WO2014155895A1 - グリーンシート製造用剥離フィルム - Google Patents

グリーンシート製造用剥離フィルム Download PDF

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Publication number
WO2014155895A1
WO2014155895A1 PCT/JP2013/085206 JP2013085206W WO2014155895A1 WO 2014155895 A1 WO2014155895 A1 WO 2014155895A1 JP 2013085206 W JP2013085206 W JP 2013085206W WO 2014155895 A1 WO2014155895 A1 WO 2014155895A1
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WIPO (PCT)
Prior art keywords
agent layer
release agent
green sheet
release film
release
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Application number
PCT/JP2013/085206
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English (en)
French (fr)
Japanese (ja)
Inventor
知巳 深谷
慎也 市川
Original Assignee
リンテック株式会社
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Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to KR1020157026162A priority Critical patent/KR102093769B1/ko
Priority to SG11201507895WA priority patent/SG11201507895WA/en
Priority to CN201380075174.8A priority patent/CN105102194B/zh
Publication of WO2014155895A1 publication Critical patent/WO2014155895A1/ja
Priority to PH12015502250A priority patent/PH12015502250A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D135/00—Coating compositions based on 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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C09J2433/005—Presence of (meth)acrylic polymer in the release coating

Definitions

  • the present invention relates to a release film for producing a green sheet.
  • a release film for producing a green sheet is used to form a green sheet.
  • the release film is generally composed of a base material and a release agent layer.
  • the green sheet is manufactured by applying a ceramic slurry in which ceramic particles and a binder resin are dispersed and dissolved in an organic solvent on such a release film and drying the slurry. Moreover, the manufactured green sheet peels from a peeling film, and is used for manufacture of a ceramic capacitor.
  • the release film is generally stored and transported in a roll-shaped state, and is used by being unwound from the roll-shaped state when forming a green sheet.
  • static electricity is generated on the surface of the release film, and foreign matter such as dust adheres to the release film due to the generated static electricity.
  • a pinhole would generate
  • the smaller the unevenness on the surface of the release film the more remarkable the generation of static electricity as described above.
  • An object of the present invention is to provide a release film for producing a green sheet that can prevent the occurrence of pinholes and partial thickness variations on the surface of the green sheet and can produce a highly reliable green sheet. There is to do.
  • a release film for producing a green sheet used for producing a green sheet A substrate having a first surface and a second surface; A release agent layer provided on the first surface of the substrate;
  • the release agent layer comprises an active energy ray-curable compound (A) having at least one reactive functional group selected from the group consisting of a (meth) acryloyl group, an alkenyl group and a maleimide group, and a polyorganosiloxane (B )
  • a carbon nanomaterial (C) is applied to the coating layer formed by applying a release agent layer forming material on the first surface side and irradiated with active energy rays.
  • the arithmetic average roughness Ra 1 of the outer surface of the release agent layer is 8 nm or less, and the maximum protrusion height Rp 1 of the outer surface of the release agent layer is 50 nm or less. Release film.
  • the polyorganosiloxane (B) is a polyorganosiloxane having a linear or branched molecular chain, and at the end and / or side chain of the molecular chain, a (meth) acryloyl group, an alkenyl group and (1) to (3) wherein a reactive functional group having at least one selected from the group consisting of maleimide groups is bonded to a silicon atom in the molecular chain directly or via a divalent linking group.
  • the release film for producing a green sheet according to any one of 1).
  • the present invention it is possible to provide a release film for producing a green sheet that is excellent in the smoothness of the outer surface of the release agent layer and has excellent antistatic properties and peelability. Thereby, it can prevent that the unevenness
  • the release film for producing the green sheet of the present invention has moderate conductivity. For this reason, the resistance value of the surface of the release film for producing a green sheet can be lowered. Thereby, it can suppress that static electricity generate
  • FIG. 1 is a cross-sectional view of a release film for producing a green sheet of the present invention.
  • the release film for producing a green sheet of the present invention is used for producing a green sheet.
  • the manufactured green sheet is used for manufacture of a ceramic capacitor etc., for example.
  • FIG. 1 is a cross-sectional view of a release film for producing a green sheet of the present invention.
  • the upper side in FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.
  • the release film 1 for producing a green sheet includes a base material 11 having a first surface 111 and a second surface 112, and a release provided on the first surface 111 of the base material 11. And an agent layer 12. That is, as shown in FIG. 1, the release film 1 for producing a green sheet has a two-layer structure in which a base material 11 and a release agent layer 12 are laminated so as to be joined to each other in this order.
  • the green sheet when manufacturing a green sheet using the peeling film 1 for green sheet manufacture, applies the ceramic slurry which melt
  • the release film 1 for producing a green sheet has a substrate 11 and a release agent layer 12.
