WO2019131449A1 - Mold release film for production of ceramic green sheet - Google Patents
Mold release film for production of ceramic green sheet Download PDFInfo
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- WO2019131449A1 WO2019131449A1 PCT/JP2018/047027 JP2018047027W WO2019131449A1 WO 2019131449 A1 WO2019131449 A1 WO 2019131449A1 JP 2018047027 W JP2018047027 W JP 2018047027W WO 2019131449 A1 WO2019131449 A1 WO 2019131449A1
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- layer
- green sheet
- ceramic green
- film
- release
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
Definitions
- the present invention relates to a release film for producing an ultra-thin layer ceramic green sheet, and more specifically, a production method for suppressing the occurrence of process defects due to pinholes and uneven thickness and peeling defects at the time of producing an ultra-thin layer ceramic green sheet
- the present invention relates to a release film for producing an ultra-thin layer ceramic green sheet that can be produced.
- a release film having a polyester film as a base material and a release layer laminated thereon is used for forming a ceramic green sheet such as a multilayer ceramic capacitor (hereinafter referred to as MLCC), a ceramic substrate or the like.
- MLCC multilayer ceramic capacitor
- the ceramic green sheet is molded by coating and drying a slurry containing a ceramic component such as barium titanate and a binder resin on a release film. After printing an electrode on a molded ceramic green sheet and peeling it from a release film, a laminated ceramic capacitor is manufactured by laminating, pressing and cutting the ceramic green sheet, and firing and applying an external electrode.
- the thickness of ceramic green sheets has been further reduced, and ceramic green sheets having a thickness of 1.0 ⁇ m or less, more specifically 0.2 ⁇ m to 1.0 ⁇ m, have been required. Therefore, higher smoothness is required on the surface of the release layer.
- the strength of the ceramic green sheet decreases as the thickness of the ceramic green sheet decreases, not only the surface of the release layer is smoothed, but also the peel strength when peeling the ceramic green sheet from the release film is low and uniform. It is preferable to reduce the load applied to the ceramic green sheet as much as possible when peeling the ceramic green sheet from the release film, and to prevent the ceramic green sheet from being damaged.
- the mold release layer is used by using an active energy ray curing component in the mold release layer
- an active energy ray curing component in the mold release layer
- measures have been studied for suppressing the elastic deformation of the release layer at the time of peeling of the ceramic green sheet and reducing the peeling force (for example, Patent Documents 2 and 3).
- the surface is exfoliated because the smoothness is too high, the exfoliation force is increased, and the green sheet may be cracked.
- JP 2000-117899 A International Publication No. 2013/145864 International Publication No. 2013/145865 International Publication No. 2014/203702 JP, 2016-127120, A JP, 2017-081805, A
- the present inventors continuously form a low protrusion having a constant shape on the surface of the mold release layer, thereby causing the above-described heavy peeling, the deterioration of processing suitability, and the generation of a defect factor.
- I determined that I could suppress it.
- the object of the present invention is to provide a release film for forming a ceramic green sheet which is excellent in releasability and hardly causes damage such as a pinhole defect or a crack at the time of exfoliation to an extremely thin ceramic green sheet to be formed. It is.
- the present invention has the following constitution.
- a release film in which a release layer of 0.2 to 3.5 ⁇ m is laminated on at least one surface of a polyester film directly or through another layer, and the area surface roughness (Sa) of the release layer surface is A release film for producing a ceramic green sheet, having a maximum peak height (Rp) of 60 nm or less and 5 to 40 nm. 2.
- the polyester film is a laminated polyester film comprising at least a surface layer A and two or more layers including a surface layer B opposite to the surface layer A, and a release layer is laminated on the surface layer A.
- the surface layer B contains particles, the particles are silica particles and / or calcium carbonate particles, and the total content of particles is 5000 to 15000 ppm with respect to the total mass of the surface layer B. Release film for ceramic green sheet production. 6.
- Release film for ceramic green sheet production. 7 A method for producing a ceramic green sheet, wherein the ceramic green sheet is formed by using the release film for producing a ceramic green sheet according to any one of the first to sixth aspects, wherein the formed ceramic green sheet has a thickness of 0.2 ⁇ m to A method of producing a ceramic green sheet characterized by having a thickness of 1.0 ⁇ m.
- the release film for producing a ceramic green sheet of the present invention compared to the conventional release film for producing a ceramic green sheet, the peeling force is not too heavy, the processability is excellent, and the large protrusion is formed on the release layer. Since there is no film, it has become possible to provide a release film for producing a ceramic green sheet capable of reducing defects such as pinholes in an ultrathin ceramic green sheet having a thickness of 1 ⁇ m or less.
- the release film for producing an ultrathin ceramic green sheet of the present invention has a release layer on at least one side of the polyester film directly or through another layer, and the surface roughness (Sa of the release layer surface) (Sa And the maximum peak height (Rp) is preferably 60 nm or less. And, the release layer is incompatible with the energy ray curable compound (I) having three or more reactive groups in one molecule, and the energy ray curable compound (I), and a sea-island structure by phase separation.
- a mold release film for producing a ceramic green sheet, in which a coating film containing at least a resin (II) forming the resin and a mold release component (III) is cured is a preferred embodiment.
- polyester film The polyester constituting the polyester film used as the substrate in the release film of the present invention is not particularly limited, and polyester film generally used as a release film substrate can be film-molded, but Preferably, it is a crystalline linear saturated polyester composed of an aromatic dibasic acid component and a diol component, for example, polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, polytrimethylene terephthalate or these Further preferred is a copolymer having as a main component a component of the resin of (1), and particularly preferred is a polyester film formed of polyethylene terephthalate.
- the repeating unit of ethylene terephthalate is preferably 90 mol% or more, more preferably 95 mol% or more, and small amounts of other dicarboxylic acid components and diol components may be copolymerized, but from the viewpoint of cost And those produced solely from terephthalic acid and ethylene glycol.
- known additives for example, an antioxidant, a light stabilizer, an ultraviolet light absorber, a crystallizing agent and the like may be added within a range not to inhibit the effect of the film of the present invention.
- the polyester film is preferably a polyester film because of the height of the elastic modulus in both directions and the like.
- the intrinsic viscosity of the polyethylene terephthalate film is preferably 0.50 to 0.70 dl / g, more preferably 0.52 to 0.62 dl / g.
- the intrinsic viscosity is 0.50 dl / g or more, breakage is less likely to occur in the stretching step, which is preferable.
- it is 0.70 dl / g or less, it is preferable because the cutting property when cutting into a predetermined product width is good and dimensional defects do not occur.
- the raw material be sufficiently vacuum dried.
- the method for producing the polyester film in the present invention is not particularly limited, and a method generally used conventionally can be used.
- the polyester is melted by an extruder, extruded into a film, cooled by a rotary cooling drum to obtain an unstretched film, and obtained by uniaxially or biaxially stretching the unstretched film.
- a biaxially stretched film can be obtained by sequentially biaxially stretching a longitudinally or transversely uniaxially stretched film in the transverse direction or longitudinal direction, or by simultaneously biaxially stretching an unstretched film in the longitudinal direction and transverse direction. It can.
- the stretching temperature at the time of stretching the polyester film is preferably at least the secondary transition point (Tg) of the polyester. It is preferable to stretch 1 to 8 times, particularly 2 to 6 times in each of the longitudinal and transverse directions.
- the polyester film preferably has a thickness of 12 to 50 ⁇ m, more preferably 12 to 38 ⁇ m, and still more preferably 15 to 31 ⁇ m. If the thickness of the film is 12 ⁇ m or more, it is preferable because there is no risk of deformation due to heat at the time of film production, processing step of the release layer, and molding of the ceramic green sheet. On the other hand, if the thickness of the film is 50 ⁇ m or less, the amount of film discarded after use is not extremely large, which is preferable in reducing the environmental impact, and furthermore, the material per area of the release film used is small. It is also preferable from the economic point of view.
- the polyester film substrate may be a single layer or a multilayer of two or more layers, but it is a laminated polyester film having a surface layer A substantially free of inorganic particles on at least one side. preferable.
- a laminated polyester film having a multilayer structure of two or more layers it is preferable to have a surface layer B capable of containing particles and the like on the opposite surface of the surface layer A substantially free of inorganic particles.
- the layer configuration in the thickness direction is the release layer.
- the surface layer B can also contain no particles. In that case, it is preferable to provide a coat layer (D) containing particles and a binder on the surface layer B in order to impart slipperiness for winding the film into a roll.
- the surface layer A forming the surface to which the release layer is applied does not substantially contain inorganic particles.
- the area average surface roughness (Sa) of the surface layer A is preferably 7 nm or less. If Sa is 7 nm or less, even if the thickness of the release layer is 2.0 ⁇ m or less, and even a thin film such as 0.5 ⁇ m or less, pinholes or the like occur during molding of the ultra-thin ceramic green sheet to be laminated Hard and preferred.
- the area average surface roughness (Sa) of the surface layer A is preferably as small as possible, but may be 0.1 nm or more. However, when providing the below-mentioned anchor coat layer etc.
- an inorganic particle is not included in a coat layer substantially, and the field surface average roughness (Sa) after coat layer lamination is within the above-mentioned range.
- substantially free of inorganic particles is defined as 50 ppm or less when the inorganic element is quantified by fluorescent X-ray analysis, preferably 10 ppm or less, and most preferably below the detection limit. Content. This is because, even if the inorganic particles are not positively added to the film, contamination components derived from extraneous foreign matter, stains attached to the lines and devices in the manufacturing process of the raw material resin or the film are peeled off and mixed in the film. It is because there is a case.
- the surface layer B forming the surface opposite to the surface layer A to which the release layer is applied is in the form of particles from the viewpoint of film slipperiness and air escapeability. It is preferable to contain, in particular, silica particles and / or calcium carbonate particles. The content of particles contained is preferably 5,000 to 15,000 ppm in total of particles in the surface layer B.
- the area average surface roughness (Sa) of the film of the surface layer B is preferably in the range of 1 to 40 nm. More preferably, it is in the range of 5 to 35 nm.
- the total of the silica particles and / or calcium carbonate particles in the surface layer B is 5000 ppm or more and Sa is 1 nm or more, air can be uniformly released when the film is rolled up, and the winding appearance is good.
- the good planarity makes it suitable for the production of ultra-thin ceramic green sheets.
- the total amount of silica particles and / or calcium carbonate particles is 15000 ppm or less and Sa is 40 nm or less, aggregation of the lubricant is difficult to occur and coarse protrusions can not be formed, so the ceramic green sheet of ultrathin layer is wound after molding Even in this case, the ceramic green sheet is preferable without causing defects such as pinholes.
- silica particles and / or calcium carbonate particles As particles contained in the surface layer B, it is more preferable to use silica particles and / or calcium carbonate particles from the viewpoint of transparency and cost.
- inert inorganic particles and / or heat resistant organic particles can be used, and examples of other inorganic particles that can be used include alumina-silica composite oxide particles, hydroxyapatite particles, etc.
- heat resistant organic particles crosslinked polyacrylic particles, crosslinked polystyrene particles, benzoguanamine particles and the like can be mentioned.
- porous colloidal silica is preferable, and when calcium carbonate particles are used, light calcium carbonate which has been surface-treated with a polyacrylic acid-based polymer compound is preferable from the viewpoint of preventing the slippage of the lubricant. .
