WO2012144366A1 - セラミックグリーンシート製造工程用の剥離フィルム - Google Patents
セラミックグリーンシート製造工程用の剥離フィルム Download PDFInfo
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- WO2012144366A1 WO2012144366A1 PCT/JP2012/059678 JP2012059678W WO2012144366A1 WO 2012144366 A1 WO2012144366 A1 WO 2012144366A1 JP 2012059678 W JP2012059678 W JP 2012059678W WO 2012144366 A1 WO2012144366 A1 WO 2012144366A1
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- release agent
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- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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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
- 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
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- 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
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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
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/263—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer having non-uniform thickness
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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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
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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
- B32B2457/00—Electrical equipment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the present invention relates to a release film used in a process for producing a ceramic green sheet.
- the thickness of the ceramic green sheet has been further reduced from the current 1 to 5 ⁇ m, and a ceramic green sheet having a thickness of less than 1 ⁇ m is also manufactured.
- the process film cannot be handled by the conventional one, and further, a high performance process film, that is, excellent ceramic slurry coating property and ceramic green sheet peelability, and heat shrink wrinkles, etc.
- a process film having extremely high smoothness without protrusions that affect the sheet thickness on the surface is required.
- a release film is generally used in which an addition reaction type silicone resin is applied to a polyethylene terephthalate (PET) film as a base material to form a release agent layer.
- PET polyethylene terephthalate
- the required smoothness of the surface of the release agent layer is increasing year by year, and accordingly, a substrate having an extremely high surface smoothness is used. Therefore, it is difficult to obtain an anchor effect of a silicone resin.
- the adhesion of the release agent layer to the material is low. Therefore, in the core part at the time of winding up in roll shape, problems, such as a peeling agent layer falling off from a base material by winding down, had arisen.
- a technique for applying a primer treatment to the base material has been established. For example, a method in which an undercoat layer composed of a metal silicon compound and a silane coupling agent is previously applied to a PET film, and an addition reaction type silicone compound is applied thereon.
- a partial hydrolyzate of silicon alkoxide is previously applied on a PET film to provide a silicon oxide layer, and a release agent layer is provided thereon, thereby providing adhesion to the substrate and antistatic properties.
- the technique has been carried out.
- the adhesion between the silicon oxide layer and the substrate is lowered, and as a result, the release agent layer may fall off.
- Patent Document 1 a base material provided with an antistatic layer by applying an alkylammonium salt or the like having high antistatic properties by in-line coating during film formation of the base material is known (Patent Document 1). , 2).
- the antistatic layer becomes a catalyst poison, which causes problems in the curability and adhesion of the silicone.
- the release agent layer is provided on the surface opposite to the antistatic layer in the base material, adhesion between the highly smooth base material and the release agent layer cannot be obtained, and the coating strength of the antistatic layer is low. Since it is low and the surface is difficult to slip, the antistatic layer has fallen off due to contact with a guide roll or the like when the release agent is applied or cut.
- the release film is wound into a roll, the dropped antistatic layer is mixed as a foreign substance, which causes a dent.
- the foreign material mixed in the wound release film accumulates on a guide roll or the like in the process at the time of ceramic slurry coating, which becomes in-process contamination and causes a ceramic slurry coating failure.
- the present invention has been made in view of such a situation, and it is possible to obtain a high smoothness of the release agent layer, to effectively suppress charging, and to prevent the release agent layer from falling off.
- An object of the present invention is to provide a release film that can be used.
- the present invention provides a base material and a resin layer laminated on the first surface of the base material, containing a conductive polymer, and having a thickness of 30 to 290 nm. And a release agent layer laminated on the resin layer, wherein the maximum protrusion height (Rp) on the surface of the release agent layer is 10 to 100 nm.
- a film is provided (Invention 1).
- the arithmetic mean roughness (Ra) on the second surface of the substrate is preferably 5 to 50 nm, and the maximum protrusion height (Rp) is preferably 40 to 300 nm (Invention). 2).
- the resin layer preferably contains at least one selected from the group consisting of polyester resins, urethane resins and acrylic resins (Invention 3).
- the resin layer is at least one selected from the group consisting of a polythiophene conductive polymer, a polyaniline conductive polymer, and a polypyrrole conductive polymer as the conductive polymer. It is preferable to contain seeds (Invention 4).
- the release agent layer is preferably composed of a release agent mainly composed of an addition reaction type silicone resin (Invention 5).
- a polyester adhesive tape No. 31B 180 ° peel force (mN / 20 mm) peel force X, the surface of the release agent layer using a Gakushin friction fastness tester, the second surface of the substrate as a polishing piece, a load of 1 kg, Polishing was performed under the conditions of 10 reciprocations, and the polyester adhesive tape No.
- the 180 ° peeling force (mN / 20 mm) of 31B is the peeling force Y, (Peeling force X / peeling force Y) ⁇ 100%
- the release agent layer retention represented by the formula is preferably 85% or more (Invention 6).
- the charge amount on the surface of the release agent layer immediately after unwinding the release film having a width of 400 mm and a length of 5000 m wound up in a roll shape at 100 m / min is 10 kV or less.
- the release film of the present invention high smoothness of the release agent layer can be obtained, and charging at the time of unwinding and the like can be effectively suppressed, and the release agent layer can be removed even during long-term storage. And a thin film ceramic green sheet having no pinholes can be manufactured satisfactorily.
- the release film 1 contains a base material 11 and a conductive polymer laminated on the first surface (upper surface in FIG. 1) of the base material 11.
- a resin layer 12 and a release agent layer 13 laminated on the resin layer 12 are provided.
- the peeling film 1 in this embodiment is used in the process of manufacturing a ceramic green sheet.
- the substrate 11 is not particularly limited, and any one of conventionally known materials can be appropriately selected and used.
- a substrate 11 include films made of polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, polycarbonates, and plastics such as polyvinyl acetate.
- 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. Since 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.
- the first surface may be subjected to a surface treatment by an oxidation method or a primer treatment.
- the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like.