  • the release agent layer 12 includes an active energy ray-curable compound (A) having a predetermined reactive functional group, a polyorganosiloxane (B), and a carbon nanomaterial (C). Is applied to the first surface 111 side of the base material 11 and irradiated with active energy rays, and the release agent layer forming material is formed on the outer surface 121 of the release agent layer 12.
  • the arithmetic average roughness Ra 1 is 8 nm or less, and the maximum protrusion height Rp 1 of the outer surface 121 is 50 nm or less.
  • a release film 1 for producing a green sheet having excellent smoothness of the outer surface 121 of the release agent layer 12 and having antistatic properties and releasability. And if a green sheet is manufactured using this release film 1 for green sheet manufacture, it can prevent that the pinhole, the variation in partial thickness, etc. generate
  • the release agent layer 12 has appropriate conductivity due to the action of the carbon nanomaterial (C). For this reason, the resistance value of the surface of the release film 1 for producing a green sheet can be lowered. Thereby, when unwinding the release film 1 for manufacturing a green sheet, the generation of static electricity can be suppressed. As a result, it is possible to prevent foreign matters such as dust from adhering to the surface of the release film 1 for producing a green sheet, and it is possible to prevent occurrence of pinholes due to the attached foreign matter.
  • the release agent layer 12 exhibits excellent release properties due to the action of the polyorganosiloxane (B). For this reason, the release agent layer 12 removes the green sheet from the release film 1 for producing the green sheet by a synergistic effect of the release property by the action of the polyorganosiloxane (B) and the antistatic property by the action of the carbon nanomaterial (C). When peeling, it is possible to prevent the green sheet from being damaged or wrinkled.
  • the release agent layer forming material containing the active energy ray-curable compound (A) having a predetermined reactive functional group has appropriate fluidity and shape retention. For this reason, if the release agent layer 12 composed of the release agent layer forming material is used, the unevenness on the surface of the substrate 11 can be easily embedded (cancelled). Moreover, the embedded state can be reliably held. As a result, the outer surface 121 of the release agent layer 12 is excellent in smoothness. For this reason, generation
  • the arithmetic average roughness Ra 1 and the maximum protrusion height Rp 1 of the outer surface 121 of the release agent layer 12 are those described above, for example, even when a thin green sheet less than 1 ⁇ m is manufactured, The unevenness of the outer surface 121 of the release agent layer 12 can be prevented from being transferred to the green sheet. Thereby, it is possible to obtain a highly reliable green sheet in which the occurrence of pinholes or the like is prevented on the surface of the green sheet.
  • each layer which comprises the peeling film 1 for green sheet manufacture which concerns on this embodiment is demonstrated one by one.
  • the base material 11 has a function of imparting physical strength such as rigidity and flexibility to the release film 1 for producing a green sheet (hereinafter sometimes simply referred to as “release film 1”).
  • the base material 11 has a first surface 111 and a second surface 112.
  • the material constituting the substrate 11 is not particularly limited, and examples thereof include polyester resins such as polybutylene terephthalate resin, polyethylene terephthalate resin and polyethylene naphthalate resin, polyolefin resins such as polypropylene resin and polymethylpentene resin, and polycarbonate. Examples thereof include a film made of plastic.
  • the substrate 11 may be a single layer film or a multilayer film of two or more layers of the same type or different types. Among these, a polyester film is particularly preferable, and a biaxially stretched polyethylene terephthalate film is more preferable.
  • the polyester film is less prone to dust and the like during its processing and use. Therefore, for example, when a green sheet is manufactured using the release film 1 manufactured using a polyester film, it is possible to effectively prevent a ceramic slurry coating failure due to dust or the like. As a result, a green sheet with fewer pinholes and the like can be manufactured.
  • the base material 11 may contain a filler or the like in addition to the above materials.
  • the filler include silica, titanium oxide, calcium carbonate, kaolin, aluminum oxide, and the like, and one or more of these can be used in combination.
  • the substrate 11 is preferably an arithmetic mean roughness Ra 0 of the first surface 111 is 2 ⁇ 80 nm, the arithmetic mean roughness Ra 0 of the first surface 111, and even a 5 ⁇ 50 nm More preferred.
  • the release agent layer 12 smoothed by filling the unevenness of the first surface 111 is formed. Therefore, if the arithmetic average roughness Ra 0 is within the above range, the smoothing action is particularly remarkable.
  • the arithmetic average roughness Ra 0 of the first surface 111 exceeds the upper limit value, depending on the constituent material of the release agent layer forming material and the like, peeling may occur in order to sufficiently fill the unevenness of the first surface 111. It may be necessary to make the film thickness of the agent layer 12 relatively large.
  • maximum projection height Rp 0 of the first surface 111 is 10 ⁇ 700 nm, the maximum projection height Rp 0 of the first surface 111 and even more preferably 20 ⁇ 500 nm.
  • the base material 11 preferably has an arithmetic average roughness Ra 2 of the second surface 112 of 5 to 40 nm, and more preferably has an arithmetic average roughness Ra 2 of the second surface 112 of 10 to 30 nm. preferable.