- the average particle diameter of the particles added to the surface layer B is preferably 0.1 ⁇ m to 2.0 ⁇ m and particularly preferably 0.5 ⁇ m to 1.0 ⁇ m. If the average particle size of the particles is 0.1 ⁇ m or more, the slipperiness of the release film is good and preferable. In addition, if the average particle diameter is 2.0 ⁇ m or less, there is no possibility of generation of pinholes due to coarse particles on the surface of the release layer, which is preferable.
- grains observes the particle of the cross section of the film after a process with a scanning electron microscope, observes 100 particle
- the shape of the particles is not particularly limited as long as the object of the present invention is satisfied, and spherical particles and irregular-shaped non-spherical particles can be used.
- the particle diameter of the irregularly shaped particles can be calculated as the equivalent circle diameter.
- the equivalent circle diameter is a value obtained by dividing the area of the observed particles by the circular constant ( ⁇ ), calculating the square root and doubling it.
- the surface layer B may contain two or more types of particles different in material. Also, particles of the same type but different in average particle size may be contained.
- the surface layer B does not contain particles
- the means to provide this coating layer is not specifically limited, It is preferable to provide by what is called the in-line coating method coated in film forming of a polyester film.
- the polyester film does not need to have the surface layers A and B, and it is necessary to May be composed of a single-layer polyester film not contained.
- the area average surface roughness (Sa) of the surface layer B is preferably 40 nm or less, more preferably 35 nm or less, and still more preferably 30 nm or less. Also, when the surface layer B or the surface of the single-layer polyester film not to be laminated is provided with lubricity by the coat layer (D), Sa on the surface is the surface on which the coat layer is laminated. It is preferable that the area of the surface layer B be in the same range as the surface average roughness (Sa).
- Coat layer D Preferably, at least a binder resin and particles are contained in the coat layer D on the surface of the polyester film on the side where the release layer is not laminated.
- Binder resin of coat layer D Although it does not specifically limit as a binder resin which comprises a lubricious application layer, as a specific example of a polymer, a polyester resin, an acrylic resin, a urethane resin, polyvinyl-type resin (polyvinyl alcohol etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose , Hydroxycellulose, starches and the like. Among these, it is preferable to use a polyester resin, an acrylic resin, or a urethane resin from the viewpoint of retention of particles and adhesion. In addition, polyester resins are particularly preferable in consideration of familiarity with polyester films.
- the polyester of the binder is preferably a copolyester.
- the polyester resin may be polyurethane-modified.
- urethane resin is mentioned as another preferable binder resin which comprises the easily slipping coating layer on a polyester base film.
- Polycarbonate polyurethane resin is mentioned as a urethane resin.
- polyester resin and polyurethane resin may be used in combination, and the other binder resin described above may be used in combination.
- the slippery coating layer in order to form a crosslinked structure in the slippery coating layer, may be formed to contain a crosslinking agent.
- a crosslinking agent By including the crosslinking agent, it is possible to further improve the adhesion under high temperature and high humidity.
- Specific examples of the crosslinking agent include ureas, epoxys, melamines, isocyanates, oxazolines, carbodiimides, and aziridine.
- a catalyst etc. can be used suitably as needed.
- the slippery coating layer preferably contains lubricant particles in order to impart slipperiness to the surface.
- the particles may be inorganic particles or organic particles, and are not particularly limited.
- Inorganic particles such as magnesium and barium sulfate, (2) acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, styrene / acrylic, styrene / butadiene, polystyrene / acrylic, polystyrene / isoprene, polystyrene / Is
- the average particle diameter of the particles is preferably 10 nm or more, more preferably 20 nm or more, and still more preferably 30 nm or more.
- the average particle diameter of the particles is 10 nm or more, aggregation is difficult and slipperiness can be secured, which is preferable.
- the average particle diameter of the particles is preferably 1000 nm or less, more preferably 800 nm or less, and still more preferably 600 nm or less. Transparency is maintained as the average particle diameter of particle
- the surface layer A which is the layer on which the release layer is provided, in order to prevent mixing of particles such as a lubricant.
- the thickness ratio of surface layer A which is a layer at the side which provides the said mold release layer is 20% or more and 50% or less of the total layer thickness of a base film. If it is 20% or more, the influence of particles contained in the surface layer B or the like is not easily received from the inside of the film, and the area surface average roughness Sa easily meets the above range, which is preferable.
- regeneration raw material in surface layer B can be increased as it is 50% or less of the thickness of the whole layer of a base film, an environmental impact is small and preferable.
- the type and amount of the lubricant contained in the surface layer B, the particle diameter, and the area surface average roughness (Sa) satisfy the above range.
- a film after stretching or uniaxial stretching in the film forming process on the surface of the surface layer A and / or the surface layer B in order to improve adhesion of a release layer applied later or to prevent charging etc. May be provided with a coating layer, or may be subjected to corona treatment or the like.
- a coat layer is also provided, Sa of each layer is substituted by the measurement value of the coat layer surface.
- the release layer of the present invention is incompatible with the energy ray-curable compound (I) having three or more reactive groups in one molecule and the energy ray-curable compound (I) and is phase separated to form a sea-island structure. It is preferable to cure the coating film containing at least the resin (II) forming the resin and the mold release component (III).
- the coating film containing at least the resin (II) forming the resin and the mold release component (III) By forming the sea-island structure by the phase separation of the energy ray-curable compound (I) and the resin (II), it is possible to easily form asperities with an appropriate height, and no coarse projections are generated. No holes occur.
- the flat portion is almost absent and peeling occurs at points, even a brittle ultra-thin ceramic green sheet can be peeled without dipping, so that damage such as cracking or deformation can be suppressed. .
- an energy ray-curable compound having three or more reactive groups in one molecule can be used as the energy ray-curable compound (I) used in the present invention.
- an energy ray-curable compound having three or more reactive groups in one molecule By having three or more reactive groups in one molecule, it becomes a release layer having a high elastic modulus, and deformation of the release layer at the time of green sheet peeling can be suppressed, and heavy peeling can be suppressed.
- the solvent resistance of the release layer can be improved, the erosion of the release layer by the solvent can be prevented at the time of slurry coating, which is preferable.
- an energy ray-curable compound having three or more reactive groups in one molecule it is not particularly limited whether to react directly by energy rays or by reactive species generated indirectly.
- the content of the energy ray-curable compound (I) in the solid component in the release layer-forming coating solution is preferably 60 to 98% by mass, and more preferably 75 to 97% by mass. By adding 60% by mass or more, the degree of crosslinking can be maintained, and a high elastic modulus can be obtained.
- Examples of the reactive group of the energy ray-curable compound (I) include a (meth) acryloyl group, an alkenyl group, an acrylamide group, a maleimide group, an epoxy group and a cyclohexene oxide group. Among them, an energy ray curable compound having a (meth) acryloyl group excellent in processability is preferable.
- the energy ray-curable compound having a (meth) acryloyl group can be used without limitation to monomers, oligomers and polymers. Further, it is preferable to contain a compound having three or more reactive groups in at least one molecule, but two or more compounds such as a compound having one or two reactive groups in the molecule are mixed and used. It can also be done. By mixing a compound having a small number of reactive groups, curling and the like can be suppressed.
- energy ray curable monomers having three or more (meth) acryloyl groups in the molecule isocyanuric acid triacrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tri Methylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate ) Multifunctional (meth) acrylates such as acrylates and their ethylene oxide modified products, propylene oxide modified products, caprolactone modified products, etc. That.
- energy ray curable monomers having 1 or 2 reactive groups in the molecule methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, cyclopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, Nonyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, cyclic trimethylolpropy
- Examples of energy ray curable oligomers having 3 or more (meth) acryloyl groups in the molecule include urethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, silicone modified acrylate, etc. It can be used.
- EBECRYL series manufactured by Daicel Ornex Co., Ltd. biscoat series manufactured by Osaka Organic Chemical Industry Co., Ltd., urethane acrylate series manufactured by Kyoeisha Chemical Co., Ltd.
- Examples of energy ray-curable polymers having three or more (meth) acryloyl groups in the molecule include graft polymers in which (meth) acryloyl groups are grafted to the polymer, block polymers in which a polyfunctional acrylic monomer is added to the polymer end, etc. Can be mentioned.
- acrylic resin, epoxy resin, polyester resin, polyorganosiloxane and the like can be used, and it is not particularly limited.
- the resin (II) used in the present invention is dissolved or dispersed in the same solvent as the energy ray curable compound (I) and both are dissolved or dispersed in the state of a coating agent, but after application, the solvent is dried. It is preferable to form a sea-island structure by using the energy ray-curable compound (I) as the sea component and the resin (II) as the island component, since they are mutually incompatible in the release layer formed through curing. (II) can be used without particular limitation as long as the above requirements are satisfied. Two or more resins can also be used simultaneously.
- the content of the resin (II) in the solid content in the release layer-forming coating solution is preferably 1 to 40% by mass, and more preferably 1 to 10% by mass. Sufficient unevenness can be formed by containing 1% by mass or more, and by setting the amount to 40% by mass or less, the degree of crosslinking of the release layer is high, and the temperature dependency at peeling is low, which is preferable.
- any solvent-soluble resin such as polyester resin, acrylic resin, urethane resin, polyester urethane resin, polyimide resin, polyamideimide resin, cellulose resin can be used without particular limitation.
- the condition is that the resin is incompatible with the energy ray-curable compound (I).
- the polyester resin is not particularly limited, and commercially available resins can be used.
- Bayon (registered trademark) series manufactured by Toyobo Co., Ltd. Nichigo Polyester (registered trademark) series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., and the like can be mentioned.
- the acrylic resin is an oligomer or a polymer obtained by polymerizing an acrylic ester, and may be a homopolymer or a copolymer. Moreover, a commercially available thing can be used. For example, the acryl Corporation (registered trademark) series ARICON (trade name) manufactured by Toagosei Co., Ltd. and the like, and the like may be mentioned.
- polyester urethane resin examples include Byron (registered trademark) UR series manufactured by Toyobo Co., Ltd.
- the releasing component (III) used in the present invention is not particularly limited as long as it is a material capable of exhibiting releasing property with the green sheet, such as polyorganosiloxane, fluorine compound, long chain alkyl compound, and waxes. Moreover, the material which has a functional group which can react and couple
- the content of the release component (III) in the solid content in the release layer-forming coating solution is preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass. If the content is 0.05% by mass or more, the peeling force can be lightened, and if the content is 10% by mass or less, the transfer of the releasing component to the ceramic green sheet or the like can be suppressed, which is preferable.
- polyorganosiloxanes in addition to polydimethylsiloxane, polydiethylsiloxane, polyphenylsiloxane, etc., siloxane compounds having a partial organic modification, block polymers having polyorganosiloxanes, polymers obtained by grafting polyorganosiloxanes, etc. It can be used.
- siloxane compounds having a partial organic modification block polymers having polyorganosiloxanes, polymers obtained by grafting polyorganosiloxanes, etc. It can be used.
- BYK (registered trademark) series manufactured by Big Chemie Japan Co., Ltd., Modiper (registered trademark) series manufactured by NOF Corporation, and the like can be used.
- the fluorine compound is not particularly limited, and commercially available ones can be used.
- Megafuck (registered trademark) series manufactured by DIC Corporation can be mentioned.
- long chain alkyl compounds include acrylic polymers copolymerized with long chain alkyl acrylates, graft polymers grafted with long chain alkyl, and block polymers with long chain alkyl end-added. Moreover, it does not specifically limit, A commercially available thing can be used. For example, Tesfine (registered trademark) series manufactured by Hitachi Chemical Co., Ltd., and Peiroil (registered trademark) manufactured by Lion Specialty Chemicals, etc. may be mentioned.
