WO2015151993A1 - Release film for ceramic green sheet manufacturing process - Google Patents
Release film for ceramic green sheet manufacturing process Download PDFInfo
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- WO2015151993A1 WO2015151993A1 PCT/JP2015/059370 JP2015059370W WO2015151993A1 WO 2015151993 A1 WO2015151993 A1 WO 2015151993A1 JP 2015059370 W JP2015059370 W JP 2015059370W WO 2015151993 A1 WO2015151993 A1 WO 2015151993A1
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- release agent
- agent layer
- green sheet
- ceramic green
- release
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- 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
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- 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
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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- 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
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- 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
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- 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
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- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
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- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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- 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
Definitions
- the present invention relates to a release film used in a process for producing a ceramic green sheet.
- a ceramic green sheet is formed, and a plurality of obtained ceramic green sheets are laminated and fired.
- the ceramic green sheet is formed to have a uniform thickness by applying a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide on a release film.
- a film base is usually used which is subjected to a release treatment with a silicone compound such as polysiloxane to form a release agent layer.
- the miniaturization and multilayering of multilayer ceramic capacitors and multilayer ceramic substrates have progressed, and the ceramic green sheets have become thinner.
- the thickness of the ceramic green sheet is reduced to 3 ⁇ m or less, for example, when the ceramic slurry is applied and dried, the ceramic green sheet is caused by the surface state of the release agent layer in the release film. Defects such as pinholes and uneven thickness are likely to occur. Further, when the formed ceramic green sheet is peeled from the release film, problems such as breakage due to a decrease in strength of the ceramic green sheet are likely to occur.
- this release film is required to have a releasability that allows a thin ceramic green sheet formed on the release film to be peeled from the release film without breaking.
- Patent Document 1 proposes to use a release film having a rough arithmetic average roughness on the surface (back surface) opposite to the surface on which the release agent layer of the substrate is provided. Has been.
- the ceramic grease sheet is punched into a predetermined size together with the release film, and is peeled off from the release film and laminated.
- a peeling imparting component for example, a silicone compound
- the present invention has been made in view of such a situation, and is excellent in releasability from a ceramic green sheet, is difficult to transfer a peeling imparting component to the ceramic green sheet, and a defect occurs in the ceramic green sheet. It is another object of the present invention to provide a release film for a ceramic green sheet manufacturing process that can prevent or suppress this, and is less likely to cause blocking.
- the present invention provides a ceramic comprising a substrate having a first surface and a second surface, and a release agent layer provided on the first surface of the substrate.
- a release film for a green sheet manufacturing process wherein the release agent layer is formed from a release agent composition containing an active energy ray-curable component (A) and a photopolymerization initiator (B), and the active energy ray cure
- the component (A) is an hydroxyl group-containing (meth) acrylate (a1) having at least three (meth) acryloyl groups on average in one molecule, a polyvalent isocyanate compound (a2), and at least in one molecule.
- a linear dimethylorganopolysiloxane (a3) having one hydroxyl group and a weight average molecular weight of 500 to 8000 is converted to the (meth) acrylate (a1), the polyvalent isocyanate compound (a2). And the amount of the dimethylorganopolysiloxane (a3) to the total amount of the dimethylorganopolysiloxane (a3) is reacted so that the mass ratio is 0.01 to 0.10, and the thickness of the release agent layer Is 0.3 to 2 ⁇ m, the arithmetic average roughness (Ra1) on the surface of the release agent layer opposite to the base material is 8 nm or less, and the maximum protrusion height (Rp1) is 50 nm or less.
- the ceramic green sheet manufacturing process is characterized in that the arithmetic mean roughness (Ra2) on the second surface of the substrate is 5 to 40 nm and the maximum protrusion height (Rp2) is 60 to 500 nm.
- Ra2 arithmetic mean roughness
- Rp2 maximum protrusion height
- a film is provided (Invention 1).
- the release agent layer is composed of the release agent composition, thereby being excellent in peelability from the ceramic green sheet and the ceramic green sheet.
- the peeling imparting component is difficult to migrate to.
- the thickness of the release agent layer and the surface state of the release agent layer and the substrate as described above, it is possible to prevent and suppress the occurrence of defects in the ceramic green sheet. Blocking is unlikely to occur.
- the photopolymerization initiator (B) is preferably an ⁇ -hydroxyketone compound or an ⁇ -aminoalkylphenone compound (Invention 2).
- invention 1 and 2 after forming a polyvinyl butyral resin layer in the surface on the opposite side to the said base material of the said releasing agent layer, when peeling the said polyvinyl butyral resin layer from the said releasing agent layer.
- the silicon atomic ratio measured by photoelectron spectroscopic analysis of the surface of the polyvinyl butyral resin layer that is in contact with the release agent layer is preferably less than 1.0 atomic% (Invention 3).
- the release film for a ceramic green sheet manufacturing process it is excellent in peelability from the ceramic green sheet, the peeling imparting component is not easily transferred to the ceramic green sheet, and defects occur in the ceramic green sheet. Can be prevented / suppressed, and blocking is unlikely to occur.
- a release film 1 for a ceramic green sheet manufacturing process includes a base material 11 and a first of the base material 11. And a release agent layer 12 laminated on the surface 111 (upper surface in FIG. 1).
- the base material 11 includes a second surface 112 on the surface (the lower surface in FIG. 1) opposite to the first surface 111 of the base material 11.
- the base material 11 of the release film 1 according to the present embodiment is not particularly limited as long as the release agent layer 12 can be laminated.
- the substrate 11 include films made of polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, plastics such as polycarbonate and polyvinyl acetate, and may be a single layer. However, it may be a multilayer of two or more layers of the same type or different types.
- a polyester film is preferable, a polyethylene terephthalate film is particularly preferable, and a biaxially stretched polyethylene terephthalate film is more preferable.
- the polyethylene terephthalate film hardly generates dust or the like during processing or use, for example, it is possible to effectively prevent a ceramic slurry coating failure due to dust or the like. Furthermore, the effect which prevents a coating defect etc. can be heightened by performing an antistatic process to a polyethylene terephthalate film.
- an oxidation method or unevenness is formed on the first surface 111 or both the first surface 111 and the second surface 112 as desired.
- Surface treatment by a chemical method or the like, or primer treatment can be performed.
- the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, and the like.
- a thermal spraying method are appropriately selected depending on the type of the base film, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
- the thickness of the substrate 11 is usually 10 to 300 ⁇ m, preferably 15 to 200 ⁇ m, and particularly preferably 20 to 125 ⁇ m.
- the arithmetic average roughness (Ra0) on the first surface 111 of the substrate 11 is preferably 2 to 50 nm, and particularly preferably 5 to 30 nm.
- the maximum protrusion height (Rp0) on the first surface 111 of the substrate 11 is preferably 10 to 700 nm, and particularly preferably 30 to 500 nm.
- the arithmetic average roughness (Ra2) on the second surface 112 of the substrate 11 is 5 to 40 nm, preferably 10 to 30 nm, and particularly preferably 15 to 25 nm. Further, the maximum protrusion height (Rp2) on the second surface 112 of the substrate 11 is 60 to 500 nm, and preferably 100 to 400 nm.
- the arithmetic average roughness (Ra2) of the second surface 112 of the substrate 11 is less than 5 nm, the second surface 112 is too smooth, and the second surface 112 of the substrate 11 is wound when the release film 1 is wound.
- the second surface 112 and the highly smooth release agent layer 12 are in close contact with each other, and blocking is likely to occur.
- the arithmetic average roughness (Ra2) of the second surface 112 of the base material 11 exceeds 40 nm, the maximum protrusion height (Rp2) of the second surface 112 of the base material 11 is kept within the preferable low range. It becomes difficult.
- the maximum protrusion height (Rp2) on the second surface 112 of the base material 11 exceeds 500 nm, the protrusion on the second surface 112 of the base material 11 when the release film 1 formed with the ceramic green sheet is wound up.
- the shape is transferred to the surface of the ceramic green sheet in contact with this surface, resulting in defects such as partial thinning of the ceramic green sheet.
- a defect due to a short circuit occurs. There is a fear.
- the maximum protrusion height (Rp2) of the second surface 112 of the base material 11 is less than 60 nm, the second surface 112 of the base material 11 becomes flat. Therefore, it becomes easy to entrain air on the surface where the substrate 11 is in contact with the roll. As a result, the substrate 11 being conveyed may meander or may be unwound when wound into a roll.
- the same layer as the release agent layer 12 described later may be provided, or a layer different from the release agent layer 12 may be provided.
- the 2nd surface 112 of the base material 11 points out the surface on the opposite side to the base material 11 side among the surfaces of these layers.
- release agent layer 12 in the release film 1 includes a release agent composition (hereinafter referred to as "release agent composition") containing an active energy ray-curable component (A) and a photopolymerization initiator (B). It may be referred to as an object R ”).
- release agent composition a release agent composition containing an active energy ray-curable component (A) and a photopolymerization initiator (B). It may be referred to as an object R ”).
- the release agent layer 12 is formed by curing the release agent composition R.
- the active energy ray-curable component (A) comprises a hydroxyl group-containing (meth) acrylate (a1) having at least three (meth) acryloyl groups on average in one molecule, a polyvalent isocyanate compound (a2), 1 A linear dimethylorganopolysiloxane (a3) having at least one hydroxyl group in the molecule and having a mass average molecular weight of 500 to 8000, a (meth) acrylate (a1), a polyvalent isocyanate compound (a2) and The reaction is carried out so that the amount of dimethylorganopolysiloxane (a3) relative to the total amount of dimethylorganopolysiloxane (a3) is 0.01 to 0.10 in terms of mass ratio.
