tetralin, organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, and mixed solvents thereof, and toluene / isobutyl ketone mixed solvent (9/1) is most preferable.
　基材層にエチレン・α－オレフィンランダム共重合体（Ａ）の溶液を塗布する方法としては、当該溶液を基材層表面に塗布する方法、当該溶液に基材層を浸漬する方法、当該溶液を基材層表面に噴霧する方法等種々公知の塗工方法を採り得る。 As a method of applying a solution of the ethylene / α-olefin random copolymer (A) to the base material layer, a method of applying the solution to the surface of the base material layer, a method of immersing the base material layer in the solution, the solution Various known coating methods such as a method of spraying the surface of the substrate layer can be employed.
　基材層にエチレン・α－オレフィンランダム共重合体（Ａ）の溶液を塗布する方法としては、例えば、エアーナイフコーター、ダイレクトグラビアコーター、グラビアオフセット、アークグラビアコーター、グラビアリバースおよびジェットノズル方式等のグラビアコーター、トップフィードリバースコーター、ボトムフィードリバースコーターおよびノズルフィードリバースコーター等のリバースロールコーター、５本ロールコーター、リップコーター、バーコーター、バーリバースコーター、ダイコーター等種々公知の塗工機を用いて、エチレン・α－オレフィンランダム共重合体（Ａ）の溶液中（固形分）の量で０．０５～１０ｇ／ｍ2、好ましくは０．１～５ｇ／ｍ2となるよう塗布すればよい。 Examples of the method for applying the ethylene / α-olefin random copolymer (A) solution to the base material layer include an air knife coater, a direct gravure coater, a gravure offset, an arc gravure coater, a gravure reverse and a jet nozzle method. Using various known coating machines such as gravure coaters, top feed reverse coaters, bottom feed reverse coaters and nozzle feed reverse coaters, reverse roll coaters, 5-roll coaters, lip coaters, bar coaters, bar reverse coaters, die coaters The ethylene / α-olefin random copolymer (A) in the solution (solid content) may be applied in an amount of 0.05 to 10 g / m 2 , preferably 0.1 to 5 g / m 2 .
　溶液の塗布温度は、通常、常温、例えば、１０～４０℃、好ましくは１５～３０℃の温度範囲で行い得るが、エチレン・α－オレフィンランダム共重合体（Ａ）が、常温で、前記溶媒に溶解し難い場合は、用いる溶媒にもよるが、沸点未満の温度に加温してもよい。 The application temperature of the solution can be usually carried out at room temperature, for example, a temperature range of 10 to 40 ° C., preferably 15 to 30 ° C. The ethylene / α-olefin random copolymer (A) If it is difficult to dissolve, it may be heated to a temperature below the boiling point depending on the solvent used.
　また、塗布した溶液は、通常、７０～１２０℃、好ましくは９０～１００℃の温度で乾燥する。
　本発明に係るエチレン・α－オレフィンランダム共重合体（Ａ）の表面を照射するエネルギー線は、通常、波長領域が０．０００１～８００ｎｍの範囲のエネルギー線であり、かかるエネルギー線としては、α線、β線、γ線、Ｘ線、可視光線、紫外線、電子線等が上げられる。これらの電離性放射線の中でも、波長領域が４００～８００ｎｍの範囲の可視光線、５０～４００ｎｍの範囲の紫外線および０．０１～０．００２ｎｍの範囲の電子線が、取り扱いが容易で装置も普及しているので好ましい。 The applied solution is usually dried at a temperature of 70 to 120 ° C., preferably 90 to 100 ° C.
The energy ray that irradiates the surface of the ethylene / α-olefin random copolymer (A) according to the present invention is usually an energy ray having a wavelength range of 0.0001 to 800 nm. Examples thereof include rays, β rays, γ rays, X rays, visible rays, ultraviolet rays, and electron beams. Among these ionizing radiations, visible light in the wavelength range of 400 to 800 nm, ultraviolet light in the range of 50 to 400 nm, and electron beam in the range of 0.01 to 0.002 nm are easy to handle and equipment is widespread. Therefore, it is preferable.