- the active energy ray examples include infrared rays, visible rays, ultraviolet rays, electromagnetic waves such as X-rays, electron beams, ion beams, particle rays such as neutrons and alpha rays, and the like, among them, the production cost It is preferable to use excellent ultraviolet light.
- the atmosphere when the active energy ray is irradiated may be a general air or a nitrogen gas atmosphere.
- a nitrogen gas atmosphere the radical reaction can proceed smoothly by reducing the oxygen concentration, and the elastic modulus of the release layer can be improved. It is preferable from the economical point of view.
- photopolymerization initiator When a radical polymerization compound is used in the release layer of the present invention, it is preferable to add a photopolymerization initiator.
- the photopolymerization initiator include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, 2,4 -Diethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, ⁇ -chloro anthraquinone, (2,4,6-trimethyl And benzyl diphenyl)
- 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methylpropan-1-one which is considered to be excellent in surface curability.
- 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One is preferred, among which 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one are particularly preferred. preferable. These may be used alone or in combination of two or more.
- the addition amount of a photoinitiator is not specifically limited, For example, it is preferable to contain about 0.1 to 20 mass% as solid content in the coating liquid for release layer formation.
- the releasing layer in the present invention can contain particles having a particle diameter of 1 ⁇ m or less, but it is preferable not to contain particles forming projections such as particles from the viewpoint of generation of pinholes.
- an adhesion improver an additive such as an antistatic agent, or the like may be added to the release layer in the present invention as long as the effects of the present invention are not impaired. Further, in order to improve the adhesion to the substrate, it is also preferable to subject the polyester film surface to pretreatment such as anchor coating, corona treatment, plasma treatment, atmospheric pressure plasma treatment or the like before the release coating layer is provided.
- the thickness of the release layer may be set according to the purpose of use, and is not particularly limited, but preferably the range from 0.2 to 3.5 ⁇ m of the release layer after curing is preferable. More preferably, it is 0.5 to 3.0 ⁇ m.
- the thickness of the release layer is 0.2 ⁇ m or more, the curability of the energy ray-curable copolymer is good, and the elastic modulus of the release layer is improved. Further, when the thickness is 3.5 ⁇ m or less, curling is unlikely to occur even when the thickness of the release film is reduced, and thus it is preferable because the running property is not deteriorated in the process of molding and drying the ceramic green sheet.
- the surface of the release layer has appropriate irregularities. Therefore, it is preferable that the area surface average roughness (Sa) of the release layer surface is 5 to 40 nm. Further, it is more preferable that the above-mentioned Sa is satisfied, and the maximum projection height (Rp) on the surface of the releasing layer is 60 nm or less. Furthermore, the area surface average roughness (Sa) is preferably 5 to 20 nm, and more preferably 8.5 to 20 nm. At the same time, it is particularly preferred that the maximum projection height (Rp) be 50 nm or less.
- the zipping can be reduced at the time of peeling of the ceramic green sheet, and even an ultrathin layer green sheet can be easily peeled without damage.
- the area surface roughness (Sa) is 40 nm or less, the particle size of the ceramic is sufficiently smaller than the particle size of the ceramic, and the surface shape of the green sheet is not affected. If the above-mentioned Sa is satisfied and the maximum projection height (Rp) on the surface of the releasing layer is 60 nm or less, the possibility of causing a pinhole defect is further reduced, which is preferable.
- the maximum projection height (Rp) is preferably small, the maximum projection height (Rp) may also be 5 nm or more, 10 nm or more, because the area surface average roughness (Sa) is adjusted to 5 nm or more. It does not matter.
- various factors are related, but mainly the surface layer A of the polyester film Since the single layer polyester film does not substantially contain inorganic particles, the surface roughness on which the release layer is laminated is small, and the release layer has three or more reactive groups in one molecule.
- a curable compound (I) and the energy beam curable compound (I) as a sea component, and a resin (II) which is incompatible with the energy beam curable compound (I) and becomes an island component, are cured It can be said that what is being done is related.
- the method of adjusting the surface roughness (Sa) and the maximum projection height (Rp) of the release layer to the appropriate range as described above is not particularly limited, but mainly the energy ray-curable compound (I) and the resin ( This can be achieved preferably by adjusting the combination and content ratio of the materials of II).
- the static friction coefficient of the release layer surface of the release layer film of the present invention is preferably 0.05 or more and 2.00 or less. More preferably, it is 0.1 or more and 1.00 or less, and still more preferably 0.1 or more and 0.50 or less. If the coefficient of static friction is within the above range, the surface of the coating layer and the surface of the mold release layer slip well and no excessive force is applied, so the damage to the surface of the mold release layer is reduced and damage to the green sheet is reduced. And a good green sheet surface is obtained. Moreover, it is preferable that the dynamic friction coefficient of the mold release layer surface of the mold release film of this invention is 1.00 or less. Within the above range, a good green sheet surface can be obtained without tension abnormality occurring in the process.
- Adjusting the range of the static friction coefficient and the dynamic friction coefficient of the release layer surface is related to the range of the surface roughness (Sa) and the maximum projection height (Rp) of the release layer, and the adjustment method There is no particular limitation, but it can be preferably achieved mainly by adjusting the combination and content ratio of the materials of the energy ray-curable compound (I) and the resin (II).
- the method for forming the releasing layer is not particularly limited, and a coating liquid in which a releasing compound is dissolved or dispersed is spread on one surface of the polyester film of the substrate by coating etc.
- cure after removing by drying is used.
- coating the release layer of this invention on a base film by solution application is 50 degreeC or more and 120 degrees C or less, and is 60 degrees C or more and 100 degrees C or less More preferable.
- the drying time is preferably 30 seconds or less and more preferably 20 seconds or less.
- an active energy ray it is preferable to irradiate an active energy ray to advance the curing reaction.
- the active energy ray used at this time ultraviolet rays, electron beams, X-rays, etc. can be used, but ultraviolet rays are preferred because they are easy to use.
- the amount of ultraviolet light to be irradiated is preferably 30 to 300 mJ / cm 2 , and more preferably 30 to 200 mJ / cm 2 in light amount.
- the curing of the composition proceeds sufficiently, and by setting it to 300 mJ / cm 2 or less, the processing speed can be improved, so that the mold release film can be economically produced. preferable.
- the surface tension of the coating liquid when the release layer is applied is not particularly limited, but is preferably 30 mN / m or less.
- Any known coating method can be applied as the coating method of the above coating solution, for example, roll coating such as gravure coating or reverse coating, bar coating such as wire bar, die coating, spray coating, air knife A conventionally known method such as a coating method can be used.
- Substrate film thickness By using Millitron (electronic micro indicator), 4 pieces of 5 cm square samples are cut out from any 4 parts of the film to be measured, and each 5 pieces (20 pieces in total) are measured and averaged Thickness.
- Millitron electronic micro indicator
- the thickness of the release layer was measured using an optical interference type film thickness meter (F20, manufactured by Filmetrics, Inc.). (The refractive index of the release layer is calculated as 1.52.)
- Region surface roughness (Sa), maximum projection height (Rp) It is a value measured under the following conditions using a non-contact surface shape measurement system (VertScan R550H-M100, manufactured by Ryoka System Co., Ltd.).
- the area surface average roughness (Sa) was an average value of 5 measurements, and the maximum projection height (Rp) was 7 measurements, and the maximum value of 5 values excluding the maximum value and the minimum value was used.
- Measurement condition -Measurement mode: WAVE mode-Objective lens: 50x-0.5 x Tube lens (analysis conditions) -Face correction: 4th order correction-Interpolation: Complete interpolation
- the release film with a ceramic green sheet prepared by the above method was cut into a width of 30 mm and a length of 80 mm, and used as a sample for measurement of peel force. After removing electricity using an electric discharge machine (manufactured by Keyence Corporation, SJ-F020), using a peeling tester (VPA-3 manufactured by Kyowa Interface Science Co., Ltd.), the peeling angle is 30 degrees, the peeling temperature is 25 ° C., and the peeling speed is 10 m / m. It peeled in min. As a peeling direction, a double-sided adhesive tape (Nitto Denko Co., Ltd., No.
- the peeling angle in this evaluation method points out the angle of the direction which pulls a release film with respect to the evaluation sample axis fixed to the peeling test machine.
- the peeling temperature is a temperature at which the release film fixed by using a heater type stage system attached to the apparatus is heated. Peeling is performed after confirming that the temperature of the measurement sample has reached the relevant temperature using a handy type thermometer (HD-1400E, manufactured by Anritsu Keiki Co., Ltd.).
- PET (1) Preparation of polyethylene terephthalate pellets (PET (1))
- a continuous esterification reaction apparatus was used which was composed of a three-stage complete mixing tank having a stirrer, a partial condenser, a raw material feed port and a product outlet.
- TPA terephthalic acid
- EG ethylene glycol
- antimony trioxide is produced in an amount such that 160 ppm of Sb atoms are formed with respect to PET, and these slurries are ester
- the reaction mixture was continuously fed to the first esterification reactor of the esterification reactor, and reacted at 255 ° C.
- the EG solution contains 8% by weight of EG to the produced PET, and further contains an EG solution containing magnesium acetate tetrahydrate in an amount of 65 ppm of Mg atoms to the produced PET, and 40 ppm of P atoms to the produced PET.
- TMPA trimethyl phosphate
- the reaction product of the second esterification reaction vessel is continuously taken out of the system, supplied to the third esterification reaction vessel, and 39 MPa (400 kg / cm 2 ) using a high pressure disperser (manufactured by Nippon Seiki Co., Ltd.) 0.2% by mass of porous colloidal silica with an average particle size of 0.9 ⁇ m dispersed with an average pressure of 5 passes and an average particle of 1% by mass per ammonium carbonate of an ammonium salt of polyacrylic acid While adding 0.4 mass% of synthetic calcium carbonate having a diameter of 0.6 ⁇ m as an EG slurry of 10% each, the reaction was carried out at 260 ° C. at an average residence time of 0.5 hours under normal pressure.
- the esterification reaction product generated in the third esterification reaction vessel was continuously supplied to a three-stage continuous polycondensation reaction apparatus to conduct polycondensation, and a 95% cut diameter sintered a 20 ⁇ m stainless steel fiber After filtration with a filter, it was ultrafiltered and extruded in water, and after cooling it was cut into chips to obtain PET chips with an intrinsic viscosity of 0.60 dl / g (hereinafter abbreviated as PET (1)) .
- PET (1) an intrinsic viscosity of 0.60 dl / g
- PET (2) Preparation of polyethylene terephthalate pellets
- PET (3) Preparation of polyethylene terephthalate pellets (PET (3))
- the type and content of particles of PET (I) were changed to 0.75% by mass of synthetic calcium carbonate having an average particle diameter of 0.9 ⁇ m, in which 1% by mass of ammonium salt of polyacrylic acid was attached per calcium carbonate,
- PET (3) A PET chip was obtained in the same manner as PET (1) (hereinafter referred to as PET (3)).
- the lubricant content in the PET chip was 0.75% by mass.