- (meth) acrylate means both acrylate and methacrylate. The same applies to other similar terms.
- the (meth) acrylate (a1) forms a polymer by radical polymerization. Since dimethylorganopolysiloxane (a3), which is a release imparting component, is incorporated into the polymer by covalent bonding, it is suppressed from falling off from the release agent layer 12 that is a cured product of the release agent composition R. Therefore, migration of the peeling imparting component is suppressed with respect to the ceramic grease sheet formed on the release agent layer 12, and a highly reliable ceramic grease sheet can be formed with high yield. Moreover, when the dimethylorganopolysiloxane (a3), which is a peeling imparting component, is present as described above, the resulting release agent layer 12 exhibits good peelability.
- (Meth) acrylate (a1) is composed of a single compound or two or more compounds having a structure represented by the following general formula (1) or (2).
- X 1 to X 10 each independently represents a (meth) acryloyl group or a hydroxyl group, and at least three or more of X 1 to X 6 are (meth) acryloyl groups. And at least three of X 7 to X 10 represent a (meth) acryloyl group.
- the (meth) acrylate (a1) has at least three (meth) acryloyl groups on average in one molecule, thereby exhibiting sufficient curability and exhibiting poor curing when irradiated with active energy rays. It is prevented from waking up. From this viewpoint, the number of (meth) acryloyl groups in one molecule of (meth) acrylate (a1) is preferably 5 or more.
- the (meth) acrylate (a1) it is preferable to use a hydroxyl group-containing acrylate which does not contain a methacryloyl group and whose functional group is composed only of an acryloyl group and a hydroxyl group.
- a hydroxyl group-containing acrylate exhibits better curability.
- dipentaerythritol triacrylate dipentaerythritol tetraacrylate
- dipentaerythritol pentaacrylate dipentaerythritol hexaacrylate
- pentaerythritol triacrylate and pentane having the structure represented by the above general formula (1) or (2) It is preferable that it is one or a mixture of two or more selected from erythritol tetraacrylate, and the average content of acryloyl groups is 3 or more per molecule, and the concentration is adjusted to 8 equivalents or more per kg. Those are particularly preferred.
- the polyvalent isocyanate compound (a2) is a compound having at least two isocyanate groups in one molecule.
- aromatic polyvalent isocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, etc.
- Aliphatic polyisocyanates such as aliphatic polyisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like, and biuret and isocyanurate forms, as well as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor Examples thereof include adducts that are a reaction product with a low-molecular active hydrogen-containing compound such as oil. Among these, hexamethylene diisocyanate and its isocyanurate body, which can lower the peel force and improve the peelability, are particularly preferable.
- the said polyvalent isocyanate compound (a2) can be used individually by 1 type or in combination of 2 or more types.
- the dimethylorganopolysiloxane (a3) Since the dimethylorganopolysiloxane (a3) is reacted with the (meth) acrylate (a1) via the polyvalent isocyanate compound (a2), it needs to have at least one hydroxyl group in one molecule. In order to develop good peelability, the dimethylorganopolysiloxane (a3) needs to be linear and have a mass average molecular weight of 500 to 8000. When the mass average molecular weight is within this range, stable releasability is exhibited and coatability is also improved.
- the mass average molecular weight is preferably 500 to 6000, particularly preferably 500 to 5000.
- the mass mean molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
- Examples of the dimethylorganopolysiloxane (a3) include those having a structure represented by the following general formula (3), (4) or (5). Especially, what has the structure shown in General formula (3) is preferable, and according to this, especially peel force can be made low and peelability can be improved. A combination of a compound having the structure represented by the general formula (5) and an isocyanurate of hexamethylene diisocyanate as the polyvalent isocyanate compound (a2) is also preferable because the peelability can be improved.
- R 1 , R 3 and R 6 each independently represent an alkyl group or an alkylene ether group
- R 2 , R 4 , R 5 and R 7 Each independently represents an alkylene group or an alkylene ether group.
- n represents a positive integer.
- dimethylorganopolysiloxane examples include Silaplane FM-4411, FM-4421, FM-4421, FMDA4, FMDA11, FMDA21, FM0411, FM0421, FM0425 manufactured by Chisso Corporation, X22-160AS, KF-6001 manufactured by Shin-Etsu Chemical Co., Ltd.
- Examples thereof include KF-6002, KF-6003, X-22-170BX, X-22-170DX, X22-176DX, X-22-176F, among which silaplane FMDA11, FMDA21 and FM0411 are preferable.
- the amount of dimethylorganopolysiloxane (a3) relative to the total amount of (meth) acrylate (a1), polyvalent isocyanate compound (a2) and dimethylorganopolysiloxane (a3) is in a mass ratio.
- the reaction was carried out to 0.01 to 0.10. If the mass ratio is less than 0.01, it becomes difficult to obtain stable peelability. On the other hand, if the mass ratio exceeds 0.10, the charge amount of the release film increases when the release film wound up in a roll shape is fed out. For this reason, it becomes easy for foreign matter etc. to adhere to the surface of a peeling film, and when applying slurry, there is a possibility of generating a pinhole etc.
- the mass ratio is preferably 0.01 to 0.07, and particularly preferably 0.01 to 0.05.
- the value obtained by subtracting the total hydroxyl group content of the dimethylorganopolysiloxane (a3) from the total isocyanate group amount of the polyvalent isocyanate compound (a2) is greater than the total hydroxyl group content of the (meth) acrylate (a1). It is preferable to adjust so that it may become small. Further, when the active energy ray-curable component (A) is produced, the polyvalent isocyanate compound (a2) and the dimethylorganopolysiloxane (a3) are reacted first, and the (meth) acrylate (a1) is reacted therewith. It is preferable. By doing so, the amount of the dimethylorganopolysiloxane (a3) remaining without reacting with the (meth) acrylate (a1) can be reduced. The amount of siloxane (a3) transferred to the ceramic green sheet can be reduced.
- Examples of the photopolymerization initiator (B) contained in the release agent composition R include ⁇ -hydroxy ketone compounds, ⁇ -aminoalkylphenone compounds, aromatic ketones containing thioxanthone, acylphosphine oxides, and the like. Is mentioned. Among these, ⁇ -hydroxyketone compounds and ⁇ -aminoalkylphenone compounds are preferable from the viewpoint of promoting a polymerization reaction and improving curability.
- the said photoinitiator (B) can be used individually by 1 type or in combination of 2 or more types.
- Examples of ⁇ -hydroxy ketone compounds include 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propan-1-one. 2-hydroxy-4′-hydroxyethoxy-2-methylpropiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, oligo ⁇ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] Propanone ⁇ and the like.
- Examples of the ⁇ -aminoalkylphenone compound 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 and the like.
- the content of the photopolymerization initiator (B) in the release agent composition R is preferably 2 to 15 parts by mass, particularly 4 to 12 parts per 100 parts by mass of the active energy ray-curable component (A). It is preferable that it is a mass part.
- the release agent composition R according to the present embodiment may contain silica, an antistatic agent, a starting aid, a dye, a pigment and other additives as necessary in addition to the above components.
- the thickness of the release agent layer 12 in the release film 1 according to the present embodiment is 0.3 to 2 ⁇ m, preferably 0.3 to 1.5 ⁇ m, particularly 0.3 to 1.2 ⁇ m. Is preferred.
- the thickness of the release agent layer 12 is less than 0.3 ⁇ m, the concave portion between the protrusions existing on the first surface 111 of the substrate 11 cannot be filled, and the smoothness of the surface 112 of the release agent layer 12 is obtained. It becomes insufficient, and pinholes and uneven thickness easily occur in the ceramic green sheet.
- the thickness of the release agent layer 12 exceeds 2 ⁇ m, the release film 1 is likely to curl due to curing shrinkage of the release agent layer 12.
- the peeling film 1 is wound up in a roll shape, the second surface 112 of the substrate 11 and blocking are likely to occur.
- the arithmetic average roughness (Ra1) of the surface 121 of the release agent layer 12 is 8 nm or less, preferably 6 nm or less, and particularly preferably 4 nm or less. Further, the maximum protrusion height (Rp1) of the surface 121 of the release agent layer 12 is 50 nm or less, preferably 40 nm or less, and particularly preferably 30 nm or less.
- the surface 121 of the release agent layer 12 is made sufficiently high and smooth. For example, even when a thin film ceramic green sheet having a thickness of 1 ⁇ m or less is formed on the surface 121 of the release agent layer 12, defects such as pinholes and uneven thickness are hardly generated in the thin film ceramic green sheet. Slurry coatability is shown.
- the peelability from the ceramic green sheet becomes excellent, for example Even when a thin film ceramic green sheet having a thickness of 1 ⁇ m or less is peeled from the release agent layer 12, the ceramic green sheet is hardly broken.
- the release agent layer 12 obtained by curing the release agent composition R is laminated on the first surface 111 of the substrate 11, the arithmetic average roughness (Ra1) and the maximum on the surface 121 of the release agent layer 12.
- the projection height (Rp1) can be within the above-described range.
- the release agent composition R the release agent obtained by effectively filling the concave portions between the protrusions present on the first surface 111 of the substrate 11 mainly with the cured product of the active energy ray-curable component.
- the surface 121 of the layer 12 can be highly smoothed.