　本発明に係る前記エチレン・α‐オレフィンランダム共重合体（Ａ）にエネルギー線を照射することにより、アクリル樹脂系粘・接着剤、エポキシ樹脂系接着剤などの粘・接着剤との剥離強度が、０．１～１Ｎ／５０ｍｍ、好ましくは０．１～０．７Ｎ／５０ｍｍの範囲になる理由は定かではないが、エネルギー線が照射されることにより、エチレン・α‐オレフィンランダム共重合体（Ａ）が凝集して、剥離強度が変化するのではないかと推察する。 By irradiating the ethylene / α-olefin random copolymer (A) according to the present invention with energy rays, the peel strength from the adhesive / adhesive such as acrylic resin-based adhesive / epoxy resin-based adhesive can be increased. The reason why it is in the range of 0.1 to 1 N / 50 mm, preferably 0.1 to 0.7 N / 50 mm is not clear, but by irradiation with energy rays, an ethylene / α-olefin random copolymer ( It is inferred that A) aggregates and the peel strength changes.
　なお、本発明に係る前記エチレン・α‐オレフィンランダム共重合体（Ａ）にエネルギー線を照射しても、エチレン・α‐オレフィンランダム共重合体（Ａ）の融点（Ｔｍ）に変化は見られない。 Even when the ethylene / α-olefin random copolymer (A) according to the present invention is irradiated with energy rays, the melting point (Tm) of the ethylene / α-olefin random copolymer (A) is changed. Absent.
　次に、本発明を実施例によりさらに具体的に説明するが、本発明はこれら実施例により何等限定されるものではない。
　実施例及び比較例で用いたエチレン・α－オレフィンランダム共重合体を以下に示す。 EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples.
The ethylene / α-olefin random copolymers used in Examples and Comparative Examples are shown below.
　（１）エチレン・α－オレフィンランダム共重合体（Ａ）
　（１－１）エチレン・プロピレンランダム共重合体（Ａ１）
　密度＝８６１ｋｇ／ｍ3、融点（Ｔｍ）＝２８℃、ＭＦＲ＝２．９ｇ／１０分（三井化学株式会社製：商品名　タフマーＰ－０２７５）。 (1) Ethylene / α-olefin random copolymer (A)
(1-1) Ethylene / propylene random copolymer (A1)
Density = 861 kg / m 3 , melting point (Tm) = 28 ° C., MFR = 2.9 g / 10 minutes (manufactured by Mitsui Chemicals, Inc., trade name: Toughmer P-0275).
　（１－２）エチレン・プロピレンランダム共重合体（Ａ２）
　密度＝８５９ｋｇ／ｍ3、融点（Ｔｍ）＝２９℃、ＭＦＲ＝１．８ｇ／１０分（三井化学株式会社製：商品名　タフマーＰ－０３７５）。 (1-2) Ethylene / propylene random copolymer (A2)
Density = 859 kg / m 3 , melting point (Tm) = 29 ° C., MFR = 1.8 g / 10 minutes (manufactured by Mitsui Chemicals, Inc., trade name: TAFMER P-0375).
　（１－３）エチレン・プロピレンランダム共重合体（Ａ３）
　密度＝８６９ｋｇ／ｍ3、融点（Ｔｍ）＝４２℃、ＭＦＲ＝４．４ｇ／１０分（三井化学株式会社製：商品名　タフマーＰ－０１８０）。 (1-3) Ethylene / propylene random copolymer (A3)
Density = 869 kg / m 3 , melting point (Tm) = 42 ° C., MFR = 4.4 g / 10 minutes (manufactured by Mitsui Chemicals, Inc., trade name: Toughmer P-0180).
　（１－４）エチレン・プロピレンランダム共重合体（Ａ４）
　密度＝８６９ｋｇ／ｍ3、融点（Ｔｍ）＝３８℃、ＭＦＲ＝３．０ｇ／１０分（三井化学株式会社製：商品名　タフマーＰ－０２８０）。 (1-4) Ethylene / propylene random copolymer (A4)
Density = 869 kg / m 3 , melting point (Tm) = 38 ° C., MFR = 3.0 g / 10 min (manufactured by Mitsui Chemicals, Inc., trade name: TAFMER P-0280).
　（１－５）エチレン・プロピレンランダム共重合体（Ａ５）
　密度＝８６９ｋｇ／ｍ3、融点（Ｔｍ）＝４３℃、ＭＦＲ＝１．１ｇ／１０分（三井化学株式会社製：商品名　タフマーＰ－０４８０）。 (1-5) Ethylene / propylene random copolymer (A5)
Density = 869 kg / m 3 , melting point (Tm) = 43 ° C., MFR = 1.1 g / 10 minutes (manufactured by Mitsui Chemicals, Inc., trade name: TAFMER P-0480).