- the 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 maximum protrusion height (Rp) on the first surface of the substrate 11 is preferably 10 to 100 nm, and particularly preferably 20 to 50 nm. By setting the maximum protrusion height (Rp) on the first surface of the substrate 11 within this range, it is easy to keep the maximum protrusion height (Rp) on the surface of the release agent layer 13 within the range described later. Become.
- the arithmetic average roughness (Ra) on the second surface of the substrate 11 is preferably 5 to 50 nm, particularly 10 to 30 nm. Preferably there is.
- the maximum protrusion height (Rp) on the second surface of the substrate 11 is preferably 40 to 300 nm, and particularly preferably 60 to 220 nm.
- the arithmetic mean roughness (Ra) of the second surface of the substrate 11 is too small, the second surface is too smooth, and the second surface of the substrate 11 is highly smooth when the release film 1 is wound up.
- the release agent layer 13 is in close contact with each other, and blocking is likely to occur.
- the arithmetic average roughness (Ra) of the second surface of the substrate 11 is too large, it is difficult to keep the maximum protrusion height (Rp) of the second surface of the substrate 11 in the above preferred low range. May be.
- the maximum protrusion height (Rp) on the second surface of the substrate 11 is too large, the protrusion shape of the second surface of the substrate 11 that adheres to the ceramic green sheet when wound up after the formation of the ceramic green sheet. May be transferred to the ceramic green sheet, and the thickness of the ceramic green sheet may be partially reduced.
- the maximum protrusion height (Rp) of the second surface of the base material 11 is too small, the unevenness of the second surface of the base material 11 becomes uniform and the second surface becomes flat. In the step of forming the layer 13 or the like, air is easily entrapped on the surface where the substrate 11 contacts the roll. As a result, the substrate 11 being conveyed may meander or may be unwound when wound into a roll.
- the amount of the conductive polymer added as an antistatic agent to the resin layer 12 of the release film 1 according to this embodiment is increased, there is a problem that the adhesiveness of the release agent layer 13 is lowered. May occur. Therefore, it is preferable to reduce the addition amount, but in such a case, sufficient antistatic properties may not be obtained, and the unwinding charge amount of the release film 1 described later may increase.
- the arithmetic average roughness (Ra) and the maximum protrusion height (Rp) on the second surface of the substrate 11 are in the above ranges, blocking is suppressed, so that the release film 1 according to this embodiment is wound. The effect of suppressing charging at the time of taking out is more exhibited.
- the substrate 11 is It is preferable that the maximum protrusion height (Rp) of the first surface of the substrate 11 is different from the maximum protrusion height (Rp) of the second surface, that is, the surface roughness is different.
- a first filler-containing resin melt that forms the first surface and a second filler-containing resin melt that forms the second surface are used.
- the method include coextrusion film formation in which a multi-layer molding die is joined in a die, extruded into a sheet, cooled and then stretched.
- the first filler-containing resin melt contains the first filler.
- the first filler is preferably an inorganic filler that can withstand the melting temperature of the resin, and examples of the inorganic filler include aluminum oxide particles, calcium carbonate particles, and silicon dioxide.
- the average particle diameter of the first filler is preferably 0.01 to 1 ⁇ m, and more preferably 0.05 to 0.7 ⁇ m.
- a 1st filler can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- the content of the first filler in the first filler-containing resin melt is preferably 0.03 to 2 parts by mass with respect to 100 parts by mass of the total amount of resin raw material monomers.
- the second filler-containing resin melt contains the second filler.
- a preferable material for the second filler is the same as that for the first filler.
- the average particle size of the second filler is preferably 0.05 to 2 ⁇ m, and more preferably 0.1 to 1 ⁇ m.
- a 2nd filler can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- the content of the second filler in the second filler-containing resin melt is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass as the total amount of resin raw material monomers.
- the base material 11 has substantially the same maximum protrusion height (Rp) of the first surface and the maximum protrusion height (Rp) of the second surface.
- the front and back roughness may be the same.
- the base material 11 composed of a single-layer resin layer is obtained by extruding a filler-containing resin melt for forming a single-layer base material into a sheet, and stretching after cooling. The method of obtaining is mentioned. It is preferable that the filler material, particle size, and content contained in the single-layer substrate-forming filler-containing resin melt are the same as those of the second filler.
- the method of obtaining the base material 11 in which the arithmetic mean roughness (Ra) and the maximum protrusion height (Rp) of the first surface and the second surface are in the above preferable ranges is limited to that by extrusion molding.
- the substrate 11 can also be obtained by a method of casting an object and drying and removing the solvent to coat.
- the resin layer 12 in the present embodiment is made of a resin composition containing a conductive polymer.
- the resin layer 12 exhibits an antistatic property by containing a conductive polymer. Since the release film 1 according to the present embodiment has the resin layer 12, it is possible to effectively suppress charging during unwinding or the like. Further, even when a release agent using a metal catalyst for polymerization (addition reaction), such as a silicone resin release agent, is used for the release agent layer 13, the polymerization reaction is hardly inhibited and the release agent is cured well. Is easy to obtain.
- the resin layer 12 preferably contains at least one selected from the group consisting of polyester resin, urethane resin and acrylic resin as a main component.
- a resin layer 12 exhibits good adhesion to both the base material 11 and the release agent layer 13. Specifically, since the resin layer 12 is appropriately swollen with respect to the organic solvent contained in the release agent, the resin component of the release agent and the resin component of the resin layer 12 are mixed at the interface, thereby improving the adhesion. To do. Due to this adhesion, it is possible to suppress the release agent layer 13 from dropping even during long-term storage.
- the above resins may be used alone or in combination of two different types.
- the base material 11 is made of a polyester-based material
- the polyester resin alone the adhesion to the polyester-based substrate 11 is sufficient, but since it is a relatively brittle resin, it tends to cause cohesive failure at the time of cutting.
- the polyurethane resin alone has a polyester-based substrate. 11 is inferior in adhesion.
- containing a polyester resin and a polyurethane resin also means that a polymer containing a polyester structure and a polyurethane structure in one molecule is included alone.
- any one of conventionally known conductive polymers can be appropriately selected and used. Among them, polythiophene-based, polyaniline-based, or polypyrrole-based conductive polymers are preferable.