- PET chips are melted at 285 ° C., melted at 290 ° C. by a separate melt extruder extruder, and a 95% cut diameter sintered filter of 15 ⁇ m stainless steel fibers, 95% cut diameter
- Two-stage filtration of a filter made of sintered 15 ⁇ m stainless steel particles is carried out and merged in a feed block to make PET (1) a surface layer B (a reverse surface side layer), PET (2) a surface Layer A (release surface side layer) is laminated, extruded in a sheet shape at a speed of 45 m / min (casting), and electrostatically adhered and cooled on a casting drum at 30 ° C. by an electrostatic adhesion method.
- A4100 Cosmo Shine (registered trademark), manufactured by Toyobo Co., Ltd.) having a thickness of 25 ⁇ m was used.
- A4100 has the structure which provided the coating layer which contained particle
- Sa of the surface layer A of the laminated film X3 was 1 nm, and Sa of the surface layer B was 2 nm.
- Example 1 Apply coating solution 1 of the following composition onto the surface layer A of the laminated film X1 using reverse gravure so that the thickness of the release layer after drying is 2.5 ⁇ m, and after drying for 30 seconds at 90 ° C., high pressure
- a release film for producing an ultrathin ceramic green sheet was obtained by irradiating ultraviolet rays so as to be 200 mJ / cm 2 using a mercury lamp.
- the release film thickness, area surface roughness Sa, maximum protrusion height Rp, pinhole evaluation of ceramic green sheet, damage evaluation to ceramic green sheet, static friction coefficient, dynamic friction coefficient are evaluated for the obtained release film.
- the (Coating solution 1) Compound (I) 100.00 parts by mass (Dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd. A-DPH, solid concentration 100%)
- Resin (II) Polyester resin 9.47 parts by mass (Toyobo Co., Ltd.
- Release agent (III) 1.26 parts by mass (modified polydimethylsiloxane having an acryloyl group, BYK-UV 3505, manufactured by Byk Chem Japan, solid content 40% by mass)
- Photopolymerization initiator 5.25 parts by mass (OMNIRAD (registered trademark) 907, manufactured by IGM Japan GK, solid content concentration 100% by mass)
- Example 2 Resin (II) was changed to polyester urethane resin (Toyobo Co., Ltd. Byron (registered trademark) UR1400, solid content concentration 30 mass%), and the following coating solution 2 was used.
- the solid content concentration of the coating solution 2 was reduced as compared to the coating solution 1 of Example 1. It applied so that the release layer film thickness after drying might be 1.5 micrometers.
- a release film was obtained in the same manner as in Example 1 except that the coating solution 2 was used and the coating was performed so that the thickness of the release layer after drying was 1.5 ⁇ m.
- the release film thickness, area surface roughness Sa, maximum protrusion height Rp, pinhole evaluation of ceramic green sheet, damage evaluation to ceramic green sheet, static friction coefficient, dynamic friction coefficient are evaluated for the obtained release film.
- the (Coating solution 2) Compound (I) 100.00 parts by mass (Dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd. A-DPH, solid content concentration 100%) Resin (II) polyester urethane resin 31.50 parts by mass (Toyobo Co., Ltd.
- Example 3 The following coating solution 3 was used, in which the proportion of the releasing agent (III) was increased as compared with that in Example 2. It applied so that the release layer film thickness after drying might be set to 1.8 micrometers. A release film was obtained in the same manner as in Example 1 except that the coating solution 3 was used and the coating was performed so that the thickness of the release layer after drying was 1.8 ⁇ m. The release film thickness, area surface roughness Sa, maximum protrusion height Rp, pinhole evaluation of ceramic green sheet, damage evaluation to ceramic green sheet, static friction coefficient, dynamic friction coefficient are evaluated for the obtained release film.
- the (Coating solution 3) Compound (I) 100.00 parts by mass (Dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd. A-DPH, solid content concentration 100%) Resin (II) polyester urethane resin 31.50 parts by mass (Toyobo Co., Ltd.
- Release agent (III) 1.26 parts by mass (modified polydimethylsiloxane having an acryloyl group, BYK-UV 3505, manufactured by Byk Chem Japan, solid content 40% by mass)
- Photopolymerization initiator 5.25 parts by mass (OMNIRAD (registered trademark) 907, manufactured by IGM Japan GK, solid content 100% by mass)
- Example 4 The coating solution 3 used in Example 3 was applied onto the surface layer A of the laminated film X2.
- a release film was obtained in the same manner as in Example 3, except that the laminated film X2 was used.
- the release film thickness, area surface roughness Sa, maximum protrusion height Rp, pinhole evaluation of ceramic green sheet, damage evaluation to ceramic green sheet, static friction coefficient, dynamic friction coefficient are evaluated for the obtained release film.
- Example 5 The coating liquid 3 used in Example 3 was coated on the surface layer A of the laminated film X3.
- a release film was obtained in the same manner as in Example 3, except that the laminated film X3 was used.
- the release film thickness, area surface roughness Sa, maximum protrusion height Rp, pinhole evaluation of ceramic green sheet, damage evaluation to ceramic green sheet, static friction coefficient, dynamic friction coefficient are evaluated for the obtained release film.
- Example 1 Compared with Example 1, the resin (II) is not contained, and the release agent (III) is an acryloyl group-containing polyether-modified polydimethylsiloxane (BYK UV-3500, 100% solid concentration by Big Chemie Japan)
- the following coating solution 4 was used in which the amount of addition was increased and the dilution solvent was changed.
- a release film was obtained in the same manner as in Example 1 except that the coating solution 4 was used and the coating was performed so that the thickness of the release layer after drying was 1.0 ⁇ m.
- the release film thickness, area surface roughness Sa, maximum protrusion height Rp, pinhole evaluation of ceramic green sheet, damage evaluation to ceramic green sheet, static friction coefficient, dynamic friction coefficient are evaluated for the obtained release film.
- the (Coating solution 4) Compound (I) 100.00 parts by mass (Dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd. A-DPH, solid content concentration 100%)
- Releasing agent (III) 1.00 parts by mass (Acryloyl group-containing polyether-modified polydimethylsiloxane BYK UV-3500, 100% solid concentration by Big Chemie Japan)
- the peeling force does not become too heavy as compared with the conventional release film for producing a ceramic green sheet, and the processability is excellent and the release layer is large. Since there is no protrusion, it has become possible to provide a release film for producing a ceramic green sheet capable of reducing defects such as pinholes in an ultrathin ceramic green sheet having a thickness of 1 ⁇ m or less.
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Abstract
Description
1. ポリエステルフィルムの少なくとも片面に直接又は他の層を介して0.2~3.5μmの離型層が積層された離型フィルムであって、前記離型層表面の領域表面粗さ(Sa)が5~40nm、最大山高さ(Rp)が60nm以下であるセラミックグリーンシート製造用離型フィルム。
2. 離型層が、1分子内に3以上の反応性基を有するエネルギー線硬化型化合物(I)と、前記エネルギー線硬化型化合物(I)を海成分とし、前記エネルギー線硬化型化合物(I)と非相溶であり島成分となる樹脂(II)と、離型成分(III)を少なくとも含む塗膜が硬化されてなる上記第1に記載のセラミックグリーンシート製造用離型フィルム。
3. 離型層が実質的に無機粒子を含有しない上記第1又は第2に記載のセラミックグリーンシート製造用離型フィルム。
4. ポリエステルフィルムが、少なくとも表面層Aと、前記表面層Aとは反対側の表面層Bを含む2層以上からなる積層ポリエステルフィルムであって、前記表面層A上に離型層が積層されており、表面層Aには実質的に無機粒子が含有されていない上記第1~第3のいずれかに記載のセラミックグリーンシート製造用離型フィルム。
5. 表面層Bが粒子を含有し、前記粒子がシリカ粒子及び/又は炭酸カルシウム粒子であり、合計の粒子の含有量が表面層Bの総質量に対して5000~15000ppmである上記第4に記載のセラミックグリーンシート製造用離型フィルム。
6. ポリエステルフィルムが実質的に無機粒子を含有しておらず、ポリエステルフィルムの離型層が積層されていない側に粒子を含むコーティング層が積層されている上記第1~第3のいずれかに記載のセラミックグリーンシート製造用離型フィルム。
7. 上記第1~第6のいずれかに記載のセラミックグリーンシート製造用離型フィルムを用いてセラミックグリーンシートを成型するセラミックグリーンシートの製造方法であって、成型されたセラミックグリーンシートが0.2μm~1.0μmの厚みであることを特徴とするセラミックグリーンシートの製造方法。 That is, the present invention has the following constitution.
1. A release film in which a release layer of 0.2 to 3.5 μm is laminated on at least one surface of a polyester film directly or through another layer, and the area surface roughness (Sa) of the release layer surface is A release film for producing a ceramic green sheet, having a maximum peak height (Rp) of 60 nm or less and 5 to 40 nm.
2. An energy ray-curable compound (I), wherein the releasing layer has three or more reactive groups in one molecule, and the energy ray-curable compound (I) as a sea component, the energy ray-curable compound (I) The release film for producing a ceramic green sheet according to the first above, wherein a coating film containing at least a resin (II) which is incompatible with the resin and which becomes an island component and a releasing component (III) is cured.
3. The mold release film for producing a ceramic green sheet according to the first or second form, wherein the mold release layer is substantially free of inorganic particles.
4. The polyester film is a laminated polyester film comprising at least a surface layer A and two or more layers including a surface layer B opposite to the surface layer A, and a release layer is laminated on the surface layer A. The release film for producing a ceramic green sheet according to any one of the first to the third, wherein the surface layer A contains substantially no inorganic particles.
5. The surface layer B contains particles, the particles are silica particles and / or calcium carbonate particles, and the total content of particles is 5000 to 15000 ppm with respect to the total mass of the surface layer B. Release film for ceramic green sheet production.
6. The polyester film according to any one of the above 1 to 3, wherein the polyester film is substantially free of inorganic particles and a coating layer containing the particles is laminated on the side of the polyester film on which the release layer is not laminated. Release film for ceramic green sheet production.
7. A method for producing a ceramic green sheet, wherein the ceramic green sheet is formed by using the release film for producing a ceramic green sheet according to any one of the first to sixth aspects, wherein the formed ceramic green sheet has a thickness of 0.2 μm to A method of producing a ceramic green sheet characterized by having a thickness of 1.0 μm.
本発明の離型フィルムにおいて基材として用いるポリエステルフィルムを構成するポリエステルは、特に限定されず、離型フィルム基材として通常一般に使用されているポリエステルをフィルム成型したものを使用することが出来るが、好ましくは、芳香族二塩基酸成分とジオール成分からなる結晶性の線状飽和ポリエステルであるのが良く、例えば、ポリエチレンテレフタレート、ポリエチレン-2,6-ナフタレート、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート又はこれらの樹脂の構成成分を主成分とする共重合体がさらに好適であり、とりわけポリエチレンテレフタレートから形成されたポリエステルフィルムが好適である。ポリエチレンテレフタレートは、エチレンテレフタレートの繰り返し単位が好ましくは90モル%以上、より好ましくは95モル%以上であり、他のジカルボン酸成分、ジオール成分が少量共重合されていてもよいが、コストの点から、テレフタル酸とエチレングリコールのみから製造されたものが好ましい。また、本発明のフィルムの効果を阻害しない範囲内で、公知の添加剤、例えば、酸化防止剤、光安定剤、紫外線吸収剤、結晶化剤などを添加してもよい。ポリエステルフィルムは双方向の弾性率の高さ等の理由からポリエステルフィルムであることが好ましい。 (Polyester film)
The polyester constituting the polyester film used as the substrate in the release film of the present invention is not particularly limited, and polyester film generally used as a release film substrate can be film-molded, but Preferably, it is a crystalline linear saturated polyester composed of an aromatic dibasic acid component and a diol component, for example, polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, polytrimethylene terephthalate or these Further preferred is a copolymer having as a main component a component of the resin of (1), and particularly preferred is a polyester film formed of polyethylene terephthalate. In polyethylene terephthalate, the repeating unit of ethylene terephthalate is preferably 90 mol% or more, more preferably 95 mol% or more, and small amounts of other dicarboxylic acid components and diol components may be copolymerized, but from the viewpoint of cost And those produced solely from terephthalic acid and ethylene glycol. In addition, known additives, for example, an antioxidant, a light stabilizer, an ultraviolet light absorber, a crystallizing agent and the like may be added within a range not to inhibit the effect of the film of the present invention. The polyester film is preferably a polyester film because of the height of the elastic modulus in both directions and the like.