- the release agent layer 12 formed by curing the release agent composition R as described above, the transfer of the release imparting component to the ceramic grease sheet formed on the release agent layer 12 is suppressed. .
- the release agent layer 12 in the polyvinyl butyral resin layer comes into contact.
- the amount of silicone transferred on the surface that has been reduced decreases.
- the amount of silicone transferred can be evaluated by the silicon atom ratio measured by X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- the silicon atom ratio obtained by measuring the surface is preferably less than 1.0 atom%, particularly preferably less than 0.5 atom%, and more preferably 0.3 atom % Or less is preferable.
- the silicon atomic ratio is used as an evaluation standard for the migration amount of the silicone compound that is the release imparting component of the release agent layer 12. Can be used.
- the release agent layer on the ceramic green sheet is formed. 12 when the silicon atomic ratio of the surface in contact with the release agent layer 12 in the polyvinyl butyral resin layer is within the above range, the release agent layer on the ceramic green sheet is formed. 12 can be suppressed.
- the release film 1 includes a release agent layer containing a release agent composition R and an organic solvent as required on the first surface 111 of the substrate 11. After the forming material is applied, it can be produced by drying as necessary and curing by irradiation with active energy rays to form the release agent layer 12.
- a coating method of the release agent layer forming material for example, a gravure coating method, a bar coating method, a spray coating method, a spin coating method, a knife coating method, a roll coating method, a die coating method and the like can be used.
- organic solvent a conventionally known organic solvent can be used as long as the components of the release agent layer forming material have good solubility and are not reactive.
- aliphatic hydrocarbons such as hexane, heptane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol (isopropyl alcohol), butanol, 1- Alcohols such as methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, cellosolv solvents such as ethyl cellosolve, mixed solvents thereof and the like are used.
- the amount of the organic solvent used is preferably adjusted so that the solid content concentration is in the range
- the active energy ray ultraviolet rays, electron beams and the like are usually used, and ultraviolet rays are particularly preferable.
- the dose of the active energy ray varies depending on the type of the energy ray, for example, in the case of ultraviolet rays, preferably 50 ⁇ 1000mJ / cm 2 in quantity, especially 100 ⁇ 500mJ / cm 2 preferably. In the case of an electron beam, about 0.1 to 50 kGy is preferable.
- the irradiation of the active energy ray causes the active energy ray-curable component (A) in the release agent composition R to be polymerized and cured, thereby forming the release agent layer 12.
- the ceramic green sheet is formed by applying a ceramic slurry to the surface 121 of the release agent layer 12 and drying using a slot die coating method, a doctor blade method, or the like. Mold.
- a ceramic green sheet having high smoothness is formed even when a thin ceramic green sheet having excellent slurry coating properties and low strength is formed into a release agent layer. It is possible to suppress the occurrence of pinholes and uneven thickness.
- the formed ceramic green sheet is easy to peel from the release film 1, and the peeling imparting component (silicone compound) is not easily transferred to the ceramic green sheet.
- the release film 1 on which the ceramic green sheet is formed is stored in a rolled state or transported by roll-to-roll, the surface state of the second surface 112 of the substrate 11 is maintained. As a result, the occurrence of defects such as partial thinning of the ceramic green sheet is suppressed. Furthermore, according to the release film 1, since blocking is unlikely to occur, it is possible to suppress problems such as winding failure and increase in charge amount during unwinding and adhesion of foreign matters. Therefore, according to the peeling film 1 which concerns on a present Example, a highly reliable ceramic green sheet can be manufactured with sufficient yield with favorable productivity.
- another layer such as an antistatic layer may be provided between the surface of the substrate 11 opposite to the release agent layer 12 and between the substrate 11 and the release agent layer 12.
- the number of (meth) acryloyl groups in the (meth) acrylate (a1), the molecular weight of the dimethylorganopolysiloxane (a3), and Mass ratio of the amount of dimethylorganopolysiloxane (a3) to the total amount of (meth) acrylate (a1), polyvalent isocyanate compound (a2) and dimethylorganopolysiloxane (a3) (a3) / [(a1) + (a2 ) + (A3)]) is shown in Table 1.
- Example 1 100 parts by mass of the active energy ray-curable component (A1) and 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-) as an ⁇ -hydroxyketone photopolymerization initiator (B1) 5 parts by mass of propionyl) -benzyl] -phenyl ⁇ -2-methyl-propan-1-one (manufactured by BASF, product name “IRGACURE127”) in a mixed solvent of isopropyl alcohol and methyl ethyl ketone (mass ratio 3: 1) The solid content concentration was diluted to 20% by mass to obtain a release agent layer forming material.
- the obtained release agent layer forming material was used as a biaxially stretched polyethylene terephthalate (PET) film as a substrate (thickness 31 ⁇ m, arithmetic average roughness Ra0: 16 nm on the first surface, maximum protrusion height on the first surface)
- the first surface has a thickness Rp0: 196 nm
- the second surface has an arithmetic average roughness Ra2: 16 nm
- the second surface has a maximum protrusion height Rp2: 196 nm.
- the bar has a thickness of 1 ⁇ m after curing. It was applied by a coater and dried at 80 ° C. for 1 minute.
- the thickness of the release agent layer is a result measured by a measurement method described later (the following examples and the like are the same).
- Example 2 A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A2) was blended in place of the active energy ray-curable component (A1).
- Example 3 A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A3) was blended in place of the active energy ray-curable component (A1).
- Example 4 A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A4) was blended in place of the active energy ray-curable component (A1).
- Example 5 A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A5) was blended in place of the active energy ray-curable component (A1).
- Example 6 A release film was produced in the same manner as in Example 1 except that the thickness of the release agent layer was changed to 0.5 ⁇ m.
- Example 7 A release film was produced in the same manner as in Example 1 except that the thickness of the release agent layer was changed to 1.9 ⁇ m.
- Example 8 instead of the photopolymerization initiator (B1), 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1- as an ⁇ -aminoalkylphenone photopolymerization initiator (B2)
- a release film was produced in the same manner as in Example 1 except that ON (made by BASF, product name “IRGACURE907”) was blended.
- Example 9 instead of the base material in Example 1, a biaxially stretched PET film (thickness 38 ⁇ m, arithmetic average roughness Ra0: 15 nm of the first surface, maximum protrusion height Rp0: 98 nm of the first surface, second surface A release film was produced in the same manner as in Example 1 except that the arithmetic average roughness Ra2: 15 nm and the maximum protrusion height Rp2 of the second surface (Rp2: 98 nm) were used.
- Example 10 instead of the base material in Example 1, a biaxially stretched PET film (thickness 38 ⁇ m, arithmetic average roughness Ra0: 35 nm of the first surface, maximum protrusion height Rp0: 471 nm of the first surface, second surface A release film was prepared in the same manner as in Example 1 except that the arithmetic average roughness Ra2: 35 nm and the maximum protrusion height Rp2: 471 nm of the second surface were used.
- Example 1 A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A6) was blended in place of the active energy ray-curable component (A1).
- Example 2 A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A7) was blended in place of the active energy ray-curable component (A1).
- Example 3 A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A8) was blended in place of the active energy ray-curable component (A1).
- Example 4 A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A9) was blended in place of the active energy ray-curable component (A1).
- Example 6 A release film was produced in the same manner as in Example 1 except that the thickness of the release agent layer was changed to 0.2 ⁇ m.
- Example 7 instead of the base material in Example 1, a biaxially stretched PET film (thickness 38 ⁇ m, arithmetic average roughness Ra0: 42 nm of the first surface, maximum protrusion height Rp0: 619 nm of the first surface, second surface A release film was prepared in the same manner as in Example 1 except that the average roughness Ra2 of 42 nm and the maximum protrusion height Rp2 of the second surface (Rp2: 619 nm) were used.
- Example 8 instead of the substrate in Example 1, a biaxially stretched PET film (thickness 38 ⁇ m, arithmetic average roughness Ra0 of the first surface Ra0: 15 nm, maximum protrusion height Rp0 of the first surface Rp0: 105 nm, second surface A release film was prepared in the same manner as in Example 1 except that the arithmetic average roughness Ra2: 3 nm and the maximum protrusion height Rp2 of the second surface (Rp2: 15 nm) were used.
- Test Example 1 Measurement of thickness of release agent layer
- the thickness ( ⁇ m) of the release agent layer of the release films obtained in Examples and Comparative Examples was measured using a reflective film thickness meter (product name “F20” manufactured by Filmetrics). Specifically, after the release films obtained in Examples and Comparative Examples were cut into 100 mm ⁇ 100 mm, the release film was installed on the film thickness meter so that the surface opposite to the surface to be measured was on 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 defined as the thickness of the release agent layer. The results are shown in Table 2.
- the silicone migration was evaluated according to the following criteria. The results are shown in Table 3.
- the ceramic slurry was applied over a width of 250 mm and a length of 10 m so that the film thickness after drying with a die coater would be 1 ⁇ m. And dried at 80 ° C. for 1 minute in a dryer.