- Examples of the polythiophene-based conductive polymer include polythiophene, poly (3-alkylthiophene), poly (3-thiophene- ⁇ -ethanesulfonic acid), a mixture of polyalkylenedioxythiophene and polystyrene sulfonate, and the like.
- Examples of the polyalkylene dioxythiophene include polyethylene dioxythiophene, polypropylene dioxythiophene, poly (ethylene / propylene) dioxythiophene, and the like.
- Examples of the polyaniline-based conductive polymer include polyaniline, polymethylaniline, polymethoxyaniline, and the like.
- polypyrrole-based conductive polymer examples include polypyrrole, poly-3-methylpyrrole, and poly-3-octylpyrrole. These conductive polymer compounds may be used alone or in combination of two or more. These conductive polymers are preferably used in the form of an aqueous solution dispersed in water.
- the content of the conductive polymer in the resin layer 12 is preferably 0.1 to 50% by mass in terms of solid content, particularly preferably 0.3 to 30% by mass, and more preferably 0.3 It is preferably ⁇ 10% by mass. If the content of the conductive polymer is less than 0.1% by mass, sufficient antistatic performance may not be obtained. On the other hand, when the content of the conductive polymer exceeds 50% by mass, the strength of the resin layer 12 is lowered and cohesive failure easily occurs, and the adhesiveness of the release agent layer 13 may be impaired.
- the thickness of the resin layer 12 is 30 to 290 nm, preferably 30 to 250 nm. If the thickness of the resin layer 12 is less than 30 nm, the film-forming property on the surface of the substrate 11 becomes insufficient, and pinholes due to repellency are likely to occur. On the other hand, when the thickness of the resin layer 12 exceeds 290 nm, cohesive failure of the resin layer 12 is likely to occur, and the adhesion of the release agent layer 13 may be impaired.
- the resin layer 12 may be formed by applying a resin composition coating agent containing a conductive polymer to the first surface of the substrate 11 and then drying it.
- a coating method 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, or the like can be used.
- the coating agent for the resin composition may contain a solvent capable of dissolving or dispersing each component of the resin composition. As such a solvent, an ether solvent, an alcohol solvent, a mixed solvent of an alcohol solvent and purified water, or the like is preferably used.
- Examples of the release agent constituting the release agent layer 13 include non-silicone resin-based release agents such as alkyd resin-based, olefin resin-based, acrylic-based, long-chain alkyl group-containing compound-based rubbers, as well as silicone resin-based release agents. Agents.
- the silicone resin release agent there are a solvent type and a solventless type. Since the solvent-type silicone resin is diluted with a solvent to form a coating solution, it can be widely used from a high molecular weight / high viscosity polymer to a low viscosity low molecular weight polymer (oligomer). Therefore, it is easy to control the peelability as compared with the solventless type, and it is easy to design in accordance with the required performance (quality).
- the silicone resin release agent include addition reaction type, condensation reaction type, ultraviolet curable type, and electron beam curable type.
- the addition reaction type silicone resin is highly reactive and excellent in productivity. Compared to the condensation reaction type, the addition reaction type silicone resin has advantages such as a small change in peel force after production and no cure shrinkage. It is preferable to use it as a release agent.
- the addition reaction type silicone resin is not particularly limited, and various types can be used.
- what is conventionally used as a conventional thermosetting addition reaction type silicone resin release agent can be used.
- the addition reaction type silicone resin include those having an electrophilic group such as an alkenyl group such as a vinyl group or a hydrosilyl group as a functional group in the molecule, and examples of the addition reaction type silicone resin that can be easily cured.
- polydimethylsiloxane having such a functional group, or those obtained by substituting a part or all of the methyl group of polydimethylsiloxane with an aromatic functional group such as a phenyl group can be used.
- silicone resin silicone resin
- antistatic agent dye, pigment and other additives may be added to the silicone resin-based release agent as necessary.
- either heat treatment in the oven of the coating machine or ultraviolet light irradiation in combination with the heat treatment may be used. This is preferable in terms of prevention of shrinkage wrinkle generation, silicone curability, and adhesion of the release agent to the base film.
- a photoinitiator when using ultraviolet irradiation together for hardening of a coating film, it is desirable to add a photoinitiator to a release agent.
- a photoinitiator Arbitrary things can be suitably selected and used from what is conventionally used by the thing which generate
- the photoinitiator include benzoins, benzophenones, acetophenones, ⁇ -hydroxy ketones, ⁇ -amino ketones, ⁇ -diketones, ⁇ -diketone dialkyl acetals, anthraquinones, and thioxanthones.
- an alkyd resin having a crosslinked structure is generally used as the alkyd resin release agent.
- the alkyd resin layer having a crosslinked structure can be formed by, for example, a method in which a layer made of a thermosetting resin composition containing an alkyd resin, a crosslinking agent, and optionally a curing catalyst is heated and cured.
- the alkyd resin may be a modified product such as a long-chain alkyl-modified alkyd resin or a silicone-modified alkyd resin.
- a crystalline olefin resin is used as the olefin resin release agent.
- this crystalline olefin resin polyethylene, crystalline polypropylene resin, and the like are suitable.
- polyethylene include high density polyethylene, low density polyethylene, and linear low density polyethylene.
- the crystalline polypropylene resin include a propylene homopolymer having an isotactic structure or a syndiotactic structure, a propylene- ⁇ -olefin copolymer, and the like. These crystalline olefin resins may be used alone or in combination of two or more.
- an acrylic resin having a crosslinked structure is generally used.
- the acrylic resin may be a modified product such as a long-chain alkyl-modified acrylic resin or a silicone-modified acrylic resin.
- long-chain alkyl group-containing compound-based release agent for example, polyvinyl carbamate obtained by reacting a polyvinyl alcohol polymer with a long-chain alkyl isocyanate having 8 to 30 carbon atoms, or polyethyleneimine having 8 to 30 carbon atoms.
- An alkylurea derivative obtained by reacting a long-chain alkyl isocyanate is used.
- rubber release agents include natural rubber resins and synthetic rubber resins such as butadiene rubber, isoprene rubber, styrene-butadiene rubber, methyl methacrylate-butadiene rubber, and acrylonitrile-butadiene rubber.