  • the maximum protrusion height Rp 2 of the second surface 112 of the substrate 11 is preferably 60 to 500 nm.
  • the maximum projection height Rp 2 is less than the lower limit value, during storage of the green sheet (thin film) formed before the peeling film 1, when winding the release film 1 before the green sheet formation, It is easy to entrain air and it is easy to cause winding slippage. Therefore, handling of the release film 1 becomes difficult. Moreover, the base material 11 and the release agent layer 12 are in close contact with each other, and it is difficult to sufficiently prevent blocking.
  • the maximum projection height Rp 2 exceeds the upper limit, when winding the release film 1 after the green sheet formation, the projection shape of the second surface 112 of the substrate 11 in contact with the green sheet on the green sheet It will be transcribed. For this reason, pinholes and partial thickness variations may occur in the green sheet, and it becomes difficult to sufficiently maintain the smoothness of the green sheet.
  • the maximum protrusion height Rp 2 of the second surface 112 of the substrate 11 is preferably 60 to 500 nm, more preferably 80 to 400 nm, and even more preferably 100 to 300 nm. . Thereby, the above-mentioned effect becomes more remarkable.
  • the height Rp 2 is a value obtained by measurement with a surface roughness measuring instrument SV3000S4 (stylus type) manufactured by Mitutoyo Corporation in accordance with JIS B0601-1994.
  • the “arithmetic average roughness and maximum protrusion height” refer to values obtained by measurement as described above.
  • the average film thickness of the substrate 11 is not particularly limited, but is preferably 10 to 300 ⁇ m, and more preferably 15 to 200 ⁇ m. Thereby, it is possible to make the release film 1 particularly excellent in resistance to tearing, breaking, etc. while making the flexibility of the release film 1 moderate.
  • the release agent layer 12 is provided on the first surface 111 of the substrate 11.
  • the release agent layer 12 has a function of imparting peelability and antistatic property to the release film 1.
  • the release agent layer 12 is a layer formed by irradiating the release agent layer forming material with an active energy ray and curing.
  • the release agent layer 12 is made of a release agent layer forming material.
  • the release agent layer forming material includes an active energy ray-curable compound (A) having at least one reactive functional group selected from the group consisting of a (meth) acryloyl group, an alkenyl group and a maleimide group, and a polyorganosiloxane (B) and carbon nanomaterial (C) are included.
  • the release agent layer 12 having such a configuration has moderate conductivity. For this reason, the resistance value of the outer surface 121 of the release agent layer 12 can be lowered. Thereby, it can suppress that static electricity generate
  • the release agent layer forming material before irradiating the active energy ray exists in an uncured state or a semi-cured state at room temperature.
  • the release agent layer forming material when the release agent layer forming material is applied onto the first surface 111 of the substrate 11, it has an appropriate fluidity. Therefore, if such a release agent layer forming material is used, the unevenness of the first surface 111 of the substrate 11 can be easily embedded, and the embedded state can be reliably maintained. As a result, it is possible to prevent the unevenness of the base material 11 from affecting the outer surface 121 side of the release agent layer 12 opposite to the base material 11 and to smooth the outer surface 121 of the release agent layer 12. .
  • the active energy ray-curable compound (A) is a component that contributes to the formation of the release agent layer 12 by being cured. Thereby, the mechanical strength of the release agent layer 12 can be made more appropriate.
  • the active energy ray-curable compound (A) has at least one reactive functional group selected from the group consisting of a (meth) acryloyl group, an alkenyl group, and a maleimide group.
  • the alkenyl group include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, propenyl group, and hexenyl group.
  • the release agent layer 12 can obtain excellent curability, solvent resistance, and peelability.
  • this active energy ray-curable compound (A) has appropriate fluidity and shape retention.
  • the release agent layer forming material containing the active energy ray-curable compound (A) is applied on the first surface 111 of the base material 11, the first of the base material 11 is formed by the release agent layer forming material.
  • the unevenness of the surface 111 can be accurately embedded, and the embedded state can be reliably maintained.
  • the outer surface 121 of the release agent layer 12 can be smoothed.
  • the content of the reactive functional group in the active energy ray-curable compound (A) is preferably 10 equivalents or more per kg of the active energy ray-curable compound (A).
  • active energy ray-curable compound (A) examples include dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth).
  • Acrylate pentaerythritol tri (meth) acrylate
  • polyfunctional (meth) acrylate such as pentaerythritol tetra (meth) acrylate.
  • At least one polyfunctional selected from the group consisting of dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate. It is preferable to use acrylate. Thereby, also when apply
  • the content in terms of solid content of the active energy ray-curable compound (A) in the release agent layer forming material is preferably 65 to 98.5% by mass, 71 to It is more preferable that it is 96.3 mass%.