- the fluorescent lamp was illuminated from the release film side, all the molded ceramic green sheet surfaces were visually inspected, and slurry coating property was evaluated by the following judgment criteria. The results are shown in Table 3. A ... There was no pinhole in the ceramic green sheet B ... 1-5 pinholes occurred in the ceramic green sheet C ... More than 6 pinholes occurred in the ceramic green sheet
- Test Example 7 (Ceramic green sheet peelability evaluation) A ceramic green sheet formed on the surface of the release agent layer of the release film by the same procedure as in Test Example 6 was punched out to 200 mm ⁇ 200 mm without punching the release film. Next, using the sheet peeling mechanism of the green sheet laminating machine, the punched green sheet was adsorbed on a vacuum suction stage and peeled from the release film. The peelability from the ceramic green sheet at this time was evaluated according to the following criteria. The results are shown in Table 3. A: The ceramic green sheet can be peeled off smoothly without tearing, and the ceramic green sheet did not remain on the release agent layer. B: The ceramic green sheet could be peeled off slightly without being broken, and on the release agent layer. There was no ceramic green sheet left on the surface. C ... The ceramic green sheet was torn or could not be peeled off.
- the release film was peeled from the polyvinyl butyral resin layer, and the polyvinyl butyral resin layer was transferred to a polyester adhesive tape. Thereafter, the number of dents on the surface of the polyvinyl butyral resin layer that was in contact with the surface of the release agent layer was counted. Specifically, using a light interference type surface shape observation device (product name “WYKO-1100” manufactured by Vecco), observation was performed at 50 magnifications in the PSI mode, and the obtained 91.2 ⁇ m ⁇ 119.8 ⁇ m was obtained. On the basis of the surface shape images in the range, the number of recesses having a depth of 150 nm or more was counted.
- a light interference type surface shape observation device product name “WYKO-1100” manufactured by Vecco
- the ceramic green sheet was evaluated for defects on the surface of the release agent layer according to the following criteria.
- a sample that was evaluated as “C” could not obtain a satisfactory sample for performing this test. Did not.
- the results are shown in Table 3.
- the release films obtained in Examples and Comparative Examples were bonded to the polyvinyl butyral resin layer so that the second surface of the substrate in the release film was in contact with the polyvinyl butyral resin layer.
- the laminate was cut to 100 mm ⁇ 100 mm and then pressed with a load of 5 kg / cm 2 to transfer the protrusion shape of the second surface of the substrate in the release film to the polyvinyl butyral resin layer.
- the release film is peeled from the polyvinyl butyral resin layer, and the depth of the recess in the surface of the polyvinyl butyral resin film that has been in contact with the second surface of the substrate of the release film is measured, and the number of recesses is counted. It was. Specifically, the surface in the range of 91.2 ⁇ m ⁇ 119.8 ⁇ m obtained by observing at 50 magnifications in the PSI mode using an optical interference type surface shape observation device (Vecco, WYKO-1100). Based on the shape image, the depth of the dent was measured and the number of dents was counted.
- a defect evaluation of the ceramic green sheet by the second surface of the substrate was performed according to the following criteria.
- the results are shown in Table 3.
- the obtained capacitor is likely to be short-circuited due to a decrease in withstand voltage.
- A There was no change from when it was rolled up (no blocking)
- B In the area of less than half in the width direction, a change in color due to adhesion between the films was observed (there is some blocking but can be used)
- C Over the majority region in the width direction, a change in color due to adhesion between films was observed (with blocking)
- the release films of the examples were excellent in peelability from the ceramic green sheet, and the silicone-based compound (release imparting component) was not easily transferred to the ceramic green sheet. Moreover, according to the peeling film of an Example, it was hard to produce a defect in a ceramic green sheet, and also it was hard to generate
Abstract
Description
〔セラミックグリーンシート製造工程用剥離フィルム〕
図1に示すように、本実施形態に係るセラミックグリーンシート製造工程用剥離フィルム1(以下、単に「剥離フィルム1」という場合がある。)は、基材11と、基材11の第1の面111(図1では上面)に積層された剥離剤層12とを備えて構成される。基材11は、基材11の第1の面111と反対側の面(図1では下面)に第2の面112を備えている。 Hereinafter, embodiments of the present invention will be described.
[Peeling film for ceramic green sheet manufacturing process]
As shown in FIG. 1, a
本実施形態に係る剥離フィルム1の基材11は、剥離剤層12を積層することができれば特に限定されるものではない。かかる基材11としては、例えば、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル、ポリプロピレンやポリメチルペンテン等のポリオレフィン、ポリカーボネート、ポリ酢酸ビニルなどのプラスチックからなるフィルムが挙げられ、単層であってもよいし、同種又は異種の2層以上の多層であってもよい。これらの中でもポリエステルフィルムが好ましく、特にポリエチレンテレフタレートフィルムが好ましく、さらには二軸延伸ポリエチレンテレフタレートフィルムが好ましい。ポリエチレンテレフタレートフィルムは、加工時、使用時等において、埃等が発生しにくいため、例えば、埃等によるセラミックスラリー塗工不良等を効果的に防止することができる。さらに、ポリエチレンテレフタレートフィルムに帯電防止処理を行うことで、塗工不良等を防止する効果を高めることができる。 1. Base Material The
本実施形態に係る剥離フィルム1における剥離剤層12は、活性エネルギー線硬化性成分(A)及び光重合開始剤(B)を含有する剥離剤組成物(以下「剥離剤組成物R」という場合がある。)から形成される。剥離剤層12は、当該剥離剤組成物Rを硬化させて形成される。 2. Release agent layer The
ケイ素原子比率(原子%)=[(Si元素量)/(C元素量)+(O元素量)+(Si元素量)]×100 Specifically, after the polyvinyl butyral resin layer is formed on the
Silicon atomic ratio (atomic%) = [(Si element amount) / (C element amount) + (O element amount) + (Si element amount)] × 100
本実施形態に係る剥離フィルム1は、基材11の第1の面111に、剥離剤組成物R及び所望により有機溶剤を含有する剥離剤層形成用材料を塗布した後、必要に応じて乾燥し、活性エネルギー線の照射により硬化させて剥離剤層12を形成することにより、製造することができる。剥離剤層形成用材料の塗布方法としては、例えば、グラビアコート法、バーコート法、スプレーコート法、スピンコート法、ナイフコート法、ロールコート法、ダイコート法等が使用できる。 3. Manufacturing method of release film for ceramic green sheet manufacturing process The
撹拌機、還流冷却器、滴下漏斗及び温度計を備えた反応器に、多価イソシアネート(a2)としてのヘキサメチレンジイソシアネート100質量部(固形分換算;以下同じ)と、ジメチルオルガノポリシロキサン(a3)(チッソ社製,製品名「サイラプレーンFMDA11」,数平均分子量1000;一般式(3)に示される構造を有し、一般式(3)におけるR1は-OH、R2は-(CH2)3OCH2CH2-、R3は-CH2CH3である。同製品の構造は以下同じ。)300質量部と、メチルエチルケトン400質量部とを仕込み、85℃まで昇温して7時間保温して反応させ、反応物を得た。 [Production Example 1]
In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 100 parts by mass of hexamethylene diisocyanate as a polyvalent isocyanate (a2) (in terms of solid content; the same shall apply hereinafter) and dimethylorganopolysiloxane (a3) (Manufactured by Chisso Corporation, product name “Silaplane FMDA11”, number average molecular weight 1000; having the structure represented by the general formula (3), R 1 in the general formula (3) is —OH, R 2 is — (CH 2 ) 3 OCH 2 CH 2 —, R 3 is —CH 2 CH 3. The structure of the product is the same below.) 300 parts by weight and 400 parts by weight of methyl ethyl ketone were charged, heated to 85 ° C. and heated for 7 hours. The reaction was obtained by incubating.
撹拌機、還流冷却器、滴下漏斗及び温度計を備えた反応器に、多価イソシアネート(a2)としてのヘキサメチレンジイソシアネート100質量部と、ジメチルオルガノポリシロキサン(a3)(チッソ社製,製品名「サイラプレーンFMDA11」,数平均分子量1000)300質量部と、メチルエチルケトン400質量部とを仕込み、85℃まで昇温して7時間保温して反応させ、反応物を得た。 [Production Example 2]
In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 100 parts by mass of hexamethylene diisocyanate as the polyvalent isocyanate (a2) and dimethylorganopolysiloxane (a3) (manufactured by Chisso Corporation, product name “ Thylaplane FMDA11 ", number average molecular weight 1000) 300 parts by mass and methyl ethyl ketone 400 parts by mass were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product.
撹拌機、還流冷却器、滴下漏斗及び温度計を備えた反応器に、多価イソシアネート(a2)としてのヘキサメチレンジイソシアネート100質量部と、ジメチルオルガノポリシロキサン(a3)(チッソ社製,製品名「サイラプレーンFMDA21」,数平均分子量5000;一般式(3)に示される構造を有し、一般式(3)におけるR1は-OH、R2は-(CH2)3OCH2CH2-、R3は-CH2CH3である。)1488質量部と、メチルエチルケトン1588質量部とを仕込み、85℃まで昇温して7時間保温して反応させ、反応物を得た。 [Production Example 3]
In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 100 parts by mass of hexamethylene diisocyanate as the polyvalent isocyanate (a2) and dimethylorganopolysiloxane (a3) (manufactured by Chisso Corporation, product name “ Silaplane FMDA21 ”, number average molecular weight 5000; having the structure represented by the general formula (3), R 1 in the general formula (3) is —OH, R 2 is — (CH 2 ) 3 OCH 2 CH 2 —, R 3 is —CH 2 CH 3 ) 1488 parts by mass and 1588 parts by mass of methyl ethyl ketone were charged, the temperature was raised to 85 ° C. and the reaction was continued for 7 hours to obtain a reaction product.