- the thickness of the release agent layer 13 is not particularly limited, but is preferably 0.01 to 1 ⁇ m, and more preferably 0.03 to 0.5 ⁇ m. When the thickness of the release agent layer 13 is less than 0.01 ⁇ m, the function as the release agent layer may not be sufficiently exerted depending on the material constituting the release agent layer 11 or the like. On the other hand, when the thickness of the release agent layer 13 exceeds 1 ⁇ m, when the release film 1 is wound into a roll, blocking with the second surface of the base material is likely to occur. In some cases, problems such as high chargeability during unwinding may occur.
- the release agent layer 13 can be formed by applying a release agent solution made of a release agent and, optionally, a curing agent, a diluent, and the like to the first surface of the substrate 11 and then drying and curing.
- a coating method 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, or the like can be used.
- the maximum protrusion height (Rp) on the surface of the release agent layer 13 is 10 to 100 nm, preferably 20 to 50 ⁇ m. By setting the maximum protrusion height (Rp) on the surface of the release agent layer 13 within this range, the surface of the release agent layer 13 can be made highly smooth, and a thin film ceramic green sheet having a thickness of 1 ⁇ m or less can be obtained. Even when molded on the surface of the release agent layer 13, pinholes or non-uniform portions of thickness are less likely to occur in the thin film ceramic green sheet, and good sheet moldability is exhibited.
- the release sheet 1 As described above, in the release sheet 1 according to the present embodiment, it is possible to suppress the release agent layer 13 from dropping due to the presence of the resin layer 12 having adhesion to the base material 11 and the release agent layer 13.
- Nitto Denko polyester adhesive tape No. 31B 180 ° peel force (mN / 20 mm) peel force X
- the surface of the release agent layer 13 is polished using a Gakushin friction fastness tester with the second surface of the base material 11 as a polishing piece under a load of 1 kg and 10 reciprocations.
- the release agent layer retention represented by the formula is preferably 85% or more, particularly preferably 90% or more.
- the release agent layer retention is within the above range, the release agent layer 13 is unlikely to fall off from the release film 1 during unwinding, cutting, transporting during the slurry coating process, etc. when producing the ceramic green sheet. It will be a thing. Thereby, there is no generation
- the release agent layer retention is low, when the release film 1 is stored under normal conditions, there is no problem in slurry coating, but when it is stored under adverse conditions such as higher temperature and / or humidity. In some cases, the release agent layer 13 may fall off during conveyance during the slurry coating process. When the release agent layer retention rate is in the above range, even when the release film 1 is stored under adverse conditions, the release agent layer 13 is unlikely to fall off during transportation during the slurry coating process.
- the release sheet 1 exhibits antistatic properties due to the resin layer 12 containing a conductive polymer.
- the charge amount (unwinding charge amount) on the surface of the release agent layer 13 immediately after unwinding the release film 1 having a width of 400 mm and a length of 5000 m wound up in a roll shape at 100 m / min. ) Is preferably 10 kV or less, and particularly preferably less than 8 kV.
- the unwinding charge amount of the release agent layer 13 is in the above range, preferable antistatic properties can be obtained. This prevents foreign matters from adhering to the surface of the release agent layer 13 due to charging when unwinding and causing pinholes in the ceramic slurry film coated on the release agent layer 13. Can do. In addition, it is possible to prevent fluctuation and repellency from being generated in the ceramic slurry to be applied due to electrification, and to form a uniform ceramic green sheet. Furthermore, in the process of peeling the ceramic green sheet molded on the release agent layer 13 from the release film 1, it is possible to prevent peeling failure due to charging and to peel normally without breaking the ceramic green sheet. Is possible.
- the surface resistivity of the release agent layer 13 is preferably 1 ⁇ 10 6 to 1 ⁇ 10 12 ⁇ / ⁇ , particularly 1 ⁇ 10 7 to 1 ⁇ 10 10. It is preferable that it is ⁇ / ⁇ .
- the surface resistivity is in such a range, the unwinding charge amount of the release agent layer 13 can be easily adjusted to the above preferable range.
- the surface resistivity is in such a range, and the arithmetic average roughness (Ra) and the maximum protrusion height (Rp) on the second surface of the substrate 11 are in the above-described preferable ranges, peeling It becomes easier to adjust the unwinding charge amount of the agent layer 13 to the above preferable range.
- another layer may be interposed between the base material 1 and the resin layer 12 or between the resin layer 12 and the release agent layer 13.
- Example 1 (1) Preparation of base material 86 parts by mass of terephthalic acid and 70 parts by mass of ethylene glycol were placed in a reactor, and a transesterification reaction was performed at about 250 ° C. for 4 hours. Next, 0.03 parts by mass of antimony trioxide, 0.01 parts by mass of phosphoric acid, and 0.3 parts by mass of aluminum oxide particles having an average particle size of 0.1 ⁇ m are added, and the temperature is gradually raised from 250 ° C. to 285 ° C. The pressure was gradually reduced to 0.5 mmHg. After 4 hours, the polymerization reaction was stopped to obtain polyethylene terephthalate A (filler-containing resin for forming the first surface) having an intrinsic viscosity of 0.65 dl / g.
- an intrinsic viscosity of 0.63 dl / g was obtained in the same manner as polyethylene terephthalate A except that 1 part by mass of calcium carbonate particles having an average particle size of 0.5 ⁇ m was used instead of aluminum oxide particles having an average particle size of 0.1 ⁇ m.
- Polyethylene terephthalate B filler-containing resin for forming the second surface
- polyethylene terephthalates A and B were dried in an inert gas at 180 ° C. for 4 hours.
- polyethylene terephthalate A is supplied to a single screw extruder and melted at a temperature of 290 ° C.
- polyethylene terephthalate B is supplied to another single screw extruder at a temperature of 290 ° C. And melted.
- the two-layer molding die was joined in the die so as to be layer A / layer B, extruded into a sheet, and cooled and solidified on a cooling roll set at a surface temperature of 40 ° C. To obtain an unstretched sheet.