  • the polyorganosiloxane (B) is a component that causes the release agent layer 12 to exhibit release properties.
  • Examples of the polyorganosiloxane (B) include polyorganosiloxane having a linear or branched molecular chain.
  • a reactive functional group containing a silicon atom at the end and / or side chain of the molecular chain and having at least one selected from the group consisting of a (meth) acryloyl group, a vinyl group and a maleimide group is directly or It is preferably bonded to a silicon atom in the molecular chain via a divalent linking group. What is necessary is just to have at least one said reactive functional group in 1 molecule.
  • examples of the divalent linking group include an alkylene group, an alkyleneoxy group, an oxy group, an imino group, a carbonyl group, and a divalent linking group obtained by combining them.
  • the carbon number of the divalent linking group is preferably 1-30, and more preferably 1-10.
  • polyorganosiloxane (B) can be used in combination of two or more as required.
  • Such a modified polyorganosiloxane substituted with a reactive functional group is capable of crosslinking the cured product of the active energy ray-curable compound (A) when the active energy ray-curable compound (A) is cured by irradiation with active energy. Built into the structure and fixed. Thereby, it can suppress that the polyorganosiloxane which is a component of the releasing agent layer 12 transfers to the green sheet formed in the outer surface 121 side of the releasing agent layer 12, and transfers.
  • examples of the organic group other than the reactive functional group constituting the polyorganosiloxane (B) include a monovalent hydrocarbon group having no aliphatic unsaturated bond.
  • the organic group may be a plurality of monovalent hydrocarbon groups, which may be the same or different from each other.
  • the hydrocarbon group preferably has 1 to 12 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • hydrocarbon group examples include alkyl groups such as a methyl group, an ethyl group, and a propyl group, and aryl groups such as a phenyl group and a tolyl group.
  • the organic group other than the reactive functional group having such a configuration 80 mol% or more of the organic group is preferably a methyl group. Thereby, the peelability of the release agent layer 12 can be made particularly excellent.
  • the content of the polyorganosiloxane (B) in terms of solid content in the release agent layer forming material is preferably 0.5 to 5% by mass, and more preferably 0.7 to 4% by mass.
  • the formed release agent layer 12 may be There is a possibility that sufficient peelability cannot be exhibited.
  • the content in terms of solid content of the polyorganosiloxane in the release agent layer forming material exceeds the upper limit, when the ceramic slurry is applied to the surface of the release agent layer 12 to be formed, the constituent material of the ceramic slurry For example, the ceramic slurry may be easily repelled.
  • the mass ratio B / A is 0.7 / 99.
  • a range of 3 to 5/95 is more preferable, and a range of 1/99 to 4.5 / 95.5 is particularly preferable. Thereby, the effect becomes more remarkable.
  • Carbon nanomaterial (C) The carbon nanomaterial (C) has a function of imparting antistatic properties to the release agent layer 12.
  • Examples of the carbon nanomaterial (C) include fullerene, carbon nanotube, carbon nanofiber, and carbon nanohorn, and one or more of these can be used in combination. Among these, carbon nanotubes are particularly preferable. Thereby, more moderate electroconductivity can be provided to the release agent layer 12, and the surface resistance value of the outer surface 121 of the release agent layer 12 can be lowered. For this reason, it is possible to prevent foreign matters from adhering to the outer surface 121 of the release agent layer 12. As a result, it is possible to prevent pinholes from occurring in the green sheet formed on the release agent layer 12.
  • the carbon nanotubes are in the form of fibers having a high aspect ratio (long and short). For this reason, the carbon nanotube can be easily oriented so that the fiber length is along the surface direction of the release agent layer 12. Therefore, if carbon nanotubes are used, it is possible to obtain the release agent layer 12 having an appropriate charging property and a smoother outer surface 121.
  • the average diameter (fiber diameter) of the carbon nanomaterial (C) is preferably 1 to 1000 nm, more preferably 3 to 500 nm, and further preferably 5 to 100 nm.
  • the average length (fiber length) of the carbon nanomaterial (C) is 10 nm to 200 ⁇ m, and is not particularly limited. For example, it is preferably 50 nm to 100 ⁇ m, and more preferably 100 nm to 50 ⁇ m.
  • the aspect ratio of the carbon nanomaterial (C) is, for example, preferably 10 to 10,000, more preferably 200 to 5000, and further preferably 400 to 2000.
  • the aspect ratio of the carbon nanomaterial (C) is a value measured by observing the carbon nanotube using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, product name “S-4700”).
  • the content of the carbon nanomaterial (C) in the release agent layer forming material is, for example, preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.2 More preferably, it is ⁇ 1% by mass.
  • the content of the carbon nanomaterial (C) is less than the lower limit, the surface resistivity of the release agent layer 12 may not be sufficiently reduced.
  • content of carbon nanomaterial (C) exceeds the said upper limit, the intensity
  • the release agent layer forming material may contain a photopolymerization initiator (D).