撹拌機、還流冷却器、滴下漏斗及び温度計を備えた反応器に、多価イソシアネート(a2)としてのヘキサメチレンジイソシアネート100質量部と、ジメチルオルガノポリシロキサン(a3)(チッソ社製,製品名「サイラプレーンFMDA11」,数平均分子量1000)300質量部と、メチルエチルケトン400質量部とを仕込み、85℃まで昇温して7時間保温して反応させ、反応物を得た。 [Production Example 4]
In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 100 parts by mass of hexamethylene diisocyanate as the polyvalent isocyanate (a2) and dimethylorganopolysiloxane (a3) (manufactured by Chisso Corporation, product name “ Thylaplane FMDA11 ", number average molecular weight 1000) 300 parts by mass and methyl ethyl ketone 400 parts by mass were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product.
撹拌機、還流冷却器、滴下漏斗及び温度計を備えた反応器に、多価イソシアネート(a2)としてのヘキサメチレンジイソシアネートのイソシアヌレート体100質量部と、ジメチルオルガノポリシロキサン(a3)(チッソ社製,製品名「サイラプレーンFM0411」,数平均分子量1000;一般式(5)に示される構造を有し、一般式(5)におけるR6は-OH、R7は-C3H6OC2H4-である。)175質量部と、メチルエチルケトン275質量部とを仕込み、85℃まで昇温して7時間保温して反応させ、反応物を得た。 [Production Example 5]
In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 100 parts by mass of isocyanurate of hexamethylene diisocyanate as polyvalent isocyanate (a2) and dimethylorganopolysiloxane (a3) (manufactured by Chisso Corporation) , Product name “Silaplane FM0411”, number average molecular weight 1000; having the structure represented by the general formula (5), R 6 in the general formula (5) is —OH, and R 7 is —C 3 H 6 OC 2 H 4 -. a a) and 175 parts by weight, were charged methyl ethyl ketone 275 parts by mass, and reacted by incubating was heated to 85 ° C. 7 hours to obtain a reaction product.
撹拌機、還流冷却器、滴下漏斗及び温度計を備えた反応器に、多価イソシアネート(a2)としてのヘキサメチレンジイソシアネート100質量部と、ジメチルオルガノポリシロキサン(a3)(チッソ社製,製品名「サイラプレーンFMDA11」,数平均分子量1000)300質量部と、メチルエチルケトン400質量部とを仕込み、85℃まで昇温して7時間保温して反応させ、反応物を得た。 [Production Example 6]
In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 100 parts by mass of hexamethylene diisocyanate as the polyvalent isocyanate (a2) and dimethylorganopolysiloxane (a3) (manufactured by Chisso Corporation, product name “ Thylaplane FMDA11 ", number average molecular weight 1000) 300 parts by mass and methyl ethyl ketone 400 parts by mass were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product.
撹拌機、還流冷却器、滴下漏斗及び温度計を備えた反応器に、多価イソシアネート(a2)としてのヘキサメチレンジイソシアネート100質量部と、ジメチルオルガノポリシロキサン(a3)(チッソ社製,製品名「サイラプレーンFMDA11」,数平均分子量1000)300質量部と、メチルエチルケトン400質量部とを仕込み、85℃まで昇温して7時間保温して反応させ、反応物を得た。 [Production Example 7]
In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 100 parts by mass of hexamethylene diisocyanate as the polyvalent isocyanate (a2) and dimethylorganopolysiloxane (a3) (manufactured by Chisso Corporation, product name “ Thylaplane FMDA11 ", number average molecular weight 1000) 300 parts by mass and methyl ethyl ketone 400 parts by mass were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product.
撹拌機、還流冷却器、滴下漏斗及び温度計を備えた反応器に、多価イソシアネート(a2)としてのヘキサメチレンジイソシアネート100質量部と、ジメチルオルガノポリシロキサン(a3)(チッソ社製,製品名「サイラプレーンFMDA26」,数平均分子量15000;一般式(3)に示される構造を有し、一般式(3)におけるR1は-OH、R2は-(CH2)3OCH2CH2-、R3は-CH2CH3である。)4460質量部と、メチルエチルケトン4560質量部とを仕込み、85℃まで昇温して7時間保温して反応させ、反応物を得た。 [Production Example 8]
In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 100 parts by mass of hexamethylene diisocyanate as the polyvalent isocyanate (a2) and dimethylorganopolysiloxane (a3) (manufactured by Chisso Corporation, product name “ Silaplane FMDA26 ", number average molecular weight 15000; having a structure represented by the general formula (3), R 1 in the general formula (3) is -OH, R 2 is-(CH 2 ) 3 OCH 2 CH 2- , R 3 is —CH 2 CH 3 ) 4460 parts by mass and 4560 parts by mass of methyl ethyl ketone were charged, the temperature was raised to 85 ° C., and the reaction was continued for 7 hours to obtain a reaction product.
撹拌機、還流冷却器、滴下漏斗及び温度計を備えた反応器に、多価イソシアネート(a2)としてのヘキサメチレンジイソシアネート100質量部と、ジメチルオルガノポリシロキサン(a3)(チッソ社製,製品名「サイラプレーンFMDA11」,数平均分子量1000)300質量部と、メチルエチルケトン400質量部とを仕込み、85℃まで昇温して7時間保温して反応させ、反応物を得た。 [Production Example 9]
In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 100 parts by mass of hexamethylene diisocyanate as the polyvalent isocyanate (a2) and dimethylorganopolysiloxane (a3) (manufactured by Chisso Corporation, product name “ Thylaplane FMDA11 ", number average molecular weight 1000) 300 parts by mass and methyl ethyl ketone 400 parts by mass were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product.
活性エネルギー線硬化性成分(A1)100質量部と、α-ヒドロキシケトン系の光重合開始剤(B1)としての2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]-フェニル}-2-メチル-プロパン-1-オン(BASF社製,製品名「IRGACURE127」)5質量部とを、イソプロピルアルコール及びメチルエチルケトンの混合溶剤(質量比3:1)にて固形分濃度20質量%に希釈し、剥離剤層形成用材料を得た。 [Example 1]
100 parts by mass of the active energy ray-curable component (A1) and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-) as an α-hydroxyketone photopolymerization initiator (B1) 5 parts by mass of propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (manufactured by BASF, product name “IRGACURE127”) in a mixed solvent of isopropyl alcohol and methyl ethyl ketone (mass ratio 3: 1) The solid content concentration was diluted to 20% by mass to obtain a release agent layer forming material.
活性エネルギー線硬化性成分(A1)の替わりに活性エネルギー線硬化性成分(A2)を配合した以外は、実施例1と同様にして剥離フィルムを作製した。 [Example 2]
A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A2) was blended in place of the active energy ray-curable component (A1).
活性エネルギー線硬化性成分(A1)の替わりに活性エネルギー線硬化性成分(A3)を配合した以外は、実施例1と同様にして剥離フィルムを作製した。 Example 3
A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A3) was blended in place of the active energy ray-curable component (A1).
活性エネルギー線硬化性成分(A1)の替わりに活性エネルギー線硬化性成分(A4)を配合した以外は、実施例1と同様にして剥離フィルムを作製した。 Example 4
A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A4) was blended in place of the active energy ray-curable component (A1).
活性エネルギー線硬化性成分(A1)の替わりに活性エネルギー線硬化性成分(A5)を配合した以外は、実施例1と同様にして剥離フィルムを作製した。 Example 5
A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A5) was blended in place of the active energy ray-curable component (A1).
剥離剤層の厚さを0.5μmに変更した以外は、実施例1と同様にして剥離フィルムを作製した。 Example 6
A release film was produced in the same manner as in Example 1 except that the thickness of the release agent layer was changed to 0.5 μm.
剥離剤層の厚さを1.9μmに変更した以外は、実施例1と同様にして剥離フィルムを作製した。 Example 7
A release film was produced in the same manner as in Example 1 except that the thickness of the release agent layer was changed to 1.9 μm.
光重合開始剤(B1)の替わりに、α-アミノアルキルフェノン系の光重合開始剤(B2)としての2-メチル-1[4-(メチルチオ)フェニル]-2-モリフォリノプロパン-1-オン(BASF社製,製品名「IRGACURE907」)を配合した以外は、実施例1と同様にして剥離フィルムを作製した。 Example 8
Instead of the photopolymerization initiator (B1), 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1- as an α-aminoalkylphenone photopolymerization initiator (B2) A release film was produced in the same manner as in Example 1 except that ON (made by BASF, product name “IRGACURE907”) was blended.
実施例1における基材の替わりに、二軸延伸PETフィルム(厚さ38μm,第1の面の算術平均粗さRa0:15nm,第1の面の最大突起高さRp0:98nm,第2の面の算術平均粗さRa2:15nm,第2の面の最大突起高さRp2:98nm)を用いた以外は、実施例1と同様にして剥離フィルムを作製した。 Example 9
Instead of the base material in Example 1, a biaxially stretched PET film (thickness 38 μm, arithmetic average roughness Ra0: 15 nm of the first surface, maximum protrusion height Rp0: 98 nm of the first surface, second surface A release film was produced in the same manner as in Example 1 except that the arithmetic average roughness Ra2: 15 nm and the maximum protrusion height Rp2 of the second surface (Rp2: 98 nm) were used.