- the obtained sheet was stretched 3.5 times in the longitudinal direction at 100 ° C., and stretched 3.5 times in the transverse direction at 100 ° C. with a tenter. Thereafter, heat setting was performed at 230 ° C. to obtain a polyester film having a thickness of 38 ⁇ m and different roughness between the front and back surfaces, which was used as a base material.
- the surface of the stretched A layer is the first surface
- the surface of the stretched B layer is the second surface.
- the maximum protrusion height (Rp) of the first surface of the obtained base material was 36 nm
- the arithmetic average roughness (Ra) of the second surface was 12 nm
- the maximum protrusion height (Rp) was 84 nm.
- thermosetting addition reaction type silicone manufactured by Shin-Etsu Chemical Co., Ltd., KS-847H
- platinum catalyst manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL is used.
- ⁇ 50T 2 parts by mass were mixed to prepare a coating liquid having a solid content of 1.5% by mass.
- the coating solution was uniformly applied to the surface of the resin layer so that the thickness after drying was 100 nm, and dried at 140 ° C. for 1 minute to form a release agent layer, which was used as a release film. .
- Example 2 A release film was produced in the same manner as in Example 1 except that the thickness of the resin layer was 100 nm.
- Example 3 A release film was produced in the same manner as in Example 1 except that the thickness of the resin layer was 200 nm.
- Example 4 An intrinsic viscosity of 0.64 dl / g is the same as that of polyethylene terephthalate A of Example 1 except that 1 part by mass of calcium carbonate having an average particle size of 0.3 ⁇ m is used instead of aluminum oxide particles having an average particle size of 0.1 ⁇ m.
- Polyethylene terephthalate C filler-containing resin for forming a base material composed of a single resin layer
- the obtained polyethylene terephthalate C was dried in an inert gas at 180 ° C. for 4 hours, supplied to a single screw extruder, and melted at a temperature of 290 ° C.
- the sheet was extruded from the die into a sheet and cooled and solidified on a cooling roll set at a surface temperature of 40 ° C. to obtain an unstretched sheet.
- the obtained sheet was stretched 3.5 times in the longitudinal direction at 100 ° C., and stretched 3.5 times in the transverse direction at 100 ° C. with a tenter.
- heat setting was performed at 230 ° C. to obtain a polyester film having a thickness of 38 ⁇ m and having the same front and back roughness, and this was used as a base material.
- one surface of the base material is the first surface
- the other surface is the second surface.
- the maximum protrusion height (Rp) of the first surface of the obtained base material was 44 nm, the arithmetic average roughness (Ra) of the second surface was 9 nm, and the maximum protrusion height (Rp) was 47 nm.
- a release film was produced in the same manner as in Example 1 except that this substrate was used.
- Example 1 A release film was produced in the same manner as in Example 1 except that the thickness of the resin layer was 20 nm.
- Example 2 A release film was produced in the same manner as in Example 1 except that the thickness of the resin layer was 300 nm.
- An intrinsic viscosity of 0.62 dl / g is the same as that of polyethylene terephthalate A of Example 1 except that 1 part by mass of silicon dioxide having an average particle diameter of 1.5 ⁇ m is used instead of aluminum oxide particles having an average particle diameter of 0.1 ⁇ m.
- Polyethylene terephthalate D was produced. Except that this polyethylene terephthalate D was used in place of polyethylene terephthalate C, a polyester film having a thickness of 38 ⁇ m and having the same front and back roughness was obtained and used as a base material.
- the maximum protrusion height (Rp) of the first surface of the obtained substrate was 527 nm
- the arithmetic average roughness (Ra) of the second surface was 36 nm
- the maximum protrusion height (Rp) was 532 nm.
- a release film was produced in the same manner as in Example 1 except that this substrate was used.
- Example 6 The polyester film obtained in Example 1 was used as the substrate. On the first surface of the polyester film, after drying, a coating solution obtained by diluting a partial hydrolyzate of tetraethoxysilane (Colcoat N-103X, Colcoat N-103X) with isopropyl alcohol to a solid content of 1.5% by mass was dried. The film was uniformly coated to a thickness of 100 nm and dried at 120 ° C. for 1 minute to form an antistatic layer. Then, a release agent layer was formed on the antistatic layer in the same manner as in Example 1, and this was used as a release film.
- a coating solution obtained by diluting a partial hydrolyzate of tetraethoxysilane Colcoat N-103X, Colcoat N-103X
- isopropyl alcohol to a solid content of 1.5% by mass was dried.
- the film was uniformly coated to a thickness of 100 nm and dried at 120 ° C. for 1 minute to form an antistatic layer.
- a PET film (Made by Mitsubishi Plastics, Diafoil T100G) having an antistatic layer (thickness: 20 nm) made of an alkylammonium salt on the first surface was prepared.
- This PET film has a maximum protrusion height (Rp) of 502 nm on the surface of the antistatic layer, an arithmetic average roughness (Ra) of the second surface of 36 nm, a maximum protrusion height (Rp) of 522 nm, and a thickness (charged). (Including a prevention layer) was 38 ⁇ m.
- a release agent layer was formed on the antistatic layer in the same manner as in Example 1, and this was used as a release film.
- Test Example 1 (Surface roughness measurement) First surface and second surface of base materials used in Examples and Comparative Examples in accordance with JIS B0601: 2001 using a surface roughness measuring machine (manufactured by Mitutoyo Corporation, Surf Test SV-3000S4) In addition, the arithmetic average roughness (Ra) and / or maximum protrusion height (Rp) of the surface of the release agent layer in the release films obtained in Examples and Comparative Examples were measured. The results are shown in Table 1.
- Test Example 2 Measurement of surface resistivity
- the release films obtained in Examples and Comparative Examples were cut into 100 mm ⁇ 100 mm and used as samples. After conditioning the sample for 24 hours under conditions of 23 ° C. and 50% humidity, using “R12704 Resistivity Chamber” manufactured by Advantest and “Digital Electrometer R8252” manufactured by Advantest and complying with JIS K6911 (1995) Then, the resistivity of the surface on the release agent layer side was measured. The results are shown in Table 2.
- the obtained sample was cured under conditions of 23 ° C. and 50% humidity for 24 hours, then cut into a width of 40 mm and a length of 150 mm, and a polyester adhesive at a peeling angle of 180 ° and a peeling speed of 300 m / min.