  • a photopolymerization initiator D
  • the release agent layer forming material can be cured more easily and reliably by using the photopolymerization initiator (D).
  • the photopolymerization initiator (D) is not particularly limited.
  • Such an ⁇ -aminoalkylphenone-based photopolymerization initiator is a compound that is less susceptible to oxygen inhibition when the release agent layer forming material is cured. Therefore, particularly excellent curability can also be obtained in the production of the release film 1 in an air atmosphere.
  • Examples of ⁇ -aminoalkylphenone photopolymerization initiators include 2-methyl-1 [4- (methylthio) phenyl] ⁇ ⁇ ⁇ ⁇ -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, etc. Is mentioned. Thereby, especially excellent curability, solvent resistance, and peelability can be obtained.
  • the content in terms of solid content of the photopolymerization initiator (D) in the release agent layer forming material is preferably 1 to 20% by mass, and more preferably 3 to 15% by mass.
  • a component derived from the polyorganosiloxane (B) is segregated near the outer surface 121 of the release agent layer 12.
  • the reason why such segregation occurs is as follows.
  • the polyorganosiloxane (B ) Is pushed up near the surface of the coating layer.
  • the release agent layer forming material may contain other components in addition to the components as previously described.
  • other components such as a sensitizer, an antistatic agent, and a curing agent may be included.
  • Examples of the sensitizer include 2,4-diethylthioxanthone and isopropylthioxanthone. Thereby, reactivity can be improved more.
  • the content of the other components in the release agent layer forming material in terms of solid content is preferably 0 to 10% by mass.
  • the outer surface 121 of the release agent layer 12 is an arithmetic mean roughness Ra 1 is 8nm or less and a maximum projection height Rp 1 is 50nm or less.
  • the average thickness of the release agent layer 12 is preferably 0.2 to 2 ⁇ m, and more preferably 0.3 to 1.5 ⁇ m.
  • the thickness of the release agent layer 12 is less than the lower limit, the smoothness of the outer surface 121 of the release agent layer 12 becomes insufficient.
  • the thickness of the release agent layer 12 exceeds the upper limit, curling of the release film 1 is likely to occur due to curing shrinkage of the release agent layer 12.
  • the surface resistivity of the outer surface 121 of the release agent layer 12 is preferably 1.0 ⁇ 10 12 ⁇ / ⁇ or less, and more preferably 1.0 ⁇ 10 11 ⁇ / ⁇ or less.
  • the surface resistivity is within the above range, it is possible to more reliably reduce the adhesion of foreign substances or the like due to the generation of static electricity to the outer surface 121 of the release agent layer 12.
  • surface resistivity shows the resistance per unit surface area in this specification.
  • the unit of surface resistivity is ⁇ / ⁇ in this specification.
  • the surface resistivity can be measured according to JIS K6911 (1995).
  • the manufacturing method of the peeling film 1 of this embodiment applies the base material preparation process which prepares the base material 11, and the release agent layer forming material containing a predetermined component to the 1st surface 111 of the base material 11, It has a coating layer forming step of forming a coating layer by drying it and a release agent layer forming step of forming a release agent layer 12 by irradiating the coating layer with an activation energy ray and curing it. .
  • the base material 11 is prepared.
  • the first surface 111 of the substrate 11 can be subjected to a surface treatment by an oxidation method or the like. Thereby, the adhesiveness of the base material 11 and the release agent layer 12 provided in the 1st surface 111 side of the base material 11 can be made especially excellent.
  • examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, and ultraviolet irradiation treatment. These surface treatment methods are appropriately selected according to the type of the substrate 11. In general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.
  • a release agent layer forming material is prepared.
  • a release agent layer forming material containing components such as the active energy ray-curable compound (A), polyorganosiloxane (B), and carbon nanomaterial (C) as described above is prepared. This is dissolved or dispersed in a solvent to obtain a release agent layer forming material.
  • the solvent for example, methanol, ethanol, toluene, ethyl acetate, xylene, methyl ethyl ketone, methyl butyl ketone, isopropyl alcohol and the like can be used.
  • a liquid release agent layer forming material is applied on the first surface 111 of the substrate 11 and dried. Thereby, a coating layer is obtained.
  • the unevenness of the first surface 111 of the substrate 11 can be filled.
  • the outer surface 121 of the release agent layer 12 can be smoothed.
  • Examples of methods for applying the release agent layer forming material include gravure coating, bar coating, spray coating, spin coating, air knife coating, roll coating, blade coating, gate roll coating, and die coating. Law.
  • the method for drying the release agent layer forming material is not particularly limited, and examples thereof include a method of drying in a hot air drying furnace.
  • the drying conditions are not particularly limited.