前記のポリエステルフィルムについて離型層を積層しない側の表面のコート層D中には、少なくともバインダー樹脂及び粒子が含まれていることが好ましい。 (Coat layer D)
Preferably, at least a binder resin and particles are contained in the coat layer D on the surface of the polyester film on the side where the release layer is not laminated.
易滑塗布層を構成するバインダー樹脂としては特に限定されないが、ポリマーの具体例としては、ポリエステル樹脂、アクリル樹脂、ウレタン樹脂、ポリビニル系樹脂(ポリビニルアルコール等)、ポリアルキレングリコール、ポリアルキレンイミン、メチルセルロース、ヒドロキシセルロース、でんぷん類等が挙げられる。これらの中でも粒子の保持、密着性の観点から、ポリエステル樹脂、アクリル樹脂、ウレタン樹脂を使用することが好ましい。また、ポリエステルフィルムとのなじみを考慮した場合、ポリエステル樹脂が特に好ましい。溶剤への溶解性、分散性、さらには基材フィルムや他の層との接着性を達成させるため、バインダーのポリエステルは共重合ポリエステルであることが好ましい。なお、ポリエステル樹脂はポリウレタン変性されていても良い。また、ポリエステル基材フィルム上の易滑塗布層を構成する他の好ましいバインダー樹脂としてはウレタン樹脂が挙げられる。ウレタン樹脂としてはポリカーボネートポリウレタン樹脂が挙げられる。さらに、ポリエステル樹脂、ポリウレタン樹脂は併用しても良く、上記の他のバインダー樹脂を併用してもよい。 (Binder resin of coat layer D)
Although it does not specifically limit as a binder resin which comprises a lubricious application layer, As a specific example of a polymer, a polyester resin, an acrylic resin, a urethane resin, polyvinyl-type resin (polyvinyl alcohol etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose , Hydroxycellulose, starches and the like. Among these, it is preferable to use a polyester resin, an acrylic resin, or a urethane resin from the viewpoint of retention of particles and adhesion. In addition, polyester resins are particularly preferable in consideration of familiarity with polyester films. In order to achieve the solubility in solvents, the dispersibility, and the adhesion to the substrate film and other layers, the polyester of the binder is preferably a copolyester. The polyester resin may be polyurethane-modified. Moreover, urethane resin is mentioned as another preferable binder resin which comprises the easily slipping coating layer on a polyester base film. Polycarbonate polyurethane resin is mentioned as a urethane resin. Furthermore, polyester resin and polyurethane resin may be used in combination, and the other binder resin described above may be used in combination.
本発明において、易滑塗布層中に架橋構造を形成させるために、易滑塗布層は架橋剤が含まれて形成されていてもよい。架橋剤を含有させることにより、高温高湿下での密着性を更に向上させることが可能になる。具体的な架橋剤としては、尿素系、エポキシ系、メラミン系、イソシアネート系、オキサゾリン系、カルボジイミド系、アジリジン等が挙げられる。また、架橋反応を促進させるため、触媒等を必要に応じて適宜使用することができる。 (Cross-linking agent for coat layer D)
In the present invention, in order to form a crosslinked structure in the slippery coating layer, the slippery coating layer may be formed to contain a crosslinking agent. By including the crosslinking agent, it is possible to further improve the adhesion under high temperature and high humidity. Specific examples of the crosslinking agent include ureas, epoxys, melamines, isocyanates, oxazolines, carbodiimides, and aziridine. Moreover, in order to accelerate | stimulate a crosslinking reaction, a catalyst etc. can be used suitably as needed.
易滑塗布層は、表面にすべり性を付与するために、滑剤粒子を含むことが好ましい。粒子は、無機粒子であっても、有機粒子であってもよく、特に限定されるものではないが、(1)シリカ、カオリナイト、タルク、軽質炭酸カルシウム、重質炭酸カルシウム、ゼオライト、アルミナ、硫酸バリウム、カーボンブラック、酸化亜鉛、硫酸亜鉛、炭酸亜鉛、酸化ジルコニウム、二酸化チタン、サチンホワイト、珪酸アルミニウム、ケイソウ土、珪酸カルシウム、水酸化アルミニウム、加水ハロイサイト、炭酸カルシウム、炭酸マグネシウム、リン酸カルシウム、水酸化マグネシウム、硫酸バリウム等の無機粒子、(2)アクリルあるいはメタアクリル系、塩化ビニル系、酢酸ビニル系、ナイロン、スチレン/アクリル系、スチレン/ブタジエン系、ポリスチレン/アクリル系、ポリスチレン/イソプレン系、ポリスチレン/イソプレン系、メチルメタアクリレート/ブチルメタアクリレート系、メラミン系、ポリカーボネート系、尿素系、エポキシ系、ウレタン系、フェノール系、ジアリルフタレート系、ポリエステル系等の有機粒子が挙げられるが、塗布層に適度な滑り性を与えるために、シリカが特に好ましく使用される。 (Particles in the coat layer D)
The slippery coating layer preferably contains lubricant particles in order to impart slipperiness to the surface. The particles may be inorganic particles or organic particles, and are not particularly limited. (1) Silica, kaolinite, talc, light calcium carbonate, ground calcium carbonate, zeolite, alumina, Barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, zirconium oxide, titanium dioxide, satin white, aluminum silicate, diatomaceous earth, calcium silicate, aluminum hydroxide, hydrolysed halloysite, calcium carbonate, magnesium carbonate, calcium phosphate, hydroxide Inorganic particles such as magnesium and barium sulfate, (2) acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, styrene / acrylic, styrene / butadiene, polystyrene / acrylic, polystyrene / isoprene, polystyrene / Iso Although organic particles such as styrene, methyl methacrylate / butyl methacrylate, melamine, polycarbonate, urea, epoxy, urethane, phenol, diallyl phthalate, polyester, etc. may be mentioned, suitable for the coating layer Silica is particularly preferably used to impart slip properties.
本発明の離型層は、1分子内に3以上の反応性基を有するエネルギー線硬化型化合物(I)と前記エネルギー線硬化型化合物(I)と非相溶であり相分離して海島構造を形成する樹脂(II)と、離型成分(III)とを少なくとも含む塗膜を硬化してなることが好ましい。エネルギー線硬化型化合物(I)と樹脂(II)が相分離して海島構造を形成することで、適度な高さの凹凸を簡便に形成でき、粗大突起が発生しないことから、グリーンシートにピンホールなどが発生しない。また、平面部分がほとんどなくなり、点での剥離となるため脆質な超薄層セラミックグリーンシートであっても、ジッピング無く剥離することができるため、クラックや変形などのダメージを抑制することができる。 (Release layer)
The release layer of the present invention is incompatible with the energy ray-curable compound (I) having three or more reactive groups in one molecule and the energy ray-curable compound (I) and is phase separated to form a sea-island structure. It is preferable to cure the coating film containing at least the resin (II) forming the resin and the mold release component (III). By forming the sea-island structure by the phase separation of the energy ray-curable compound (I) and the resin (II), it is possible to easily form asperities with an appropriate height, and no coarse projections are generated. No holes occur. In addition, since the flat portion is almost absent and peeling occurs at points, even a brittle ultra-thin ceramic green sheet can be peeled without dipping, so that damage such as cracking or deformation can be suppressed. .
本発明で用いるエネルギー線硬化型化合物(I)としては、1分子内に3以上の反応性基を有するエネルギー線硬化型化合物を用いることができる。1分子内に3以上の反応性基を有することで、高弾性率の離型層となり、グリーンシート剥離時の離型層の変形を抑制し、重剥離化を抑制することができる。また、離型層の耐溶剤性を向上させることができるためスラリー塗工時に溶剤による離型層の浸食なども防げるため好ましい。また、1分子内に3以上の反応性基を有するエネルギー線硬化型化合物としては、エネルギー線により直接的に反応するか、または間接的に発生した活性種により反応するかは特に限定しない。エネルギー線硬化型化合物(I)の離型層形成用塗布液中の固形分中の含有量としては、60~98質量%が好ましく、75~97質量%が好ましい。60質量%以上添加することで架橋度を維持し、高弾性率を得ることができる。 (Energy ray curable compound (I) having three or more reactive groups in one molecule)
As the energy ray-curable compound (I) used in the present invention, an energy ray-curable compound having three or more reactive groups in one molecule can be used. By having three or more reactive groups in one molecule, it becomes a release layer having a high elastic modulus, and deformation of the release layer at the time of green sheet peeling can be suppressed, and heavy peeling can be suppressed. In addition, since the solvent resistance of the release layer can be improved, the erosion of the release layer by the solvent can be prevented at the time of slurry coating, which is preferable. Moreover, as an energy ray-curable compound having three or more reactive groups in one molecule, it is not particularly limited whether to react directly by energy rays or by reactive species generated indirectly. The content of the energy ray-curable compound (I) in the solid component in the release layer-forming coating solution is preferably 60 to 98% by mass, and more preferably 75 to 97% by mass. By adding 60% by mass or more, the degree of crosslinking can be maintained, and a high elastic modulus can be obtained.
本発明で用いる樹脂(II)としては、エネルギー線硬化型化合物(I)と同一の溶媒に溶解又は分散し塗剤の状態では両者が溶解又は分散した状態であるが、塗布後、溶媒の乾燥、硬化を経て形成された離型層中では相互に非相溶であり、エネルギー線硬化型化合物(I)を海成分とし樹脂(II)を島成分として海島構造を形成することが好ましく、樹脂(II)としては前記要件を満たせば特に限定せず使用できる。2以上の樹脂を同時に用いることもできる。樹脂(II)の離型層形成用塗布液中の固形分中の含有量として、1~40質量%が好ましく、1~10質量%が好ましい。1質量%以上含有させることで十分な凹凸を形成することができ、40質量%以下にすることで離型層の架橋度が高く、剥離時の温度依存性が低く好ましい。 (Resin (II))
The resin (II) used in the present invention is dissolved or dispersed in the same solvent as the energy ray curable compound (I) and both are dissolved or dispersed in the state of a coating agent, but after application, the solvent is dried. It is preferable to form a sea-island structure by using the energy ray-curable compound (I) as the sea component and the resin (II) as the island component, since they are mutually incompatible in the release layer formed through curing. (II) can be used without particular limitation as long as the above requirements are satisfied. Two or more resins can also be used simultaneously. The content of the resin (II) in the solid content in the release layer-forming coating solution is preferably 1 to 40% by mass, and more preferably 1 to 10% by mass. Sufficient unevenness can be formed by containing 1% by mass or more, and by setting the amount to 40% by mass or less, the degree of crosslinking of the release layer is high, and the temperature dependency at peeling is low, which is preferable.