- the peeling force was measured by peeling off the tape side.
- the peel force of the non-polished part is the peel force X
- the peel force of the polished part is the peel force Y
- the results are shown in Table 2.
- the ceramic slurry was applied with a width of 250 mm and a length of 10 m so that the film thickness after drying with a die coater was 1 ⁇ m. It was made to dry at 80 degreeC with a dryer for 1 minute. About the peeling film in which the ceramic green sheet was shape
- the release films obtained in the examples had a preferable surface resistivity and a low unwinding charge amount. Further, the release agent layer retention rate was high, there was no blocking, and no pinholes were generated in the molded ceramic green sheet.
- the release film of the present invention is suitable for molding a thin film ceramic green sheet having a thickness of 1 ⁇ m or less.
Abstract
Description
(剥離力X/剥離力Y)×100%
の式で表わされる剥離剤層保持率が、85%以上であることが好ましい(発明6)。
図1に示すように、本実施形態に係る剥離フィルム1は、基材11と、基材11の第1の面(図1では上面)の上に積層された、導電性高分子を含有する樹脂層12と、樹脂層12の上に積層された剥離剤層13とを備えて構成される。なお、本実施形態における剥離フィルム1は、セラミックグリーンシートを製造する工程にて使用されるものである。
剥離剤層13に対する日東電工社製ポリエステル粘着テープNo.31Bの180°剥離力(mN/20mm)を剥離力X、
剥離剤層13の表面を、学振式摩擦堅牢試験機を用いて、基材11の第2の面を研磨片として加重1kg、往復10回の条件にて研磨し、当該研磨面に対する日東電工社製ポリエステル粘着テープNo.31Bの180°剥離力(mN/20mm)を剥離力Yとしたときに、
(剥離力X/剥離力Y)×100%
の式で表わされる剥離剤層保持率が、85%以上であることが好ましく、特に90%以上であることが好ましい。
(1)基材の作製
テレフタル酸86質量部およびエチレングリコール70質量部を反応器に取り、約250℃で4時間エステル交換反応を行った。次いで、三酸化アンチモン0.03質量部、リン酸0.01質量部、および平均粒径0.1μmの酸化アルミニウム粒子0.3質量部を加え、250℃から285℃まで徐々に昇温すると共に、圧力を徐々に減じて0.5mmHgとした。4時間後、重合反応を停止し、極限粘度0.65dl/gのポリエチレンテレフタレートA(第1の面を形成するためのフィラー含有樹脂)を得た。
次に、共重合ポリエステルおよびポリウレタンを含む混合樹脂エマルションに、導電性高分子であるポリエチレンジオキシチオフェン(PEDOT)およびポリスチレンスルホネート(PSS)が合計で0.1~1.0質量%混合された樹脂組成物(中京油脂社製,P-973,固形分10質量%)を、イソプロピルアルコールおよび精製水の混合液(混合比率1:1)にて固形分1.0質量%に希釈して、これを樹脂塗工液とした。この樹脂塗工液を、乾燥後の厚さが50nmとなるように上記基材の第1の面に均一に塗工し、120℃で1分間乾燥させて、樹脂層を形成した。
次いで、熱硬化付加反応型シリコーン(信越化学工業社製,KS-847H)100質量部をトルエンで希釈し、これに白金触媒(信越化学工業社製,CAT-PL-50T)2質量部を混合し、固形分が1.5質量%の塗工液を調製した。この塗工液を、乾燥後の厚さが100nmとなるように上記樹脂層の表面に均一に塗工し、140℃で1分間乾燥させて剥離剤層を形成し、これを剥離フィルムとした。
樹脂層の厚さを100nmとした以外は、実施例1と同様にして剥離フィルムを作製した。
樹脂層の厚さを200nmとした以外は、実施例1と同様にして剥離フィルムを作製した。
平均粒径0.1μmの酸化アルミニウム粒子の替わりに、平均粒径0.3μmの炭酸カルシウム1質量部を用いる以外は、実施例1のポリエチレンテレフタレートAと同様にして、極限粘度0.64dl/gのポリエチレンテレフタレートC(単層の樹脂層からなる基材を形成するためのフィラー含有樹脂)を製造した。得られたポリエチレンテレフタレートCを180℃で4時間、不活性ガス中で乾燥させ、一軸押出機に供給して290℃の温度で溶融させた。次いで、瀘過フイルターを経た後に、口金からシート状に押出して、表面温度40℃に設定した冷却ロール上で冷却固化させて未延伸シートを得た。得られたシートを100℃で縦方向に3.5倍に延伸し、そしてテンターにて100℃で横方向に3.5倍延伸した。その後、230℃にて熱固定を行い、厚さ38μmの表裏同粗度のポリエステルフィルムを得、これを基材とした。この基材では、基材の一方の面が第1の面であり、他方の面が第2の面である。得られた基材の第1の面の最大突起高さ(Rp)は44nm、第2の面の算術平均粗さ(Ra)は9nm、最大突起高さ(Rp)は47nmであった。この基材を使用する以外は、実施例1と同様にして剥離フィルムを作製した。
樹脂層の厚さを20nmとした以外は、実施例1と同様にして剥離フィルムを作製した。
樹脂層の厚さを300nmとした以外は、実施例1と同様にして剥離フィルムを作製した。
樹脂層を形成しなかった以外は、実施例1と同様にして剥離フィルムを作製した。
平均粒径0.1μmの酸化アルミニウム粒子の替わりに、平均粒径1.5μmの二酸化ケイ素1質量部を用いる以外は、実施例1のポリエチレンテレフタレートAと同様にして、極限粘度0.62dl/gのポリエチレンテレフタレートDを製造した。このポリエチレンテレフタレートDをポリエチレンテレフタレートCの替わりに用いた以外は、実施例4と同様にして、厚さ38μmの表裏同粗度のポリエステルフィルムを得、これを基材とした。得られた基材の第1の面の最大突起高さ(Rp)は527nm、第2の面の算術平均粗さ(Ra)は36nm、最大突起高さ(Rp)は532nmであった。この基材を使用する以外は、実施例1と同様にして剥離フィルムを作製した。
基材として、比較例4で得られたポリエステルフィルムを使用し、かつ樹脂層を形成しなかった以外は、実施例1と同様にして剥離フィルムを作製した。
基材として、実施例1で得られたポリエステルフィルムを使用した。そのポリエステルフィルムの第1の面に、テトラエトキシシランの部分加水分解物(コルコート社製,コルコートN-103X)をイソプロピルアルコールにて固形分1.5質量%に希釈した塗工液を、乾燥後の厚さが100nmとなるように均一に塗工し、120℃で1分間乾燥させて、帯電防止層を形成した。そして、この帯電防止層上に実施例1と同様にして剥離剤層を形成し、これを剥離フィルムとした。