  • the drying temperature is preferably 50 to 100 ° C., and the drying time is preferably 5 seconds to 1 minute. Thereby, unintentional alteration of the coating layer can be prevented, and the coating layer can be formed particularly efficiently. As a result, productivity of the finally obtained release film 1 can be improved.
  • the drying temperature is within the above range, particularly when the release agent layer forming material contains a solvent or the like, the occurrence of warping or cracking of the coating layer accompanied by evaporation of the solvent or the like during drying is particularly caused. Can be prevented.
  • the release agent layer 12 is formed by irradiating the application layer obtained in the application layer forming step with an activation energy ray and curing it.
  • the coating layer in which the unevenness of the first surface 111 of the substrate 11 is appropriately embedded in the coating layer forming step is cured while maintaining the smoothness of the outer surface 121.
  • the release agent layer 12 having a sufficiently smooth outer surface 121 can be obtained.
  • the release agent layer forming material contains the constituent components as described above, the release agent layer 12 having appropriate conductivity can be obtained.
  • active energy rays include electromagnetic waves such as infrared rays, visible rays, ultraviolet rays, and X-rays, electron beams, ion beams, neutron rays, and particle rays such as ⁇ rays.
  • electromagnetic waves such as infrared rays, visible rays, ultraviolet rays, and X-rays, electron beams, ion beams, neutron rays, and particle rays such as ⁇ rays.
  • ultraviolet light or visible light it is preferable to use ultraviolet light or visible light, and ultraviolet light is more preferable.
  • the release agent layer 12 can be formed more easily and reliably.
  • the wavelength of the activation energy ray is not particularly limited, but is preferably 200 to 600 nm, and more preferably 250 to 450 nm, for example. If the wavelength of the activation energy ray is within the above range, the coating layer can be uniformly cured while sufficiently shortening the curing time for curing the coating layer. Moreover, it does not specifically limit as a means to irradiate an activation energy ray, A various general means can be utilized. For example, a light source lamp such as a pressure mercury lamp, a metal halide lamp, or an excimer lamp can be used as the light source.
  • a light source lamp such as a pressure mercury lamp, a metal halide lamp, or an excimer lamp can be used as the light source.
  • the irradiation amount of the activation energy rays is preferably 50 to 400 mJ / cm 2 , and preferably 100 to 300 mJ / cm 2 . More preferably.
  • the irradiation amount of ultraviolet rays is a value within the above range, the coating layer can be cured more uniformly and reliably.
  • the time for irradiating the activation energy ray is not particularly limited, but is preferably 5 seconds to 1 minute. Thereby, the release agent layer 12 can be formed particularly efficiently. As a result, productivity of the finally obtained release film 1 can be improved.
  • the highly reliable release film 1 having excellent smoothness and antistatic properties can be easily and reliably produced.
  • a green sheet is manufactured using such a release film 1, it is possible to prevent a pinhole or the like from being generated on the surface of the green sheet.
  • a ceramic powder dispersion slurry is applied to the surface of the release agent layer of the release film and dried to form a green sheet, and then released from the release film.
  • the green sheets are laminated to obtain a laminate, and an electrode is formed on the ceramic sheet obtained by firing the laminate.
  • the release film 1 for producing a green sheet in which the release agent layer 12 is provided on the first surface 111 of the substrate 11 has been described.
  • the release film 1 for producing a green sheet is not limited to this, and an intermediate layer may be provided between the substrate 11 and the release agent layer 12. Such an intermediate layer may improve the adhesion between the substrate 11 and the release agent layer 12.
  • the configuration of the release film for producing a green sheet of the present invention can be replaced with an arbitrary configuration that can exhibit the same function, or an arbitrary configuration can be added.
  • the base material has been described as having a single-layer structure, but the present invention is not limited to this, and the base material may have a multilayer structure of two or more layers of the same type or different types.
  • the release agent layer has been described as having a single layer structure. However, the present invention is not limited to this, and the release agent layer may have a multilayer structure of two or more layers of the same type or different types.
  • the green film manufacturing release film provided with the release agent layer on the first surface of the base material has been described.
  • the release film for producing a green sheet is not limited to this, and a release agent layer may be provided on the second surface side of the substrate.
  • the manufacturing method of the peeling film for green sheet manufacture of this invention is not limited to the method mentioned above, Arbitrary processes may be added as needed.
  • the obtained release agent layer-forming material was applied onto the first surface of the substrate with a bar coater.
  • the release agent layer forming material was dried at 80 ° C. for 1 minute, and then irradiated with ultraviolet rays (integrated light amount: 250 mJ / cm 2 ) to form a release agent layer (thickness 0.97 ⁇ m), and a release film for producing a green sheet Got.
  • Example 2 A release film for producing a green sheet was produced in the same manner as in Example 1 except that the thickness of the release agent layer was changed as shown in Table 1.
  • Example 4 A release film was prepared in the same manner as in Example 1 except that the mass ratio of the active energy ray-curable compound (A) and the polyorganosiloxane (B) in the release agent layer forming material was changed as shown in Table 1. .