　（１－６）エチレン・プロピレンランダム共重合体（Ａ６）
　密度＝８６９ｋｇ／ｍ3、融点（Ｔｍ）＝４４℃、ＭＦＲ＝０．６ｇ／１０分（三井化学株式会社製：商品名　タフマーＰ－０６８０）。 (1-6) Ethylene / propylene random copolymer (A6)
Density = 869 kg / m 3 , melting point (Tm) = 44 ° C., MFR = 0.6 g / 10 minutes (manufactured by Mitsui Chemicals, Inc., trade name: TAFMER P-0680).
　（１－７）エチレン・１－ブテンランダム共重合体（Ａ７）
　密度＝８７０ｋｇ／ｍ3、融点（Ｔｍ）＝５２℃、ＭＦＲ＝３．６ｇ／１０分（三井化学株式会社製：商品名　タフマーＡ４０７０Ｓ）。 (1-7) Ethylene / 1-butene random copolymer (A7)
Density = 870 kg / m 3 , melting point (Tm) = 52 ° C., MFR = 3.6 g / 10 minutes (manufactured by Mitsui Chemicals, Inc., trade name: Toughmer A4070S).
　（１－８）エチレン・１－ブテンランダム共重合体（Ａ８）
　密度＝８６０ｋｇ／ｍ3、融点（Ｔｍ）＝３８℃、ＭＦＲ＝１．２ｇ／１０分（三井化学株式会社製：商品名　タフマーＡ１０５０Ｓ）。 (1-8) Ethylene / 1-butene random copolymer (A8)
Density = 860 kg / m 3 , melting point (Tm) = 38 ° C., MFR = 1.2 g / 10 min (manufactured by Mitsui Chemicals, Inc., trade name: TAFMER A1050S).
　（２）エチレン・α－オレフィンランダム共重合体
　（２－１）エチレン・１－ブテンランダム共重合体（Ｃ１）
　密度＝８９３ｋｇ／ｍ3、融点（Ｔｍ）＝８２℃、ＭＦＲ＝３．６ｇ／１０分（三井化学株式会社製：商品名　タフマーＡ４０９０Ｓ）。 (2) Ethylene / α-olefin random copolymer (2-1) Ethylene / 1-butene random copolymer (C1)
Density = 893 kg / m 3 , melting point (Tm) = 82 ° C., MFR = 3.6 g / 10 minutes (manufactured by Mitsui Chemicals, Inc., trade name: TAFMER A4090S).
　（３）プロピレン・エチレンランダム共重合体
　（３－１）プロピレン・エチレンランダム共重合体（Ｃ２）
　密度＝８６２ｋｇ／ｍ3、融点（Ｔｍ）＝１０８℃、ＭＦＲ＝１．４ｇ／１０分（エクソンモービルケミカル社製：商品名　Ｖｉｓｔａｍａｘｘ６１０２）。 (3) Propylene / ethylene random copolymer (3-1) Propylene / ethylene random copolymer (C2)
Density = 862 kg / m 3 , melting point (Tm) = 108 ° C., MFR = 1.4 g / 10 minutes (ExxonMobil Chemical Company, trade name: Vistamaxx6102).
　（３－２）プロピレン・エチレンランダム共重合体（Ｃ３）
　密度＝８６３ｋｇ／ｍ3、融点（Ｔｍ）＝１０７℃、ＭＦＲ＝９．１ｇ／１０分（エクソンモービルケミカル社製：商品名　Ｖｉｓｔａｍａｘｘ６２０２）。 (3-2) Propylene / ethylene random copolymer (C3)
Density = 863 kg / m 3 , melting point (Tm) = 107 ° C., MFR = 9.1 g / 10 min (ExxonMobil Chemical Co., Ltd., trade name: Vistamaxx6202).
　実施例及び比較例における物性値等は、以下の評価方法により求めた。
　＜評価方法＞
　（１）融点（Ｔｍ）（℃）の測定
　試料５ｍｇを精秤し、ティ・エイ・インスツルメンツ社製の示差走査型熱量計（ＤＳＣ　Ｑ１００）を用いて、－５０℃から１０℃／分の昇温速度で２００℃まで加熱し１０分間保持した後、１０℃／分の降温速度で－５０℃まで冷却し５分間保持した後、再度１０℃／分の昇温速度で昇温し、融解吸熱曲線が示す最大ピークの温度を融点とした。 The physical property values and the like in Examples and Comparative Examples were obtained by the following evaluation methods.