基材として、第1の面にアルキルアンモニウム塩からなる帯電防止層(厚さ:20nm)が設けられたPETフィルム(三菱樹脂社製,ダイアホイルT100G)を用意した。このPETフィルムは、帯電防止層の表面の最大突起高さ(Rp)が502nm、第2の面の算術平均粗さ(Ra)が36nm、最大突起高さ(Rp)が522nm、厚さ(帯電防止層を含む)が38μmであった。そして、この帯電防止層上に実施例1と同様にして剥離剤層を形成し、これを剥離フィルムとした。
表面粗さ測定機(株式会社ミツトヨ製,サーフテストSV-3000S4)を使用し、JIS B0601:2001に準拠して、実施例および比較例で使用した基材の第1の面および第2の面、ならびに実施例および比較例で得られた剥離フィルムにおける剥離剤層の表面の算術平均粗さ(Ra)および/または最大突起高さ(Rp)を測定した。結果を表1に示す。
実施例および比較例で得られた剥離フィルムを100mm×100mmに裁断し、これをサンプルとした。サンプルを23℃、湿度50%の条件下で24時間調湿した後、アドバンテスト社製「R12704レジスティビティチャンバ」およびアドバンテスト社製「デジタルエレクトロメータR8252」を使用し、JIS K6911(1995)に準拠して、剥離剤層側の表面の抵抗率を測定した。結果を表2に示す。
実施例および比較例で得られた剥離フィルムを60℃、湿度90%の環境下にて72時間保管した。その後、剥離フィルムの剥離剤層の表面の一部を、学振式摩擦堅牢試験機を用いて、実施例および比較例で得られた剥離フィルムに用いたのと各々同じ基材(ポリエステルフィルム)の第2の面を研磨片として加重1kg、往復10回の条件にて研磨した。次いで、剥離剤層の研磨部分と非研磨部分とに、ポリエステル粘着テープ(日東電工社製,No.31B,厚さ50μm,幅20mm)を2kgのローラ1往復にて貼合し、これをサンプルとした。
剥離剤層保持率=(剥離力X/剥離力Y)×100%
によって、剥離剤層保持率(%)を算出した。結果を表2に示す。
実施例およ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の外観を目視にて観察した。ロール状に巻き上げたときから変化がなかったものをブロッキング無し(○)、半分以下の領域の色目が異なった場合をブロッキング若干有り(△)、過半の領域にわたって色目が異なった場合をブロッキング有り(×)とした。結果を表2に示す。
実施例およ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、裁断機にて100m/分で巻き出し、春日電機社製「防爆型静電気電位測定器 KSD-0108」を使用して、巻き出し直後の剥離剤層表面の帯電量(巻き出し帯電量)を測定した。8kV未満を「A」、8以上12kV未満を「B」、12kV以上を「C」とした。結果を表2に示す。
チタン酸バリウム粉末(BaTiO3;堺化学工業社製,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(積水化学工業社製,エスレックB・K BM-2)8質量部、およ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、トルエンおよびエタノールの混合液(質量比6:4)135質量部を加え、ボールミルにて混合分散させて、セラミックスラリーを調製した。
11…基材
12…樹脂層
13…剥離剤層
Claims (7)
- 基材と、
前記基材の第1の面上に積層され、導電性高分子を含有し、厚さが30~290nmである樹脂層と、
前記樹脂層上に積層された剥離剤層と
を備え、
前記剥離剤層の表面における最大突起高さ(Rp)が10~100nm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の剥離フィルム。 - 前記基材の第2の面における算術平均粗さ(Ra)が5~50nmであり、最大突起高さ(Rp)が40~300nmであることを特徴とする請求項1に記載の剥離フィルム。
- 前記樹脂層は、ポリエステル樹脂、ウレタン樹脂およびアクリル樹脂からなる群から選ばれる少なくとも1種を含有することを特徴とする請求項1または2に記載の剥離フィルム。
- 前記樹脂層は、前記導電性高分子として、ポリチオフェン系導電性高分子、ポリアニリン系導電性高分子およびポリピロール系導電性高分子からなる群から選ばれる少なくとも1種を含有することを特徴とする請求項1~3のいずれか一項に記載の剥離フィルム。
- 前記剥離剤層は、付加反応型シリコーン樹脂を主成分とする剥離剤から構成されることを特徴とする請求項1~4のいずれか一項に記載の剥離フィルム。
- 前記剥離剤層に対する日東電工社製ポリエステル粘着テープNo.31Bの180°剥離力(mN/20mm)を剥離力X、
前記剥離剤層の表面を、学振式摩擦堅牢試験機を用いて、前記基材の第2の面を研磨片として加重1kg、往復10回の条件にて研磨し、当該研磨面に対する日東電工社製ポリエステル粘着テープNo.31Bの180°剥離力(mN/20mm)を剥離力Yとしたときに、
(剥離力X/剥離力Y)×100%
の式で表わされる剥離剤層保持率が、85%以上であることを特徴とする請求項1~5のいずれか一項に記載の剥離フィルム。 - ロール状に巻き取った幅400mm、長さ5000mの前記剥離フィルムを100m/分で巻き出した直後における前記剥離剤層の表面の帯電量が、10kV以下であることを特徴とする請求項1~6のいずれか一項に記載の剥離フィルム。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012800193569A CN103476557A (zh) | 2011-04-21 | 2012-04-09 | 陶瓷生坯片制造工序用剥离膜 |
KR1020137027954A KR20140011390A (ko) | 2011-04-21 | 2012-04-09 | 세라믹 그린 시트 제조 공정용의 박리 필름 |
SG2013077839A SG194546A1 (en) | 2011-04-21 | 2012-04-09 | Releasing film for ceramic green sheet production processes |
US14/112,060 US20140050887A1 (en) | 2011-04-21 | 2012-04-09 | Releasing film for ceramic green sheet production processes |
Applications Claiming Priority (2)
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JP2011094755A JP2012224011A (ja) | 2011-04-21 | 2011-04-21 | セラミックグリーンシート製造工程用の剥離フィルム |
JP2011-094755 | 2011-04-21 |
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WO2012144366A1 true WO2012144366A1 (ja) | 2012-10-26 |
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US (1) | US20140050887A1 (ja) |
JP (1) | JP2012224011A (ja) |
KR (1) | KR20140011390A (ja) |
CN (1) | CN103476557A (ja) |
SG (1) | SG194546A1 (ja) |