実施例1における基材の替わりに、二軸延伸PETフィルム(厚さ38μm,第1の面の算術平均粗さRa0:35nm,第1の面の最大突起高さRp0:471nm,第2の面の算術平均粗さRa2:35nm,第2の面の最大突起高さRp2:471nm)を用いた以外は、実施例1と同様にして剥離フィルムを作製した。 Example 10
Instead of the base material in Example 1, a biaxially stretched PET film (thickness 38 μm, arithmetic average roughness Ra0: 35 nm of the first surface, maximum protrusion height Rp0: 471 nm of the first surface, second surface A release film was prepared in the same manner as in Example 1 except that the arithmetic average roughness Ra2: 35 nm and the maximum protrusion height Rp2: 471 nm of the second surface were used.
活性エネルギー線硬化性成分(A1)の替わりに活性エネルギー線硬化性成分(A6)を配合した以外は、実施例1と同様にして剥離フィルムを作製した。 [Comparative Example 1]
A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A6) was blended in place of the active energy ray-curable component (A1).
活性エネルギー線硬化性成分(A1)の替わりに活性エネルギー線硬化性成分(A7)を配合した以外は、実施例1と同様にして剥離フィルムを作製した。 [Comparative Example 2]
A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A7) was blended in place of the active energy ray-curable component (A1).
活性エネルギー線硬化性成分(A1)の替わりに活性エネルギー線硬化性成分(A8)を配合した以外は、実施例1と同様にして剥離フィルムを作製した。 [Comparative Example 3]
A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A8) was blended in place of the active energy ray-curable component (A1).
活性エネルギー線硬化性成分(A1)の替わりに活性エネルギー線硬化性成分(A9)を配合した以外は、実施例1と同様にして剥離フィルムを作製した。 [Comparative Example 4]
A release film was produced in the same manner as in Example 1 except that the active energy ray-curable component (A9) was blended in place of the active energy ray-curable component (A1).
活性エネルギー線硬化性成分としてのジペンタエリスリトールヘキサアクリレート99質量部と、メタクリロイル基含有シリコーン樹脂組成物(信越化学工業社製,製品名「X-62-164A」)1質量部と、α-ヒドロキシケトン系の光重合開始剤(B1)としての2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]-フェニル}-2-メチル-プロパン-1-オン(BASF社製,製品名「IRGACURE127」)5質量部とを、イソプロピルアルコール及びメチルエチルケトンの混合溶剤(質量比3:1)にて固形分濃度20質量%に希釈し、剥離剤層形成用材料を得た。この剥離剤層形成用材料を使用して、実施例1と同様にして剥離フィルムを作製した。 [Comparative Example 5]
99 parts by mass of dipentaerythritol hexaacrylate as an active energy ray-curable component, 1 part by mass of a methacryloyl group-containing silicone resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., product name “X-62-164A”), and α-hydroxy 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1- as a ketone-based photopolymerization initiator (B1) 5 parts by mass of ON (manufactured by BASF, product name “IRGACURE127”) is diluted with a mixed solvent of isopropyl alcohol and methyl ethyl ketone (mass ratio 3: 1) to a solid content concentration of 20% by mass, and a release agent layer forming material Got. Using this release agent layer forming material, a release film was prepared in the same manner as in Example 1.
剥離剤層の厚さを0.2μmに変更した以外は、実施例1と同様にして剥離フィルムを作製した。 [Comparative Example 6]
A release film was produced in the same manner as in Example 1 except that the thickness of the release agent layer was changed to 0.2 μm.
実施例1における基材の替わりに、二軸延伸PETフィルム(厚さ38μm,第1の面の算術平均粗さRa0:42nm,第1の面の最大突起高さRp0:619nm,第2の面の算術平均粗さRa2:42nm,第2の面の最大突起高さRp2:619nm)を用いた以外は、実施例1と同様にして剥離フィルムを作製した。 [Comparative Example 7]
Instead of the base material in Example 1, a biaxially stretched PET film (thickness 38 μm, arithmetic average roughness Ra0: 42 nm of the first surface, maximum protrusion height Rp0: 619 nm of the first surface, second surface A release film was prepared in the same manner as in Example 1 except that the average roughness Ra2 of 42 nm and the maximum protrusion height Rp2 of the second surface (Rp2: 619 nm) were used.
実施例1における基材の替わりに、二軸延伸PETフィルム(厚さ38μm,第1の面の算術平均粗さRa0:15nm,第1の面の最大突起高さRp0:105nm,第2の面の算術平均粗さRa2:3nm,第2の面の最大突起高さRp2:15nm)を用いた以外は、実施例1と同様にして剥離フィルムを作製した。 [Comparative Example 8]
Instead of the substrate in Example 1, a biaxially stretched PET film (thickness 38 μm, arithmetic average roughness Ra0 of the first surface Ra0: 15 nm, maximum protrusion height Rp0 of the first surface Rp0: 105 nm, second surface A release film was prepared in the same manner as in Example 1 except that the arithmetic average roughness Ra2: 3 nm and the maximum protrusion height Rp2 of the second surface (Rp2: 15 nm) were used.
実施例及び比較例で得られた剥離フィルムの剥離剤層の厚さ(μm)を、反射式膜厚計(フィルメトリックス社製,製品名「F20」)を使用して測定した。具体的には、実施例及び比較例で得られた剥離フィルムを100mm×100mmに裁断した後、測定する側の面の反対面が吸引ステージ側となるように剥離フィルムを膜厚計に設置し、剥離剤層表面の10ヵ所について膜厚を測定し、その平均値を剥離剤層の厚さとした。結果を表2に示す。 [Test Example 1] (Measurement of thickness of release agent layer)
The thickness (μm) of the release agent layer of the release films obtained in Examples and Comparative Examples was measured using a reflective film thickness meter (product name “F20” manufactured by Filmetrics). Specifically, after the release films obtained in Examples and Comparative Examples were cut into 100 mm × 100 mm, the release film was installed on the film thickness meter so that the surface opposite to the surface to be measured was on 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 defined as the thickness of the release agent layer. The results are shown in Table 2.
ガラス板に両面テープを貼付し、実施例及び比較例で得られた剥離フィルムを、測定する側の面の反対面がガラス板側となるように上記両面テープを介してガラス板に固定した。その剥離フィルムの剥離剤層の表面(露出している表面;以下同じ)における算術平均粗さ(Ra1;nm)及び最大突起高さ(Rp1;nm)を、表面粗さ測定機(ミツトヨ社製,製品名「SV-3000S4」,触針式)を使用し、JIS B0601-1994に準拠して測定した。結果を表2に示す。 [Test Example 2] (Measurement of surface roughness of release agent layer)
A double-sided tape was affixed to the glass plate, and the release films obtained in the examples and comparative examples were fixed to the glass plate via the double-sided tape so that the surface opposite to the surface to be measured was on the glass plate side. The arithmetic average roughness (Ra1; nm) and maximum protrusion height (Rp1; nm) on the surface of the release agent layer of the release film (exposed surface; the same applies hereinafter) and the surface roughness measuring machine (Mitutoyo) , Product name “SV-3000S4”, stylus type) and measured according to JIS B0601-1994. The results are shown in Table 2.
トルエン及びエタノールの混合溶剤(質量比50:50)にて、ポリビニルブチラール樹脂(積水化学社製,製品名「エスレックB・K BL-S」,粉末状)を固形分濃度20質量%に溶解し、ポリビニルブチラール樹脂溶液を得た。得られたポリビニラール樹脂溶液を、実施例及び比較例で得られた剥離フィルムの剥離剤層表面に、乾燥後の厚さが4μmとなるようにバーコーターによって塗布し、乾燥させてポリビニラール樹脂層を形成した。 [Test Example 3] (Evaluation of silicone migration)
In a mixed solvent of toluene and ethanol (mass ratio 50:50), polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd., product name “S-REC B / K BL-S”, powder form) is dissolved to a solid content concentration of 20 mass%. A polyvinyl butyral resin solution was obtained. The obtained polyvinyl resin solution was applied to the release agent layer surface of the release film obtained in Examples and Comparative Examples with a bar coater so that the thickness after drying was 4 μm, and dried to form a polyvinyl resin layer. Formed.
ケイ素原子比率(原子%)=[(Si元素量)/(C元素量)+(O元素量)+(Si元素量)]×100 The polyvinyl resin layer is peeled from the release film, and the surface of the polyvinyl resin layer that has been in contact with the surface of the release agent layer is measured by X-ray photoelectron spectroscopy (XPS), silicon atoms (Si), carbon atoms ( Based on the amount of C) and oxygen atoms (O) (XPS count number), the silicon atom ratio (atomic%) was calculated by the following formula.
Silicon atomic ratio (atomic%) = [(Si element amount) / (C element amount) + (O element amount) + (Si element amount)] × 100
A…ケイ素原子比率が0.3原子%未満
B…ケイ素原子比率が0.3原子%以上、1.0原子%未満
C…ケイ素原子比率が1.0原子%以上 The silicone migration was evaluated according to the following criteria. The results are shown in Table 3.
A: Silicon atomic ratio is less than 0.3 atomic% B: Silicon atomic ratio is 0.3 atomic% or more and less than 1.0 atomic% C: Silicon atomic ratio is 1.0 atomic% or more
実施例及び比較例で得られた剥離フィルムについて、剥離剤層の塗工面(表面)の状態を目視にて観察し、以下の判断基準により、剥離剤層の塗工面を評価した。結果を表3に示す。
A…塗工スジによる面異常がなかった
B…塗工スジによる面異常は若干あるものの、使用上問題なかった
C…塗工スジが塗工面全体に発生した、または極端な面異常が発生した [Test Example 4] (Evaluation of coating surface of release agent layer)
About the release film obtained by the Example and the comparative example, the state of the coating surface (surface) of a release agent layer was observed visually, and the coating surface of the release agent layer was evaluated by the following judgment criteria. The results are shown in Table 3.