本発明で用いる離型成分(III)としては、ポリオルガノシロキサン、フッ素化合物、長鎖アルキル化合物、ワックス類などグリーンシートとの間で離型性を発揮できる材料であればよく特に限定はない。またこれらの材料に(メタ)アクリロイル基などを有するエネルギー線硬化型化合物(I)と反応して結合できる官能基を有する材料が好ましい。また2種以上の材料を混合して用いることもできる。離型成分(III)の離型層形成用塗布液中の固形分中の含有量としては、0.05~10質量%が好ましく、0.1~5質量%がさらに好ましい。0.05質量%以上添加されていれば剥離力が軽くでき、10質量%以下であれば離型成分のセラミックグリーンシート等への移行が抑えられるため好ましい。 (Release component (III))
The releasing component (III) used in the present invention is not particularly limited as long as it is a material capable of exhibiting releasing property with the green sheet, such as polyorganosiloxane, fluorine compound, long chain alkyl compound, and waxes. Moreover, the material which has a functional group which can react and couple | bond with energy-beam-curable compound (I) which has a (meth) acryloyl group etc. to these materials is preferable. Also, two or more kinds of materials can be mixed and used. The content of the release component (III) in the solid content in the release layer-forming coating solution is preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass. If the content is 0.05% by mass or more, the peeling force can be lightened, and if the content is 10% by mass or less, the transfer of the releasing component to the ceramic green sheet or the like can be suppressed, which is preferable.
本発明の離型層にラジカル重合系化合物を用いる場合は、光重合開始剤を添加することが好ましい。光重合開始剤としては、具体的には、ベンゾフェノン、アセトフェノン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾイン安息香酸、ベンゾイン安息香酸メチル、ベンゾインジメチルケタール、2,4-ジエチルチオキサンソン、1-ヒドロキシシクロヘキシルフェニルケトン、ベンジルジフェニルサルファイド、テトラメチルチウラムモノサルファイド、アゾビスイソブチロニトリル、ベンジル、ジベンジル、ジアセチル、β-クロールアンスラキノン、(2,4,6-トリメチルベンジルジフェニル)フォスフィンオキサイド、2-ベンゾチアゾール-N,N-ジエチルジチオカルバメート等が挙げられる。特に、表面硬化性に優れるとされる、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、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オンが好ましく、中でも2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、2-メチル-1-[4-(メチル
チオ)フェニル]-2-モルフォリノプロパン-1-オンが特に好ましい。これらは単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 (Photopolymerization initiator)
When a radical polymerization compound is used in the release layer of the present invention, it is preferable to add a photopolymerization initiator. Specific examples of the photopolymerization initiator include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, 2,4 -Diethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, β-chloro anthraquinone, (2,4,6-trimethyl And benzyl diphenyl) phosphine oxide, 2-benzothiazole-N, N-diethyldithiocarbamate and the like. In particular, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methylpropan-1-one, which is considered to be excellent in surface curability. 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One is preferred, among which 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one are particularly preferred. preferable. These may be used alone or in combination of two or more.
また、本発明の離型フィルムの離型層表面の動摩擦係数は、1.00以下であることが好ましい。前記の範囲であれば、工程中でテンション異常が起こることなく、良好なグリーンシート表面が得られる。
前記の離型層表面の静摩擦係数と動摩擦係数の範囲に調節することは、前記の離型層の表面粗さ(Sa)や最大突起高さ(Rp)の範囲と関係があり、その調節方法に特に限定はないが、主に、エネルギー線硬化型化合物(I)と樹脂(II)の材質の組合せや含有割合を調節することにより好ましく達成できる。 The static friction coefficient of the release layer surface of the release layer film of the present invention is preferably 0.05 or more and 2.00 or less. More preferably, it is 0.1 or more and 1.00 or less, and still more preferably 0.1 or more and 0.50 or less. If the coefficient of static friction is within the above range, the surface of the coating layer and the surface of the mold release layer slip well and no excessive force is applied, so the damage to the surface of the mold release layer is reduced and damage to the green sheet is reduced. And a good green sheet surface is obtained.
Moreover, it is preferable that the dynamic friction coefficient of the mold release layer surface of the mold release film of this invention is 1.00 or less. Within the above range, a good green sheet surface can be obtained without tension abnormality occurring in the process.
Adjusting the range of the static friction coefficient and the dynamic friction coefficient of the release layer surface is related to the range of the surface roughness (Sa) and the maximum projection height (Rp) of the release layer, and the adjustment method There is no particular limitation, but it can be preferably achieved mainly by adjusting the combination and content ratio of the materials of the energy ray-curable compound (I) and the resin (II).
とで加工時の速度を向上させることができるため経済的に離型フィルムを作成することができ好ましい。 It is preferable that the drying temperature of solvent drying in the case of apply | coating the release layer of this invention on a base film by solution application is 50 degreeC or more and 120 degrees C or less, and is 60 degrees C or more and 100 degrees C or less More preferable. The drying time is preferably 30 seconds or less and more preferably 20 seconds or less. Furthermore, after solvent drying, it is preferable to irradiate an active energy ray to advance the curing reaction. As the active energy ray used at this time, ultraviolet rays, electron beams, X-rays, etc. can be used, but ultraviolet rays are preferred because they are easy to use. The amount of ultraviolet light to be irradiated is preferably 30 to 300 mJ / cm 2 , and more preferably 30 to 200 mJ / cm 2 in light amount. By setting it to 30 mJ / cm 2 or more, the curing of the composition proceeds sufficiently, and by setting it to 300 mJ / cm 2 or less, the processing speed can be improved, so that the mold release film can be economically produced. preferable.
ミリトロン(電子マイクロインジケーター)を用い、測定すべきフィルムの任意の4箇所より5cm角サンプル4枚を切り取り、一枚あたり各5点(計20点)測定して平均値を厚みとした。 (1) Substrate film thickness By using Millitron (electronic micro indicator), 4 pieces of 5 cm square samples are cut out from any 4 parts of the film to be measured, and each 5 pieces (20 pieces in total) are measured and averaged Thickness.
離型層の厚みは、光干渉式膜厚計(F20、フィルメトリクス社製)を用いて測定した。(離型層の屈折率は1.52として算出) (2) Release Layer Thickness The thickness of the release layer was measured using an optical interference type film thickness meter (F20, manufactured by Filmetrics, Inc.). (The refractive index of the release layer is calculated as 1.52.)
非接触表面形状計測システム(VertScan R550H-M100、菱化システム社製)を用いて、下記の条件で測定した値である。領域表面平均粗さ(Sa)は、5回測定の平均値を採用し、最大突起高さ(Rp)は7回測定し最大値と最小値を除いた5回の最大値を使用した。
(測定条件)
・測定モード:WAVEモード
・対物レンズ:50倍
・0.5×Tubeレンズ
(解析条件)
・面補正: 4次補正
・補間処理: 完全補間 (3) Region surface roughness (Sa), maximum projection height (Rp)
It is a value measured under the following conditions using a non-contact surface shape measurement system (VertScan R550H-M100, manufactured by Ryoka System Co., Ltd.). The area surface average roughness (Sa) was an average value of 5 measurements, and the maximum projection height (Rp) was 7 measurements, and the maximum value of 5 values excluding the maximum value and the minimum value was used.
(Measurement condition)
-Measurement mode: WAVE mode-Objective lens: 50x-0.5 x Tube lens (analysis conditions)
-Face correction: 4th order correction-Interpolation: Complete interpolation
下記、材料からなる組成物を攪拌混合し、直径0.5mmのジルコニアビーズを分散媒とするビーズミルを用いて60分間分散し、セラミックスラリーを調製した。
トルエン 76.3質量部
エタノール 76.3質量部
チタン酸バリウム(富士チタン社製 HPBT-1) 35.0質量部
ポリビニルブチラール 3.5質量部
(積水化学工業社製 エスレック(登録商標)BM-S)
DOP(フタル酸ジオクチル) 1.8質量部
次いで離型フィルムサンプルの離型面にアプリケーターを用いて乾燥後のセラミックグリーンシートが0.8μmになるように塗工し90℃で2分乾燥後、離型フィルムを剥離し、セラミックグリーンシートを得た。
得られたセラミックグリーンシートのフィルム幅方向の中央領域において25cm2の範囲でセラミックスラリーの塗布面の反対面から光を当て、光が透過して見えるピンホールの発生状況を観察し、下記基準で目視判定した。測定は5回測定し平均値を採用した。
○:ピンホールの発生がほぼなし(目安:ピンホールが測定面積当たり2個以下)
△:ピンホールの発生があり(目安:ピンホールが測定面積当たり3個以上、5個以下)×:ピンホールの発生が多数あり(目安:ピンホールが測定面積当たり6個以上) (4) Pinhole Evaluation of Ceramic Green Sheet The composition consisting of the following materials was stirred and mixed, and dispersed for 60 minutes using a bead mill using zirconia beads with a diameter of 0.5 mm as a dispersion medium to prepare a ceramic slurry.
Toluene 76.3 parts by mass Ethanol 76.3 parts by mass Barium titanate (HPBT-1 manufactured by Fuji Titanium Co., Ltd.) 35.0 parts by mass Polyvinyl butyral 3.5 parts by mass (S-Rec (registered trademark) BM-S manufactured by Sekisui Chemical Co., Ltd. )
Next, 1.8 parts by mass of DOP (dioctyl phthalate) is applied to the release surface of the release film sample using an applicator so that the ceramic green sheet after drying is 0.8 μm and dried at 90 ° C. for 2 minutes, The release film was peeled off to obtain a ceramic green sheet.
In the central region of the film width direction of the obtained ceramic green sheet, light is applied from the opposite surface of the ceramic slurry application surface in the range of 25 cm 2 , and the occurrence of pinholes where light is seen to be transmitted is observed. It judged visually. The measurement was performed 5 times and the average value was adopted.
○: Occurrence of pinholes is almost nonexistent (estimate: no more than 2 pinholes per measurement area)
Δ: occurrence of pinholes (indication: 3 or more, 5 or less pinholes per measurement area) ×: many occurrence of pinholes (indication: 6 or more pinholes per measurement area)
前記方法で作成したセラミックグリーンシート付き離型フィルムを30mm幅、80mm長さにカットし、剥離力測定用サンプルとした。除電機(キーエンス社製、SJ-F020)を用いて除電した後に、剥離試験機(協和界面科学社製、VPA-3)を用いて、剥離角度30度、剥離温度25℃、剥離速度10m/minで剥離した。剥離する向きとしては、剥離試験機付属のSUS板上に両面接着テープ(日東電工社製、No.535A)を貼りつけ、その上にセラミックグリーンシート側を両面テープと接着する形で離型フィルムを固定し、離型フィルム側を引っ張る形で剥離した。剥離後のセラミックグリーンシートの離型フィルムと接していた表面に関して、フィルム幅方向の中央領域において1250μm×900μmの範囲を走査型電子顕微鏡にて100倍観察し、10回測定した平均値を採用した。下記基準で目視判定した。
○:剥離時のダメージなし(目安:クラックおよび変形の発生がなし)
△:剥離時に軽度のダメージあり(目安:クラックおよび変形が測定面積当たり1個以上、3個以下)
×:剥離時に重度のダメージあり(目安:クラックおよび変形が4個以上)
なお、本評価方法における剥離角度とは、剥離試験機に固定した評価サンプル軸に対し、離型フィルムを引っ張る方向の角度を指す。剥離温度とは、装置付属のヒーター式ステージシステムを用いて固定した離型フィルムを加熱した時の温度である。ハンディータイプ温度計(安立計器社製、HD-1400E)を用いて、測定サンプルが該当温度になったことを確認後、剥離を行っている。 (5) Evaluation of damage to ceramic green sheet The release film with a ceramic green sheet prepared by the above method was cut into a width of 30 mm and a length of 80 mm, and used as a sample for measurement of peel force. After removing electricity using an electric discharge machine (manufactured by Keyence Corporation, SJ-F020), using a peeling tester (VPA-3 manufactured by Kyowa Interface Science Co., Ltd.), the peeling angle is 30 degrees, the peeling temperature is 25 ° C., and the peeling speed is 10 m / m. It peeled in min. As a peeling direction, a double-sided adhesive tape (Nitto Denko Co., Ltd., No. 535A) is stuck on a SUS plate attached to a peeling tester, and a release film is formed by bonding the ceramic green sheet side to the double-sided tape on it. Were fixed and peeled off in the form of pulling the release film side. With respect to the surface of the ceramic green sheet after peeling, which was in contact with the mold release film, a range of 1250 μm × 900 μm was observed 100 times with a scanning electron microscope in the central region in the film width direction, and an average value measured ten times was adopted. . It judged visually according to the following standard.