<Evaluation method>
(1) Measurement of melting point (Tm) (° C) 5 mg of a sample was accurately weighed and increased from -50 ° C to 10 ° C / min using a differential scanning calorimeter (DSC Q100) manufactured by TI Instruments. Heat to 200 ° C. at a temperature rate and hold for 10 minutes, then cool to −50 ° C. at a rate of 10 ° C./min and hold for 5 minutes, then increase the temperature again at a rate of 10 ° C./min to endotherm The temperature of the maximum peak indicated by the curve was taken as the melting point.
　（２）溶液の調製
　上記記載のエチレン・α－オレフィンランダム共重合体を常温で、トルエン／メチルイソブチルケトン＝９／１（質量比）の濃度１質量％の溶液として調製した。 (2) Preparation of Solution The ethylene / α-olefin random copolymer described above was prepared at room temperature as a 1% by mass solution of toluene / methyl isobutyl ketone = 9/1 (mass ratio).
　なお、共重合体のトルエン溶解性は、○：常温（１５～３０℃）で撹拌すると溶解、△：４０℃で撹拌すると溶解、×：４０℃で撹拌しても溶解しない、で表わした。
　（３）剥離力［Ｎ／５０ｍｍ］
　実施例及び比較例で得た離型フィルムを水平台の上に離型層を上にして載置し、離型層面にアクリル系粘着剤層を有するポリエステル粘着テープ[日東電工（株）製、品番Ｎｏ．３１Ｂ]のアクリル系粘着剤層を貼り付けて２００ｍｍ×５０ｍｍの大きさにカットし、さらにそのポリエステル粘着テープの上から２０ｇ／ｃｍ2となるように荷重を載せ、７０℃で２０時間エージングした。 The toluene solubility of the copolymer was expressed as follows: ○: dissolved when stirred at room temperature (15-30 ° C.), Δ: dissolved when stirred at 40 ° C., x: not dissolved even when stirred at 40 ° C.
(3) Peeling force [N / 50mm]
The release films obtained in Examples and Comparative Examples were placed on a horizontal table with the release layer facing up, and the polyester adhesive tape having an acrylic adhesive layer on the release layer surface [manufactured by Nitto Denko Corporation, Part No. 31B] was pasted and cut into a size of 200 mm × 50 mm, and a load was placed on the polyester pressure-sensitive adhesive tape so as to be 20 g / cm 2 , followed by aging at 70 ° C. for 20 hours.
　エージング後、引張試験機にて引張速度３００ｍｍ／分で１８０°剥離を行い、剥離が安定した領域における平均剥離荷重をポリエステル粘着テープ幅で除した値を剥離力として求めた。
　（４）残留接着率［％］：
　実施例及び比較例で得た離型フィルムを水平台の上に離型層を上にして載置し、離型層面にアクリル系粘着剤層を有するポリエステル粘着テープ[日東電工（株）製、品番Ｎｏ．３１Ｂ]のアクリル系粘着剤層を貼り付けて２００ｍｍ×５０ｍｍの大きさにカットし、さらにそのポリエステル粘着テープの上から２０ｇ／ｃｍ2となるように荷重を載せ、７０℃で２０時間エージングした。 After aging, 180 ° peeling was performed at a tensile speed of 300 mm / min with a tensile tester, and the value obtained by dividing the average peeling load in the region where peeling was stable by the width of the polyester adhesive tape was determined as the peeling force.
(4) Residual adhesion rate [%]:
The release films obtained in Examples and Comparative Examples were placed on a horizontal table with the release layer facing up, and the polyester adhesive tape having an acrylic adhesive layer on the release layer surface [manufactured by Nitto Denko Corporation, Part No. 31B] was pasted and cut into a size of 200 mm × 50 mm, and a load was placed on the polyester pressure-sensitive adhesive tape so as to be 20 g / cm 2 , followed by aging at 70 ° C. for 20 hours.