TW (1) | TW201302478A (ja) |
WO (1) | WO2012144366A1 (ja) |
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CN106029315A (zh) * | 2014-02-28 | 2016-10-12 | 琳得科株式会社 | 印刷电路基板制造用剥离膜、印刷电路基板制造用剥离膜的制造方法、印刷电路基板的制造方法、及印刷电路基板 |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003291291A (ja) * | 2002-04-02 | 2003-10-14 | Mitsubishi Polyester Film Copp | 離型フィルム用ポリエステルフィルム |
JP2005153250A (ja) * | 2003-11-25 | 2005-06-16 | Lintec Corp | 帯電防止性を有する離型フィルム及びその製造方法 |
JP2006176773A (ja) * | 2004-12-21 | 2006-07-06 | Mitsubishi Polyester Film Gmbh | 二軸延伸ポリエステルフィルム及びその製造方法 |
JP2007069360A (ja) * | 2005-09-02 | 2007-03-22 | Lintec Corp | 高平滑性剥離シート及びその製造方法 |
JP2008150515A (ja) * | 2006-12-19 | 2008-07-03 | Lintec Corp | 付加反応型シリコーン系剥離剤組成物、及び剥離フィルム |
JP2009083271A (ja) * | 2007-09-28 | 2009-04-23 | Tdk Corp | 積層フィルムおよび積層セラミック電子部品の製造方法 |
JP2011231329A (ja) * | 2011-06-15 | 2011-11-17 | Nitto Denko Corp | 粘着シート |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4160731B2 (ja) * | 2001-02-15 | 2008-10-08 | Tdk株式会社 | 薄膜製造用剥離フィルムの製造方法および薄膜製造用剥離フィルム |
CN100384622C (zh) * | 2003-04-02 | 2008-04-30 | Tdk株式会社 | 剥离膜及其制造方法 |
JP4611084B2 (ja) * | 2005-03-31 | 2011-01-12 | リンテック株式会社 | 剥離フィルム |
US7641946B2 (en) * | 2005-08-08 | 2010-01-05 | Nitto Denko Corporation | Adhesive film and image display device |
-
2011
- 2011-04-21 JP JP2011094755A patent/JP2012224011A/ja active Pending
-
2012
- 2012-04-09 KR KR1020137027954A patent/KR20140011390A/ko not_active Application Discontinuation
- 2012-04-09 SG SG2013077839A patent/SG194546A1/en unknown
- 2012-04-09 CN CN2012800193569A patent/CN103476557A/zh active Pending
- 2012-04-09 US US14/112,060 patent/US20140050887A1/en not_active Abandoned
- 2012-04-09 WO PCT/JP2012/059678 patent/WO2012144366A1/ja active Application Filing
- 2012-04-11 TW TW101112743A patent/TW201302478A/zh unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003291291A (ja) * | 2002-04-02 | 2003-10-14 | Mitsubishi Polyester Film Copp | 離型フィルム用ポリエステルフィルム |
JP2005153250A (ja) * | 2003-11-25 | 2005-06-16 | Lintec Corp | 帯電防止性を有する離型フィルム及びその製造方法 |
JP2006176773A (ja) * | 2004-12-21 | 2006-07-06 | Mitsubishi Polyester Film Gmbh | 二軸延伸ポリエステルフィルム及びその製造方法 |
JP2007069360A (ja) * | 2005-09-02 | 2007-03-22 | Lintec Corp | 高平滑性剥離シート及びその製造方法 |
JP2008150515A (ja) * | 2006-12-19 | 2008-07-03 | Lintec Corp | 付加反応型シリコーン系剥離剤組成物、及び剥離フィルム |
JP2009083271A (ja) * | 2007-09-28 | 2009-04-23 | Tdk Corp | 積層フィルムおよび積層セラミック電子部品の製造方法 |
JP2011231329A (ja) * | 2011-06-15 | 2011-11-17 | Nitto Denko Corp | 粘着シート |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013146295A1 (ja) * | 2012-03-30 | 2013-10-03 | リンテック株式会社 | グリーンシート製造用剥離フィルム |
CN105189068A (zh) * | 2013-03-15 | 2015-12-23 | 琳得科株式会社 | 印刷电路基板制造用剥离膜及印刷电路基板制造用剥离膜的制造方法 |
CN105189068B (zh) * | 2013-03-15 | 2017-09-29 | 琳得科株式会社 | 印刷电路基板制造用剥离膜及印刷电路基板制造用剥离膜的制造方法 |
CN106029315A (zh) * | 2014-02-28 | 2016-10-12 | 琳得科株式会社 | 印刷电路基板制造用剥离膜、印刷电路基板制造用剥离膜的制造方法、印刷电路基板的制造方法、及印刷电路基板 |
JP2017007227A (ja) * | 2015-06-23 | 2017-01-12 | 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 |
Also Published As
Publication number | Publication date |
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TW201302478A (zh) | 2013-01-16 |
US20140050887A1 (en) | 2014-02-20 |
CN103476557A (zh) | 2013-12-25 |
JP2012224011A (ja) | 2012-11-15 |
SG194546A1 (en) | 2013-12-30 |
KR20140011390A (ko) | 2014-01-28 |
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