  • Example 5 A release film was produced in the same manner as in Example 1 except that the mass ratio of the active energy ray-curable compound (A) and the carbon nanomaterial (C) was changed as shown in Table 1.
  • Example 7 Biaxially stretched polyethylene terephthalate film (thickness: 38 ⁇ m, arithmetic average roughness Ra 0 of the first surface: 15 nm, maximum protrusion height Rp 0 of the first surface: 98 nm, arithmetic average of the second surface A release film was produced in the same manner as in Example 1 except that the roughness Ra 2 was 15 nm and the maximum protrusion height Rp 2 of the second surface was 98 nm.
  • Example 8 A release film was produced in the same manner as in Example 1 except that the thickness of the release agent layer was changed as shown in Table 1.
  • Example 9 Biaxially stretched polyethylene terephthalate film (thickness: 31 ⁇ m, first surface arithmetic average roughness Ra 0 : 7 nm, first surface maximum protrusion height Rp 0 : 43 nm, second surface arithmetic average A release film was produced in the same manner as in Example 1 except that the roughness Ra 2 was 34 nm and the maximum protrusion height Rp 2 of the second surface was 250 nm.
  • Example 1 A release film was prepared in the same manner as in Example 1 except that the mass ratio of the active energy ray-curable compound (A) and the polyorganosiloxane (B) in the release agent layer forming material was changed as shown in Table 1. .
  • Example 4 A release film was produced in the same manner as in Example 1 except that the mass ratio of the active energy ray-curable compound (A) and the carbon nanomaterial (C) was changed as shown in Table 1.
  • thermosetting silicone manufactured by Shin-Etsu Chemical Co., Ltd., KS-847H, solid content 30% by mass
  • the release agent is 99.72% by mass as the solid content
  • the multi-walled carbon nanotube manufactured by Philgen
  • This dilute solution is mixed with 0.04% by mass of platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T, solid content of 2% by mass) as a solid content, and a release agent solution with a solid content of 5.0% by mass.
  • platinum catalyst manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T, solid content of 2% by mass
  • a release agent solution with a solid content of 5.0% by mass.
  • release agent solution Uniformly apply the obtained release agent solution to one surface (first surface) of the same substrate as in Example 1 so that the thickness of the formed release agent layer after drying is 0.3 ⁇ m. did.
  • the release agent solution was dried at 140 ° C. for 1 minute to form a release agent layer, which was used as a release film.
  • Example 9 A release film for producing a green sheet was produced in the same manner as in Example 1 except that the following materials were used as the release agent layer forming material.
  • Table 1 summarizes the configurations and the like of the release films for producing green sheets of each Example and each Comparative Example.
  • dipentaerythritol hexaacrylate solid content: 100% by mass
  • polyether-modified acryloyl group-containing polydimethylsiloxane as the polyorganosiloxane (B).
  • the film thicknesses of the base material and the release agent layer in each Example and each Comparative Example were measured using a reflective film thickness meter “F20” [manufactured by Filmetrics Co., Ltd.]. Specifically, the release film for green sheet production obtained in each example and each comparative example was cut into a size of 100 ⁇ 100 mm. Then, the release film for green sheet manufacture was installed in the film thickness meter so that the surface opposite to the surface on which the film thickness was measured was the suction stage side. The film thickness was measured at 10 locations on the surface of the release agent layer, and the average value was calculated. The average value was taken as the thickness of the release agent layer.
  • the arithmetic average roughness Ra 0 and the maximum protrusion height Rp 0 of the first surface of the base material, the arithmetic average roughness Ra 2 and the maximum protrusion height Rp 2 of the second surface of the base material, and the release agent layer The arithmetic average roughness Ra 1 and the maximum protrusion height Rp 1 of the outer surface were measured as follows. First, a double-sided tape was affixed to a glass plate. Next, the release film for producing green sheets obtained in each Example and each Comparative Example was fixed on the double-sided tape so that the surface on which the arithmetic average roughness and the maximum protrusion were measured was up.
  • the arithmetic average roughness Ra 0 , Ra 2 , Ra 1 , and the maximum protrusion height Rp 0 , Rp 2 , Rp 1 are converted into a surface roughness measuring machine SV3000S4 (Mitutoyo Co., Ltd.) according to JIS B0601-1994. Measured with a needle type).
  • A The release agent layer does not dissolve or fall off.
  • B Dissolution was observed in a part of the release agent layer.
  • C The release agent layer was completely dissolved and dropped from the substrate.
  • A The sum total of the height of each corner is less than 50 mm.
  • B The sum total of the height of each corner is 50 mm or more and less than 100 mm.
  • C The sum total of the height of each corner is 100 mm or more.
  • A The charge amount is ⁇ 5 kV or less.
  • B Charge amount is ⁇ 5 to 10 kV.