　エージング後、離型フィルムを剥がし、ポリエステル粘着テープをステンレス板に２ｋｇゴムローラーにて３往復圧着し、７０℃で２時間加熱処理する。次いで、ＪＩＳ－Ｃ－２１０７（ステンレス板に対する粘着力、１８０°引き剥がし法）の方法に準じて接着力Ｆを測定する。ポリエステル粘着テープを直接ステンレス板に粘着・剥離した際の接着力Ｆ０に対するＦの百分率（Ｆ／Ｆ０×１００）を残留接着率として求めた。 After aging, the release film is peeled off, and the polyester adhesive tape is pressure-bonded 3 times with a 2 kg rubber roller to a stainless steel plate and heat-treated at 70 ° C. for 2 hours. Next, the adhesive force F is measured according to the method of JIS-C-2107 (adhesive strength to stainless steel plate, 180 ° peeling method). The percentage of F (F / F0 × 100) relative to the adhesive force F0 when the polyester adhesive tape was directly adhered to and peeled from the stainless steel plate was determined as the residual adhesion rate.
　〔実施例１〕
　基材フィルムとして、厚さ：３１μｍ、延伸倍率：３×３の二軸延伸ポリエチレンテレフタレートフィルム（東レ株式会社製　商品名　ルミラー　Ｒ５８）の片面に、離型層として、前記記載の方法で調整したエチレン・プロピレンランダム共重合体（Ａ１）の溶液を、メイヤーバーＮｏ．４を用いて、塗工し、９５℃のオーブンで２０秒乾燥させて離型フィルムの前駆体を得た。
　ついで、当該前駆体の離型層面に、紫外線（ＵＶ）照射（２００ｍＷ／ｃｍ2、１００ｍＪ／ｃｍ2）して、離型フィルムを得た。
　得られた前駆体、及び離型フィルムを前記記載の方法で評価した。結果を表１に示す。 [Example 1]
Ethylene prepared by the above-described method as a release layer on one side of a biaxially stretched polyethylene terephthalate film (trade name Lumirror R58 manufactured by Toray Industries, Inc.) having a thickness of 31 μm and a stretching ratio of 3 × 3 as a base film. A solution of the propylene random copolymer (A1) was added to the Mayer bar No. 4 was applied and dried in an oven at 95 ° C. for 20 seconds to obtain a release film precursor.
Subsequently, the release layer surface of the precursor was irradiated with ultraviolet rays (UV) (200 mW / cm 2 , 100 mJ / cm 2 ) to obtain a release film.
The obtained precursor and release film were evaluated by the method described above. The results are shown in Table 1.
　〔実施例２〕
　実施例１で用いたエチレン・プロピレンランダム共重合体（Ａ１）に替えて、エチレン・プロピレンランダム共重合体（Ａ２）を用いる以外は、実施例１と同様に行い離型フィルムを得た。得られた前駆体、及び離型フィルムの結果を表１に示す。 [Example 2]
A release film was obtained in the same manner as in Example 1 except that instead of the ethylene / propylene random copolymer (A1) used in Example 1, an ethylene / propylene random copolymer (A2) was used. Table 1 shows the results of the obtained precursor and the release film.
　〔実施例３〕
　実施例１で用いたエチレン・プロピレンランダム共重合体（Ａ１）に替えて、エチレン・プロピレンランダム共重合体（Ａ３）を用いる以外は、実施例１と同様に行い離型フィルムを得た。得られた前駆体、及び離型フィルムの結果を表１に示す。 Example 3
A release film was obtained in the same manner as in Example 1 except that the ethylene / propylene random copolymer (A1) used in Example 1 was used instead of the ethylene / propylene random copolymer (A1). Table 1 shows the results of the obtained precursor and the release film.
　〔実施例４〕
　実施例１で用いたエチレン・プロピレンランダム共重合体（Ａ１）に替えて、エチレン・プロピレンランダム共重合体（Ａ４）を用いる以外は、実施例１と同様に行い離型フィルムを得た。得られた前駆体、及び離型フィルムの結果を表１に示す。 Example 4
A release film was obtained in the same manner as in Example 1 except that instead of the ethylene / propylene random copolymer (A1) used in Example 1, an ethylene / propylene random copolymer (A4) was used. Table 1 shows the results of the obtained precursor and the release film.
　〔実施例５〕
　実施例１で用いたエチレン・プロピレンランダム共重合体（Ａ１）に替えて、エチレン・プロピレンランダム共重合体（Ａ５）を用いる以外は、実施例１と同様に行い離型フィルムを得た。得られた前駆体、及び離型フィルムの結果を表１に示す。 Example 5
A release film was obtained in the same manner as in Example 1, except that the ethylene / propylene random copolymer (A1) used in Example 1 was used instead of the ethylene / propylene random copolymer (A5). Table 1 shows the results of the obtained precursor and the release film.