A: There was no surface abnormality due to coating stripes B: Although there were some surface abnormalities due to coating stripes, there was no problem in use C: Coating stripes occurred on the entire coated surface, or extreme surface abnormalities occurred
実施例及び比較例で得られた剥離フィルムについて、メチルエチルケトンを含ませたウエス(小津産業社製,製品名「BEMCOT AP-2」)によって、剥離剤層の表面を荷重1kg/cm2で往復10回研磨した。その後、剥離剤層の表面を目視で観察し、以下の判断基準により剥離剤層の硬化性を評価した。なお、本試験(試験例5)において、評価が「C」であったものについては、他の試験を行うのに満足な試料を得ることができなかったため、他の試験は行わなかった。結果を表3に示す。
A…剥離剤層の溶解・脱落がなかった
B…剥離剤層の一部溶解が見られた
C…剥離剤層が完全に溶解し、基材から脱落した [Test Example 5] (Evaluation of curability of release agent layer)
For the release films obtained in Examples and Comparative Examples, the surface of the release agent layer was reciprocated at a load of 1 kg / cm 2 with a waste containing methyl ethyl ketone (product name “BEMCOT AP-2”) containing methyl ethyl ketone. Polished twice. Thereafter, the surface of the release agent layer was visually observed, and the curability of the release agent layer was evaluated according to the following criteria. In addition, in this test (Test Example 5), for samples with an evaluation of “C”, a sample satisfactory for performing other tests could not be obtained, and thus other tests were not performed. The results are shown in Table 3.
A: The release agent layer did not dissolve / drop off B: Part of the release agent layer was found to be dissolved C: The release agent layer was completely dissolved and dropped from the substrate
チタン酸バリウム粉末(BaTiO3;堺化学工業社製,製品名「BT-03」)100質量部、バインダーとしてのポリビニルブチラール樹脂(積水化学工業社製,製品名「エスレックB・K BM-2」)8質量部、及び可塑剤としてのフタル酸ジオクチル(関東化学社製,フタル酸ジオクチル 鹿1級)4質量部に、トルエン及びエタノールの混合液(質量比6:4)135質量部とを、ジルコニアビーズの存在下で、ボールミルにて混合し分散させて、ビーズを除去してセラミックスラリーを調製した。 [Test Example 6] (Slurry coating property evaluation)
100 parts by weight of barium titanate powder (BaTiO 3 ; manufactured by Sakai Chemical Industry Co., Ltd., product name “BT-03”), polyvinyl butyral resin as a binder (manufactured by Sekisui Chemical Co., Ltd., product name “S-REC B / K BM-2”) ) 8 parts by mass and 4 parts by mass of dioctyl phthalate (manufactured by Kanto Chemical Co., Ltd., dioctyl phthalate deer grade 1) as a plasticizer, 135 parts by mass of a mixed solution of toluene and ethanol (mass ratio 6: 4), In the presence of zirconia beads, they were mixed and dispersed by a ball mill, and the beads were removed to prepare a ceramic slurry.
A…セラミックグリーンシートにピンホールがなかった
B…セラミックグリーンシートに1~5個のピンホールが発生した
C…セラミックグリーンシートに6個以上のピンホールが発生した On the surface of the release agent layer of the release films obtained in Examples and Comparative Examples, the ceramic slurry was applied over a width of 250 mm and a length of 10 m so that the film thickness after drying with a die coater would be 1 μm. And dried at 80 ° C. for 1 minute in a dryer. About the release film in which the ceramic green sheet was shape | molded, the fluorescent lamp was illuminated from the release film side, all the molded ceramic green sheet surfaces were visually inspected, and slurry coating property was evaluated by the following judgment criteria. The results are shown in Table 3.
A ... There was no pinhole in the ceramic green sheet B ... 1-5 pinholes occurred in the ceramic green sheet C ... More than 6 pinholes occurred in the ceramic green sheet
試験例6と同じ手順により剥離フィルムの剥離剤層表面に成形したセラミックグリーンシートを、剥離フィルムを打ち抜かないようにして200mm×200mmに打ち抜いた。次いで、グリーンシート積層機のシート剥離機構を利用して、打ち抜かれたグリーンシートを真空吸引ステージに吸着させ、剥離フィルムから剥離した。このときのセラミックグリーンシートからの剥離性を、以下の判断基準により評価した。結果を表3に示す。
A…セラミックグリーンシートが破れることなく、スムーズに剥離でき、剥離剤層上にセラミックグリーンシートが残らなかった
B…セラミックグリーンシートが破れることなく、ややスムーズさに欠けるものの剥離でき、剥離剤層上にセラミックグリーンシートが残らなかった
C…セラミックグリーンシートが破れるか、剥離できなかった [Test Example 7] (Ceramic green sheet peelability evaluation)
A ceramic green sheet formed on the surface of the release agent layer of the release film by the same procedure as in Test Example 6 was punched out to 200 mm × 200 mm without punching the release film. Next, using the sheet peeling mechanism of the green sheet laminating machine, the punched green sheet was adsorbed on a vacuum suction stage and peeled from the release film. The peelability from the ceramic green sheet at this time was evaluated according to the following criteria. The results are shown in Table 3.
A: The ceramic green sheet can be peeled off smoothly without tearing, and the ceramic green sheet did not remain on the release agent layer. B: The ceramic green sheet could be peeled off slightly without being broken, and on the release agent layer. There was no ceramic green sheet left on the surface. C ... The ceramic green sheet was torn or could not be peeled off.
トルエン及びエタノールの混合溶剤(質量比60:40)にて、ポリビニルブチラール樹脂(積水化学社製,製品名「エスレックB・K BL-S」,粉末状)を固形分濃度20質量%に溶解し、ポリビニルブチラール樹脂溶液を得た。得られたポリビニルブチラール樹脂溶液を、実施例及び比較例で得られた剥離フィルムの剥離剤層の上に、乾燥後の厚さが3μmとなるように塗布し、80℃で1分間乾燥させてポリビニルブチラール樹脂層を成形した。そして、そのポリビニルブチラール樹脂層の表面にポリエステル粘着テープを貼付した。 [Test Example 8] (Defect evaluation of ceramic green sheet on the surface of the release agent layer)
In a mixed solvent of toluene and ethanol (mass ratio 60:40), polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd., product name “S-REC B / K BL-S”, powdered) is dissolved to a solid content concentration of 20% by mass. A polyvinyl butyral resin solution was obtained. The obtained polyvinyl butyral resin solution was applied on the release agent layer of the release film obtained in Examples and Comparative Examples so that the thickness after drying was 3 μm, and dried at 80 ° C. for 1 minute. A polyvinyl butyral resin layer was molded. And the polyester adhesive tape was stuck on the surface of the polyvinyl butyral resin layer.
A…凹みの数が0個
B…凹みの数が1~5個
C…凹みの数が6個以上
なお、上記評価Cの凹みが存在するセラミックグリーンシートでコンデンサを製造した場合、得られるコンデンサは、耐電圧低下によるショートが発生し易いものとなる。 Based on the number of depressions, the ceramic green sheet was evaluated for defects on the surface of the release agent layer according to the following criteria. In addition, in the above-described test for evaluating the peelability of the ceramic green sheet (Test Example 7), a sample that was evaluated as “C” could not obtain a satisfactory sample for performing this test. Did not. The results are shown in Table 3.
A: Number of dents is 0 B: Number of dents is 1-5 C: Number of dents is 6 or more Capacitors obtained when a capacitor is manufactured from a ceramic green sheet having the above-mentioned evaluation C Is likely to cause a short circuit due to a decrease in withstand voltage.
トルエン及びエタノールの混合溶剤(質量比60:40)にて、ポリビニルブチラール樹脂(積水化学社製,製品名「エスレックB・K BL-S」,粉末状)を固形分濃度20質量%に溶解し、ポリビニルブチラール樹脂溶液を得た。得られたポリビニルブチラール樹脂溶液を、厚さ50μmのPETフィルム上に、乾燥後の厚さが3μmとなるように塗布し、80℃で1分間乾燥させてポリビニルブチラール樹脂層を成形した。 [Test Example 9] (Defect evaluation of ceramic green sheet by the second surface of the substrate)
In a mixed solvent of toluene and ethanol (mass ratio 60:40), polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd., product name “S-REC B / K BL-S”, powdered) is dissolved to a solid content concentration of 20% by mass. A polyvinyl butyral resin solution was obtained. The obtained polyvinyl butyral resin solution was applied onto a 50 μm thick PET film so that the thickness after drying was 3 μm, and dried at 80 ° C. for 1 minute to form a polyvinyl butyral resin layer.
A…深さ300nm以上の凹みの数が0個
B…深さ500nm以上の凹みの数が0個で、深さ300nm以上500nm未満の凹みの数が1個以上
C…深さ500nm以上の凹みの数が1個以上
なお、上記評価Cの凹みが存在するセラミックグリーンシートでコンデンサを製造した場合、得られるコンデンサは、耐電圧低下によるショートが発生し易いものとなる。 Based on the depth and number of the dents, a defect evaluation of the ceramic green sheet by the second surface of the substrate was performed according to the following criteria. The results are shown in Table 3.