  • C Charge amount is more than ⁇ 10 kV.
  • the ceramic slurry is dried with a die coater so that the thickness after drying is 1 ⁇ m, the width is 250 mm, and the length is 10 m. And coated to obtain a coating layer. Thereafter, the coating layer was dried at 80 ° C. for 1 minute with a dryer to obtain a release film for producing a green sheet on which a ceramic green sheet was formed. About the release film for green sheet manufacture in which the ceramic green sheet was shape
  • the release film for green sheet production was peeled from the polyvinyl butyral resin layer, and the number of recesses on the surface of the polyvinyl butyral resin layer that was in contact with the release agent layer of the release film for green sheet production was determined. I counted. Specifically, the surface of the polyvinyl butyral resin layer was observed at 50 magnifications in the PSI mode using an optical interference type surface shape observation device (Veeco, WYKO-1100). The number of recesses was counted based on the surface shape image in the range of 91.2 ⁇ 119.8 ⁇ m on the surface of the polyvinyl butyral resin layer. The concave portion had a depth of 150 nm or more.
  • the number of recesses was evaluated according to the following criteria, and the defects on the surface of the release agent layer were evaluated.
  • the green film manufacturing release film whose criterion was “C” was not a green sheet manufacturing release film that was satisfactory for this evaluation, and thus this evaluation was not performed.
  • the release film for producing a green sheet of the present invention was excellent in the smoothness of the outer surface. Moreover, the release film for producing the green sheet of the present invention had a relatively low charge amount and excellent blocking properties. In addition, the release film for producing a green sheet of the present invention was excellent in peelability from the green sheet. In addition, no pinholes were observed on the green sheet formed using the release film for producing the green sheet of the present invention. On the other hand, satisfactory results were not obtained in the comparative example.
  • the release film for producing a green sheet of the present invention has a base material and a release agent layer, and the release agent layer is at least one selected from the group consisting of a (meth) acryloyl group, an alkenyl group and a maleimide group.
  • a release agent layer forming material containing an active energy ray-curable compound having a reactive functional group (A), a polyorganosiloxane (B), and a carbon nanomaterial (C) is applied to the first surface.
  • the coating layer formed Te is formed by irradiation with an active energy ray, the arithmetic average roughness Ra 1 of the outer surface of the release agent layer is not more 8nm or less and the outer surface of the release agent layer
  • the maximum protrusion height Rp 1 is 50 nm or less.

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PCT/JP2013/085206 2013-03-28 2013-12-27 グリーンシート製造用剥離フィルム WO2014155895A1 (ja)

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SG11201507895WA SG11201507895WA (en) 2013-03-28 2013-12-27 Release film for green sheet production
CN201380075174.8A CN105102194B (zh) 2013-03-28 2013-12-27 印刷电路基板制造用剥离膜
PH12015502250A PH12015502250A1 (en) 2013-03-28 2015-09-28 Release film for green sheet production

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WO2016133092A1 (ja) * 2015-02-18 2016-08-25 リンテック株式会社 離型フィルム
JP6468924B2 (ja) * 2015-03-31 2019-02-13 リンテック株式会社 セラミックグリーンシート製造工程用剥離フィルムおよびセラミックグリーンシート製造方法
TWI564149B (zh) * 2015-08-05 2017-01-01 Nanya Plastics Corp 一種離型膜及其製造方法
KR102572480B1 (ko) * 2017-03-01 2023-08-30 도요보 가부시키가이샤 세라믹 그린 시트 제조용 이형 필름 및 그의 제조 방법
KR102422462B1 (ko) * 2017-11-02 2022-07-21 도요보 가부시키가이샤 세라믹 그린 시트 제조용 이형 필름
JP7188537B2 (ja) * 2017-12-27 2022-12-13 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP7188536B2 (ja) * 2017-12-27 2022-12-13 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP7188535B2 (ja) * 2017-12-27 2022-12-13 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP6973054B2 (ja) * 2017-12-27 2021-11-24 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP7101553B2 (ja) * 2018-07-10 2022-07-15 リンテック株式会社 セラミックグリーンシート製造工程用剥離フィルム
JP6813124B2 (ja) * 2018-09-03 2021-01-13 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP7338359B2 (ja) * 2018-09-26 2023-09-05 東レ株式会社 光学用ポリエステルフィルムロール
TWI848029B (zh) * 2018-12-20 2024-07-11 日商東洋紡股份有限公司 離型膜、離型膜之製造方法、陶瓷生坯之製造方法、以及陶瓷電容器之製造方法
CN114025960B (zh) 2019-06-28 2024-05-24 东洋纺株式会社 陶瓷生片制造用脱模薄膜
CN115210052A (zh) * 2020-03-04 2022-10-18 Tdk株式会社 剥离膜卷、陶瓷部件片材及其制造方法、以及陶瓷部件及其制造方法

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MY173627A (en) 2020-02-12
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