　〔実施例６〕
　実施例１で用いたエチレン・プロピレンランダム共重合体（Ａ１）に替えて、エチレン・プロピレンランダム共重合体（Ａ６）を用いる以外は、実施例１と同様に行い離型フィルムを得た。得られた前駆体、及び離型フィルムの結果を表１に示す。 Example 6
A release film was obtained in the same manner as in Example 1 except that the ethylene / propylene random copolymer (A1) used in Example 1 was used instead of the ethylene / propylene random copolymer (A6). Table 1 shows the results of the obtained precursor and the release film.
　〔実施例７〕
　実施例１で用いたエチレン・プロピレンランダム共重合体（Ａ１）に替えて、エチレン・１－ブテンランダム共重合体（Ａ７）を用いる以外は、実施例１と同様に行い離型フィルムを得た。得られた前駆体、及び離型フィルムの結果を表１に示す。 Example 7
A release film was obtained in the same manner as in Example 1 except that the ethylene / 1-butene random copolymer (A7) was used instead of the ethylene / propylene random copolymer (A1) used in Example 1. . Table 1 shows the results of the obtained precursor and the release film.
　〔実施例８〕
　実施例１で用いたエチレン・プロピレンランダム共重合体（Ａ１）に替えて、エチレン・１－ブテンランダム共重合体（Ａ８）を用いる以外は、実施例１と同様に行い離型フィルムを得た。得られた前駆体、及び離型フィルムの結果を表１に示す。 Example 8
A release film was obtained in the same manner as in Example 1 except that the ethylene / 1-butene random copolymer (A8) was used instead of the ethylene / propylene random copolymer (A1) used in Example 1. . Table 1 shows the results of the obtained precursor and the release film.
　〔比較例１〕
　実施例１で用いたエチレン・プロピレンランダム共重合体（Ａ１）に替えて、エチレン・１－ブテンランダム共重合体（Ｃ１）を用いたが、Ｃ１はトルエン／メチルイソブチルケトンに不溶であり、離型フィルムを得ることができなかった。 [Comparative Example 1]
An ethylene / 1-butene random copolymer (C1) was used in place of the ethylene / propylene random copolymer (A1) used in Example 1, but C1 was insoluble in toluene / methylisobutylketone and separated. A mold film could not be obtained.
　〔比較例２〕
　実施例１で用いたエチレン・プロピレンランダム共重合体（Ａ１）に替えて、プロピレン・エチレンランダム共重合体（Ｃ２）を用いる以外は、実施例１と同様に行い離型フィルムを得た。得られた前駆体、及び離型フィルムの結果を表１に示す。 [Comparative Example 2]
A release film was obtained in the same manner as in Example 1 except that the propylene / ethylene random copolymer (C2) was used instead of the ethylene / propylene random copolymer (A1) used in Example 1. Table 1 shows the results of the obtained precursor and the release film.
　〔比較例３〕
　実施例１で用いたエチレン・プロピレンランダム共重合体（Ａ１）に替えて、プロピレン・エチレンランダム共重合体（Ｃ３）を用いる以外は、実施例１と同様に行い離型フィルムを得た。得られた前駆体、及び離型フィルムの結果を表１に示す。 [Comparative Example 3]
A release film was obtained in the same manner as in Example 1 except that the propylene / ethylene random copolymer (C3) was used instead of the ethylene / propylene random copolymer (A1) used in Example 1. Table 1 shows the results of the obtained precursor and the release film.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から明らかなように、ＵＶを照射する前の前駆体フィルムは、離型層の剥離強度が４．８～１３．９Ｎ／１５ｍｍであるのに対し、離型層にＵＶを照射したフィルム（離型フィルム）は、離型層の剥離強度が０．１８～０．６０Ｎ／５０ｍｍと低剥離強度になり、離型性に優れる離型フィルムが得られることが判る。 As is apparent from Table 1, the precursor film before UV irradiation has a release layer peel strength of 4.8 to 13.9 N / 15 mm, whereas the release layer is irradiated with UV. (Release film) shows that the release layer has a release strength as low as 0.18 to 0.60 N / 50 mm, and a release film having excellent release properties can be obtained.