○: no damage at peeling (indication: no occurrence of cracks and deformation)
:: Mild damage occurred during peeling (Indication: 1 or more and 3 or less cracks and deformations per measurement area)
X: There is severe damage at the time of exfoliation (Indication: 4 or more cracks and deformations)
In addition, the peeling angle in this evaluation method points out the angle of the direction which pulls a release film with respect to the evaluation sample axis fixed to the peeling test machine. The peeling temperature is a temperature at which the release film fixed by using a heater type stage system attached to the apparatus is heated. Peeling is performed after confirming that the temperature of the measurement sample has reached the relevant temperature using a handy type thermometer (HD-1400E, manufactured by Anritsu Keiki Co., Ltd.).
テンシロン万能試験機((エー・アンド・デイ(株)製、RTG-1210)を用いて、フィルムの離型層表面と、SUS板を接するように重ねたときの、接触面の静摩擦係数(μs)と動摩擦係数(μd)をJIS K-7125に順じて下記条件で測定した。
試験片:幅50mm×長さ60mm
荷重:4.4kg
試験速度:200mm/min
被摩擦材: SUS板 (6) Coefficient of static friction, coefficient of dynamic friction When using a Tensilon universal tester (RTG-1210, manufactured by A & D Co., Ltd.), the mold release layer surface of the film is overlapped with the SUS plate in contact with it The static friction coefficient (μs) and the dynamic friction coefficient (μd) of the contact surface were measured in accordance with JIS K-7125 under the following conditions.
Specimen: Width 50 mm × Length 60 mm
Load: 4.4 kg
Test speed: 200 mm / min
Friction material: SUS plate
エステル化反応装置として、攪拌装置、分縮器、原料仕込口及び生成物取出口を有する3段の完全混合槽よりなる連続エステル化反応装置を用いた。TPA(テレフタル酸)を2トン/時とし、EG(エチレングリコール)をTPA1モルに対して2モルとし、三酸化アンチモンを生成PETに対してSb原子が160ppmとなる量とし、これらのスラリーをエステル化反応装置の第1エステル化反応缶に連続供給し、常圧にて平均滞留時間4時間、255℃で反応させた。次いで、第1エステル化反応缶内の反応生成物を連続的に系外に取り出して第2エステル化反応缶に供給し、第2エステル化反応缶内に第1エステル化反応缶から留去されるEGを生成PETに対して8質量%供給し、さらに、生成PETに対してMg原子が65ppmとなる量の酢酸マグネシウム四水塩を含むEG溶液と、生成PETに対してP原子が40ppmのとなる量のTMPA(リン酸トリメチル)を含むEG溶液を添加し、常圧にて平均滞留時間1時間、260℃で反応させた。次いで、第2エステル化反応缶の反応生成物を連続的に系外に取り出して第3エステル化反応缶に供給し、高圧分散機(日本精機社製)を用いて39MPa(400kg/cm2)の圧力で平均処理回数5パスの分散処理をした平均粒子径が0.9μmの多孔質コロイダルシリカ0.2質量%と、ポリアクリル酸のアンモニウム塩を炭酸カルシウムあたり1質量%付着させた平均粒子径が0.6μmの合成炭酸カルシウム0.4質量%とを、それぞれ10%のEGスラリーとして添加しながら、常圧にて平均滞留時間0.5時間、260℃で反応させた。第3エステル化反応缶内で生成したエステル化反応生成物を3段の連続重縮合反応装置に連続的に供給して重縮合を行い、95%カット径が20μmのステンレススチール繊維を焼結したフィルターで濾過を行ってから、限外濾過を行って水中に押出し、冷却後にチップ状にカットして、固有粘度0.60dl/gのPETチップを得た(以後、PET(1)と略す)。PETチップ中の滑剤含有量は0.6質量%であった。 (Preparation of polyethylene terephthalate pellets (PET (1)))
As an esterification reaction apparatus, a continuous esterification reaction apparatus was used which was composed of a three-stage complete mixing tank having a stirrer, a partial condenser, a raw material feed port and a product outlet. TPA (terephthalic acid) is 2 tons / hour, EG (ethylene glycol) is 2 moles with respect to 1 mole of TPA, antimony trioxide is produced in an amount such that 160 ppm of Sb atoms are formed with respect to PET, and these slurries are ester The reaction mixture was continuously fed to the first esterification reactor of the esterification reactor, and reacted at 255 ° C. for 4 hours at an average residence time under normal pressure. Then, the reaction product in the first esterification reaction vessel is continuously taken out of the system, supplied to the second esterification reaction vessel, and distilled from the first esterification reaction vessel in the second esterification reaction vessel. The EG solution contains 8% by weight of EG to the produced PET, and further contains an EG solution containing magnesium acetate tetrahydrate in an amount of 65 ppm of Mg atoms to the produced PET, and 40 ppm of P atoms to the produced PET The EG solution containing the following amount of TMPA (trimethyl phosphate) was added, and the reaction was carried out at 260.degree. C. under an atmospheric pressure for an average residence time of 1 hour. Then, the reaction product of the second esterification reaction vessel is continuously taken out of the system, supplied to the third esterification reaction vessel, and 39 MPa (400 kg / cm 2 ) using a high pressure disperser (manufactured by Nippon Seiki Co., Ltd.) 0.2% by mass of porous colloidal silica with an average particle size of 0.9 μm dispersed with an average pressure of 5 passes and an average particle of 1% by mass per ammonium carbonate of an ammonium salt of polyacrylic acid While adding 0.4 mass% of synthetic calcium carbonate having a diameter of 0.6 μm as an EG slurry of 10% each, the reaction was carried out at 260 ° C. at an average residence time of 0.5 hours under normal pressure. The esterification reaction product generated in the third esterification reaction vessel was continuously supplied to a three-stage continuous polycondensation reaction apparatus to conduct polycondensation, and a 95% cut diameter sintered a 20 μm stainless steel fiber After filtration with a filter, it was ultrafiltered and extruded in water, and after cooling it was cut into chips to obtain PET chips with an intrinsic viscosity of 0.60 dl / g (hereinafter abbreviated as PET (1)) . The lubricant content in the PET chip was 0.6% by mass.
一方、上記PETチップの製造において、炭酸カルシウム、シリカ等の粒子を全く含有しない固有粘度0.62dl/gのPETチップを得た(以後、PET(2)と略す。) (Preparation of polyethylene terephthalate pellets (PET (2)))
On the other hand, in the manufacture of the above PET chip, a PET chip having an intrinsic viscosity of 0.62 dl / g containing no particles such as calcium carbonate and silica was obtained (hereinafter referred to as PET (2)).
PET(I)の粒子の種類、含有量をポリアクリル酸のアンモニウム塩を炭酸カルシウムあたり1質量%付着させた平均粒子径が0.9μmの合成炭酸カルシウム0.75質量%に変更した以外は、PET(1)と同様にしてPETチップを得た(以後、PET(3)と略す)。PETチップ中の滑剤含有量は0.75質量%であった。 (Preparation of polyethylene terephthalate pellets (PET (3)))
The type and content of particles of PET (I) were changed to 0.75% by mass of synthetic calcium carbonate having an average particle diameter of 0.9 μm, in which 1% by mass of ammonium salt of polyacrylic acid was attached per calcium carbonate, A PET chip was obtained in the same manner as PET (1) (hereinafter referred to as PET (3)). The lubricant content in the PET chip was 0.75% by mass.
これらのPETチップを乾燥後、285℃で溶融し、別個の溶融押出し機押出機により290℃で溶融し、95%カット径が15μmのステンレススチール繊維を焼結したフィルターと、95%カット径が15μmのステンレススチール粒子を焼結したフィルターの2段の濾過を行って、フィードブロック内で合流して、PET(1)を表面層B(反離型面側層)、PET(2)を表面層A(離型面側層)となるように積層し、シート状に45m/分のスピードで押出(キャスティング)し、静電密着法により30℃のキャスティングドラム上に静電密着・冷却させ、固有粘度が0.59dl/gの未延伸ポリエチレンテレフタレートシートを得た。層比率は各押出機の吐出量計算でPET(1)/(2)=60%/40%となるように調整した。次いで、この未延伸シートを赤外線ヒーターで加熱した後、ロール温度80℃でロール間のスピード差により縦方向に3.5倍延伸した。その後、テンターに導き、140℃で横方向に4.2倍の延伸を行なった。次いで、熱固定ゾーンにおいて、210℃で熱処理した。その後、横方向に170℃で2.3%の緩和処理をして、厚さ31μmの二軸延伸ポリエチレンテレフタレートフィルムX1を得た。得られたフィルムX1の表面層AのSaは2nm、表面層BのSaは29nmであった。 (Manufacture of laminated film X1)
After drying, these PET chips are melted at 285 ° C., melted at 290 ° C. by a separate melt extruder extruder, and a 95% cut diameter sintered filter of 15 μm stainless steel fibers, 95% cut diameter Two-stage filtration of a filter made of sintered 15 μm stainless steel particles is carried out and merged in a feed block to make PET (1) a surface layer B (a reverse surface side layer), PET (2) a surface Layer A (release surface side layer) is laminated, extruded in a sheet shape at a speed of 45 m / min (casting), and electrostatically adhered and cooled on a casting drum at 30 ° C. by an electrostatic adhesion method. An unstretched polyethylene terephthalate sheet having an intrinsic viscosity of 0.59 dl / g was obtained. The layer ratio was adjusted so that PET (1) / (2) = 60% / 40% in discharge amount calculation of each extruder. Next, this unstretched sheet was heated by an infrared heater and then stretched 3.5 times in the longitudinal direction at a roll temperature of 80 ° C. due to the speed difference between the rolls. Thereafter, it was introduced into a tenter and stretched 4.2 times in the transverse direction at 140 ° C. It was then heat treated at 210 ° C. in the heat setting zone. Thereafter, the film was subjected to a relaxation treatment at 2.3 ° C. in the horizontal direction at 170 ° C. to obtain a 31 μm-thick biaxially stretched polyethylene terephthalate film X1. The Sa of the surface layer A of the obtained film X1 was 2 nm, and the Sa of the surface layer B was 29 nm.