A: The number of recesses having a depth of 300 nm or more is 0 B: The number of recesses having a depth of 500 nm or more is 0, and the number of recesses having a depth of 300 nm or more and less than 500 nm is 1 or more C: A recess having a depth of 500 nm or more In addition, when a capacitor is manufactured with the ceramic green sheet in which the dent of the evaluation C exists, the obtained capacitor is likely to be short-circuited due to a decrease in withstand voltage.
実施例及び比較例で得られた剥離フィルムをロール状にする際のハンドリング性について評価した。具体的には、接触した剥離フィルム同士の滑り性、ロール状にする際の空気抜けの良さ、及び剥離フィルムの巻きズレの生じ難さについて、以下の判断基準により評価した。結果を表3に示す。
A…接触した剥離フィルム同士の滑り性が良く、かつ剥離フィルムをロール状にするときの空気抜けが良く、剥離フィルムの巻きズレを防止できた
B…接触した剥離フィルム同士の滑り性が若干悪く、かつ剥離フィルムをロール状に巻いたときの空気の抜けが若干悪く、巻きズレが若干生じるものの支障はなかった
C…接触した剥離フィルム同士の滑り性が悪く、かつ剥離フィルムをロール状に巻いたときの空気の抜けが悪く、巻きズレが顕著に生じた [Test Example 10] (Handling evaluation)
The handling properties when the release films obtained in Examples and Comparative Examples were made into rolls were evaluated. Specifically, the following judgment criteria evaluated the slipperiness | slidability of the peeling films which contacted, the good air bleed at the time of making it into a roll shape, and the difficulty of generating the winding gap of a peeling film. The results are shown in Table 3.
A ... Good slipperiness between peeled release films and good air escape when making the release film into a roll, and prevented winding film from slipping. B ... Slightly slippery contacted release films were slightly worse. When the release film was wound into a roll, the air escape was slightly worse, and there was no hindrance although some winding deviation occurred. C ... The slipperiness between the release films contacted was poor, and the release film was wound into a roll. The air escape was bad and the winding deviation was noticeable.
実施例及び比較例で得られた剥離フィルムを、幅400mm、長さ5000mのロール状に巻き上げた。この剥離フィルムロールを40℃、湿度50%以下の環境下に30日間保管し、剥離フィルムロールそのままの状態での外観を目視にて観察し、以下の判断基準によりブロッキング性を評価した。結果を表3に示す。
A…ロール状に巻き上げたときから変化がなかった(ブロッキング無し)
B…幅方向における半分以下の領域にて、フィルム同士の密着に起因する色目の変化が見られた(ブロッキングは若干有るが使用可能)
C…幅方向における過半の領域にわたって、フィルム同士の密着に起因する色目の変化が見られた(ブロッキング有り) [Test Example 11] (Evaluation of blocking properties)
The release films obtained in Examples and Comparative Examples were rolled up into a roll having a width of 400 mm and a length of 5000 m. This release film roll was stored for 30 days in an environment of 40 ° C. and a humidity of 50% or less. The appearance of the release film roll as it was was visually observed, and the blocking property was evaluated according to the following criteria. The results are shown in Table 3.
A: There was no change from when it was rolled up (no blocking)
B: In the area of less than half in the width direction, a change in color due to adhesion between the films was observed (there is some blocking but can be used)
C: Over the majority region in the width direction, a change in color due to adhesion between films was observed (with blocking)
11…基材
111…第1の面
112…第2の面
12…剥離剤層
121…表面 DESCRIPTION OF
Claims (3)
- 第1の面及び第2の面を有する基材と、前記基材の第1の面に設けられた剥離剤層とを備えたセラミックグリーンシート製造工程用剥離フィルムであって、
前記剥離剤層は、活性エネルギー線硬化性成分(A)及び光重合開始剤(B)を含有する剥離剤組成物から形成され、
前記活性エネルギー線硬化性成分(A)は、
1分子中に平均して少なくとも3個の(メタ)アクリロイル基を有する水酸基含有(メタ)アクリレート(a1)と、
多価イソシアネート化合物(a2)と、
1分子中に少なくとも1個の水酸基を有し、質量平均分子量が500~8000の直鎖状のジメチルオルガノポリシロキサン(a3)とを、
前記(メタ)アクリレート(a1)、前記多価イソシアネート化合物(a2)及び前記ジメチルオルガノポリシロキサン(a3)の合計量に対する前記ジメチルオルガノポリシロキサン(a3)の量が質量比で0.01~0.10となるように反応させてなり、
前記剥離剤層の厚さは0.3~2μmであり、
前記剥離剤層の前記基材とは反対側の面における算術平均粗さ(Ra1)が8nm以下であり、かつ最大突起高さ(Rp1)が50nm以下であり、
前記基材の第2の面における算術平均粗さ(Ra2)が5~40nmであり、かつ最大突起高さ(Rp2)が60~500nmである
ことを特徴とするセラミックグリーンシート製造工程用剥離フィルム。 A release film for a ceramic green sheet manufacturing process comprising a substrate having a first surface and a second surface, and a release agent layer provided on the first surface of the substrate,
The release agent layer is formed from a release agent composition containing an active energy ray-curable component (A) and a photopolymerization initiator (B),
The active energy ray-curable component (A) is
A hydroxyl group-containing (meth) acrylate (a1) having an average of at least three (meth) acryloyl groups in one molecule;
A polyvalent isocyanate compound (a2);
A linear dimethylorganopolysiloxane (a3) having at least one hydroxyl group in one molecule and having a mass average molecular weight of 500 to 8000,
The amount of the dimethylorganopolysiloxane (a3) relative to the total amount of the (meth) acrylate (a1), the polyvalent isocyanate compound (a2) and the dimethylorganopolysiloxane (a3) is 0.01 to 0. Let it react to be 10,
The release agent layer has a thickness of 0.3-2 μm,
The arithmetic average roughness (Ra1) on the surface of the release agent layer opposite to the substrate is 8 nm or less, and the maximum protrusion height (Rp1) is 50 nm or less,
A release film for a ceramic green sheet manufacturing process, wherein the arithmetic mean roughness (Ra2) on the second surface of the substrate is 5 to 40 nm and the maximum protrusion height (Rp2) is 60 to 500 nm . - 前記光重合開始剤(B)が、α-ヒドロキシケトン系化合物又はα-アミノアルキルフェノン系化合物であることを特徴とする請求項1に記載のセラミックグリーンシート製造工程用剥離フィルム。 2. The release film for producing a ceramic green sheet according to claim 1, wherein the photopolymerization initiator (B) is an α-hydroxyketone compound or an α-aminoalkylphenone compound.
- 前記剥離剤層の前記基材とは反対側の面にポリビニルブチラール樹脂層を形成した後、前記ポリビニルブチラール樹脂層を前記剥離剤層から剥離したときに、前記ポリビニルブチラール樹脂層における前記剥離剤層に接触していた面について、光電子分光分析で測定したケイ素原子比率が、1.0原子%未満であることを特徴とする請求項1又は2に記載のセラミックグリーンシート製造工程用剥離フィルム。 After the polyvinyl butyral resin layer is formed on the surface of the release agent layer opposite to the substrate, the release agent layer in the polyvinyl butyral resin layer is peeled off when the polyvinyl butyral resin layer is released from the release agent layer. The release film for a ceramic green sheet production process according to claim 1, wherein the silicon atom ratio measured by photoelectron spectroscopy analysis is less than 1.0 atomic% with respect to the surface in contact with the ceramic green sheet.
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JP7092685B2 (en) * | 2017-02-03 | 2022-06-28 | リンテック株式会社 | Peeling sheet and manufacturing method of peeling sheet |
CN110312602B (en) * | 2017-03-01 | 2021-12-14 | 东洋纺株式会社 | Release film for producing ceramic green sheet and method for producing same |
KR102499440B1 (en) * | 2017-03-09 | 2023-02-13 | 린텍 가부시키가이샤 | Release film for green sheet formation |
WO2018163924A1 (en) * | 2017-03-09 | 2018-09-13 | リンテック株式会社 | Peeling film for green sheet formation |
JP7183530B2 (en) * | 2017-06-01 | 2022-12-06 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
JP6852720B2 (en) * | 2017-10-12 | 2021-03-31 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
JP7236388B2 (en) * | 2017-11-07 | 2023-03-09 | 株式会社きもと | Sheet for supporting processing of adherend |
JP6962217B2 (en) * | 2017-12-27 | 2021-11-05 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
KR102518776B1 (en) * | 2017-12-27 | 2023-04-10 | 도요보 가부시키가이샤 | Release Film for Ceramic Green Sheet Manufacturing |
KR20190123079A (en) | 2018-04-23 | 2019-10-31 | 도레이첨단소재 주식회사 | Release film and manufacturing method thereof |
JP7102267B2 (en) * | 2018-07-10 | 2022-07-19 | リンテック株式会社 | Release film for ceramic green sheet manufacturing process |
JP7101553B2 (en) * | 2018-07-10 | 2022-07-15 | リンテック株式会社 | Release film for ceramic green sheet manufacturing process |
MY194551A (en) * | 2018-09-27 | 2022-12-01 | Toyo Boseki | Release film for production of ceramic green sheet |
WO2020105312A1 (en) * | 2018-11-22 | 2020-05-28 | Tdk株式会社 | Release film, ceramic component sheet, release film production method, ceramic component sheet production method, and layered ceramic capacitor production method |
JP7202253B2 (en) * | 2019-05-10 | 2023-01-11 | 信越化学工業株式会社 | Radiation-curable organopolysiloxane composition and release sheet |
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