　一方、比較例１で用いた密度および融点（Ｔｍ）が上限を超えるエチレン・α－オレフィンランダム共重合体はトルエンなどの溶媒に不溶で、塗布することができなかった。
　また、比較例２、３に示すように、融点（Ｔｍ）が６３℃を超えるプロピレン・エチレンランダム共重合体を用いた場合は、ＵＶを照射しても剥離強度は変化せず、離型性に優れる離型フィルムを得ることはできなかった。 On the other hand, the ethylene / α-olefin random copolymer having a density and melting point (Tm) exceeding the upper limit used in Comparative Example 1 was insoluble in a solvent such as toluene and could not be applied.
Further, as shown in Comparative Examples 2 and 3, when a propylene / ethylene random copolymer having a melting point (Tm) exceeding 63 ° C. was used, the peel strength did not change even when irradiated with UV, and the releasability was improved. It was not possible to obtain a release film excellent in.
　本発明の離型フィルムは、離型性に優れており、アクリル粘着剤やエポキシ粘着剤に対する離型フィルムとして使用ができ、半導体製造工程のバックグラインドテープやダイシングテープの離型フィルムや、プリント配線基板、フレキシブルプリント配線基板、多層プリント配線基板などの工程用離型フィルムに用いられる。 The release film of the present invention is excellent in releasability, and can be used as a release film for acrylic adhesives and epoxy adhesives. It is used for a release film for a process such as a substrate, a flexible printed circuit board, a multilayer printed circuit board.

Claims (8)

  1. 　基材層の片面に、密度が８５０～８８０ｋｇ／ｍ3、融点（Ｔｍ）が６３℃以下のエチレン・α‐オレフィンランダム共重合体（Ａ）から得られる離型層が積層されてなり、当該離型層が、アクリル樹脂系粘・接着剤との剥離強度が０．１～１Ｎ／５０ｍｍであることを特徴とする離型フィルム。 A release layer obtained from an ethylene / α-olefin random copolymer (A) having a density of 850 to 880 kg / m 3 and a melting point (Tm) of 63 ° C. or less is laminated on one side of the base material layer. A release film, wherein the release layer has a peel strength of 0.1 to 1 N / 50 mm from the acrylic resin-based adhesive / adhesive.
  2. 　基材層の片面に、密度が８５０～８８０ｋｇ／ｍ3、融点（Ｔｍ）が６３℃以下のエチレン・α‐オレフィンランダム共重合体（Ａ）から得られる離型層が、エネルギー線が照射されてなることを特徴とする離型フィルム。 A release layer obtained from an ethylene / α-olefin random copolymer (A) having a density of 850 to 880 kg / m 3 and a melting point (Tm) of 63 ° C. or less is irradiated with energy rays on one side of the base material layer. A release film characterized by comprising
  3. 　基材層が、ポリエステルフィルムである請求項１または２に記載の離型フィルム。 The release film according to claim 1 or 2, wherein the base material layer is a polyester film.
  4. 　離型層の厚さが、０．０１μｍ以上～１．０μｍ未満である請求項１～３の何れか１項に記載の離型フィルム。 The release film according to any one of claims 1 to 3, wherein a thickness of the release layer is 0.01 µm or more and less than 1.0 µm.
  5. 　エネルギー線が紫外線である請求項２に記載の離型フィルム。 The release film according to claim 2, wherein the energy rays are ultraviolet rays.
  6. 　基材層の片面に、離型層として、密度が８５０～８８０ｋｇ／ｍ3、融点（Ｔｍ）が６３℃以下のエチレン・α‐オレフィンランダム共重合体（Ａ）の溶液を塗布・乾燥した後、エチレン・α‐オレフィンランダム共重合体（Ａ）の表面にエネルギー線を照射することを特徴とする離型フィルムの製造方法。 After applying and drying a solution of an ethylene / α-olefin random copolymer (A) having a density of 850 to 880 kg / m 3 and a melting point (Tm) of 63 ° C. or less as a release layer on one side of the base material layer A method for producing a release film, wherein the surface of the ethylene / α-olefin random copolymer (A) is irradiated with energy rays.
  7. 　エネルギー線が紫外線である請求項６に記載の離型フィルムの製造方法。 The method for producing a release film according to claim 6, wherein the energy rays are ultraviolet rays.
  8. 　離型層が、アクリル樹脂系粘・接着剤との剥離強度が０．１～１Ｎ／５０ｍｍである請求項６または７に記載の離型フィルムの製造方法。 The method for producing a release film according to claim 6 or 7, wherein the release layer has a peel strength of 0.1 to 1 N / 50 mm with respect to the acrylic resin-based adhesive / adhesive.
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