積層フィルムX1と同様の層構成、延伸条件は変更せずに、キャスティング時の速度を変更することで厚みを調整し、25μmの厚みの二軸延伸ポリエチレンテレフタレートフィルムX2を得た。得られたフィルムX2の表面層AのSaは3nm、表面層BのSaは29nmであった。 (Production of laminated film X2)
The thickness was adjusted by changing the speed at the time of casting without changing the layer configuration and the stretching conditions similar to the laminated film X1 to obtain a biaxially stretched polyethylene terephthalate film X2 having a thickness of 25 μm. In the surface layer A of the obtained film X2, Sa was 3 nm, and Sa of the surface layer B was 29 nm.
積層フィルムX3としては、厚み25μmのA4100(コスモシャイン(登録商標)、東洋紡社製)を使用した。A4100は、フィルム中に粒子を実質的に含有せず、表面層B側にインラインコートで粒子を含んだコート層を設けた構成をしている。積層フィルムX3の表面層AのSaは1nm、表面層BのSaは2nmであった。 (Laminated film X3)
As the laminated film X3, A4100 (Cosmo Shine (registered trademark), manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm was used. A4100 has the structure which provided the coating layer which contained particle | grains by in-line coating in the surface layer B side substantially without containing particle | grains in a film. Sa of the surface layer A of the laminated film X3 was 1 nm, and Sa of the surface layer B was 2 nm.
積層フィルムX1の表面層A上に以下組成の塗布液1をリバースグラビアを用いて乾燥後の離型層膜厚が2.5μmになるように塗工し、90℃で30秒乾燥後、高圧水銀ランプを用いて200mJ/cm2となるように紫外線を照射することで超薄層セラミックグリーンシート製造用離型フィルムを得た。得られた離型フィルムについて、離型層厚み、領域表面粗さSa、最大突起高さRp、セラミックグリーンシートのピンホール評価、セラミックグリーンシートへのダメージ評価、静摩擦係数、動摩擦係数の評価を行った。
(塗布液1)
化合物(I) 100.00質量部
(ジペンタエリスリトールヘキサアクリレート、新中村化学工業社製 A-DPH、固形分濃度100%)
樹脂(II) ポリエステル樹脂 9.47質量部
(東洋紡社製バイロン(登録商標)RV280、固形分濃度100質量%)
離型剤(III) 1.26質量部
(アクリロイル基を有する変性ポリジメチルシロキサン、BYK-UV3505、ビックケミージャパン社製、固形分濃度40質量%)
光重合開始剤 5.25質量部
(OMNIRAD(登録商標)907、IGM Japan GK社製、固形分濃度100質量%)
希釈溶剤(MEK/トルエン=1/1) 459.79質量部 Example 1
Apply coating solution 1 of the following composition onto the surface layer A of the laminated film X1 using reverse gravure so that the thickness of the release layer after drying is 2.5 μm, and after drying for 30 seconds at 90 ° C., high pressure A release film for producing an ultrathin ceramic green sheet was obtained by irradiating ultraviolet rays so as to be 200 mJ / cm 2 using a mercury lamp. The release film thickness, area surface roughness Sa, maximum protrusion height Rp, pinhole evaluation of ceramic green sheet, damage evaluation to ceramic green sheet, static friction coefficient, dynamic friction coefficient are evaluated for the obtained release film. The
(Coating solution 1)
Compound (I) 100.00 parts by mass
(Dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd. A-DPH, solid concentration 100%)
Resin (II) Polyester resin 9.47 parts by mass (Toyobo Co., Ltd. Byron (registered trademark) RV 280, solid content concentration 100% by mass)
Release agent (III) 1.26 parts by mass (modified polydimethylsiloxane having an acryloyl group, BYK-UV 3505, manufactured by Byk Chem Japan, solid content 40% by mass)
Photopolymerization initiator 5.25 parts by mass (OMNIRAD (registered trademark) 907, manufactured by IGM Japan GK, solid content concentration 100% by mass)
Diluted solvent (MEK / toluene = 1/1) 459.79 parts by mass
樹脂(II)をポリエステルウレタン樹脂(東洋紡社製バイロン(登録商標)UR1400、固形分濃度30質量%)に変更し、下記塗布液2を使用した。塗布液2の固形分濃度は実施例1の塗布液1に比べ減少させた。乾燥後の離型層膜厚が1.5μmになるように塗工した。塗布液2を用いた点と、乾燥後の離型層膜厚が1.5μmになるように塗工した点を除いては、実施例1と同様にして、離型フィルムを得た。得られた離型フィルムについて、離型層厚み、領域表面粗さSa、最大突起高さRp、セラミックグリーンシートのピンホール評価、セラミックグリーンシートへのダメージ評価、静摩擦係数、動摩擦係数の評価を行った。
(塗布液2)
化合物(I) 100.00質量部
(ジペンタエリスリトールヘキサアクリレート、新中村化学工業社製 A-DPH、固形分濃度100%)
樹脂(II) ポリエステルウレタン樹脂 31.50質量部
(東洋紡社製バイロン(登録商標)UR1400、固形分濃度30質量%)
離型剤(III) 0.42質量部
(アクリロイル基を有する変性ポリジメチルシロキサン、BYK-UV3505、ビックケミージャパン社製、固形分濃度40質量%)
光重合開始剤 5.25質量部
(OMNIRAD(登録商標)907、IGM Japan GK社製、固形分濃度100質量%)
希釈溶剤(MEK/トルエン=1/1) 975.42質量部 (Example 2)
Resin (II) was changed to polyester urethane resin (Toyobo Co., Ltd. Byron (registered trademark) UR1400, solid content concentration 30 mass%), and the following coating solution 2 was used. The solid content concentration of the coating solution 2 was reduced as compared to the coating solution 1 of Example 1. It applied so that the release layer film thickness after drying might be 1.5 micrometers. A release film was obtained in the same manner as in Example 1 except that the coating solution 2 was used and the coating was performed so that the thickness of the release layer after drying was 1.5 μm. The release film thickness, area surface roughness Sa, maximum protrusion height Rp, pinhole evaluation of ceramic green sheet, damage evaluation to ceramic green sheet, static friction coefficient, dynamic friction coefficient are evaluated for the obtained release film. The
(Coating solution 2)
Compound (I) 100.00 parts by mass (Dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd. A-DPH, solid content concentration 100%)
Resin (II) polyester urethane resin 31.50 parts by mass (Toyobo Co., Ltd. Byron (registered trademark) UR1400, solid content concentration 30 mass%)
Release agent (III) 0.42 parts by mass (Modified polydimethylsiloxane having an acryloyl group, BYK-UV 3505, manufactured by Bick Chemie Japan, solid content concentration 40% by mass)
Photopolymerization initiator 5.25 parts by mass (OMNIRAD (registered trademark) 907, manufactured by IGM Japan GK, solid content concentration 100% by mass)
Diluted solvent (MEK / toluene = 1/1) 975.42 parts by mass
離型剤(III)の比率を実施例2に比べ増加させた、下記塗布液3を使用した。乾燥後の離型層膜厚が1.8μmになるように塗工した。塗布液3を用いた点と、乾燥後の離型層膜厚が1.8μmになるように塗工した点を除いては、実施例1と同様にして、離型フィルムを得た。得られた離型フィルムについて、離型層厚み、領域表面粗さSa、最大突起高さRp、セラミックグリーンシートのピンホール評価、セラミックグリーンシートへのダメージ評価、静摩擦係数、動摩擦係数の評価を行った。
(塗布液3)
化合物(I) 100.00質量部
(ジペンタエリスリトールヘキサアクリレート、新中村化学工業社製 A-DPH、固形分濃度100%)
樹脂(II) ポリエステルウレタン樹脂 31.50質量部 (東洋紡社製バイロン(登録商標)UR1400、固形分濃度30質量%)
離型剤(III) 1.26質量部
(アクリロイル基を有する変性ポリジメチルシロキサン、BYK-UV3505、ビックケミージャパン社製、固形分濃度40質量%)
光重合開始剤 5.25質量部
(OMNIRAD(登録商標)907、IGM Japan GK社製、固形分100質量%)
希釈溶剤(MEK/トルエン=1/1) 982.98質量部 (Example 3)
The following coating solution 3 was used, in which the proportion of the releasing agent (III) was increased as compared with that in Example 2. It applied so that the release layer film thickness after drying might be set to 1.8 micrometers. A release film was obtained in the same manner as in Example 1 except that the coating solution 3 was used and the coating was performed so that the thickness of the release layer after drying was 1.8 μm. The release film thickness, area surface roughness Sa, maximum protrusion height Rp, pinhole evaluation of ceramic green sheet, damage evaluation to ceramic green sheet, static friction coefficient, dynamic friction coefficient are evaluated for the obtained release film. The
(Coating solution 3)
Compound (I) 100.00 parts by mass (Dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd. A-DPH, solid content concentration 100%)
Resin (II) polyester urethane resin 31.50 parts by mass (Toyobo Co., Ltd. Byron (registered trademark) UR1400, solid content concentration 30 mass%)
Release agent (III) 1.26 parts by mass (modified polydimethylsiloxane having an acryloyl group, BYK-UV 3505, manufactured by Byk Chem Japan, solid content 40% by mass)
Photopolymerization initiator 5.25 parts by mass (OMNIRAD (registered trademark) 907, manufactured by IGM Japan GK, solid content 100% by mass)
Diluted solvent (MEK / toluene = 1/1) 982.98 parts by mass
実施例3にて使用した塗布液3を、積層フィルムX2の表面層A上に塗工した。積層フィルムX2を用いた点を除いては、実施例3と同様にして、離型フィルムを得た。得られた離型フィルムについて、離型層厚み、領域表面粗さSa、最大突起高さRp、セラミックグリーンシートのピンホール評価、セラミックグリーンシートへのダメージ評価、静摩擦係数、動摩擦係数の評価を行った。 (Example 4)
The coating solution 3 used in Example 3 was applied onto the surface layer A of the laminated film X2. A release film was obtained in the same manner as in Example 3, except that the laminated film X2 was used. The release film thickness, area surface roughness Sa, maximum protrusion height Rp, pinhole evaluation of ceramic green sheet, damage evaluation to ceramic green sheet, static friction coefficient, dynamic friction coefficient are evaluated for the obtained release film. The
実施例3にて使用した塗布液3を、積層フィルムX3の表面層A上に塗工した。積層フィルムX3を用いた点を除いては、実施例3と同様にして、離型フィルムを得た。得られた離型フィルムについて、離型層厚み、領域表面粗さSa、最大突起高さRp、セラミックグリーンシートのピンホール評価、セラミックグリーンシートへのダメージ評価、静摩擦係数、動摩擦係数の評価を行った。 (Example 5)
The coating liquid 3 used in Example 3 was coated on the surface layer A of the laminated film X3. A release film was obtained in the same manner as in Example 3, except that the laminated film X3 was used. The release film thickness, area surface roughness Sa, maximum protrusion height Rp, pinhole evaluation of ceramic green sheet, damage evaluation to ceramic green sheet, static friction coefficient, dynamic friction coefficient are evaluated for the obtained release film. The
実施例1に比べて、樹脂(II)を含まず、離型剤(III)をアクリロイル基を有する含有ポリエーテル変性ポリジメチルシロキサン(BYK UV-3500、ビッグケミー・ジャパン社製 固形分濃度100%)に変更し添加量を増加させ、希釈溶剤を変更した下記塗布液4を使用した。塗布液4を用いた点と、乾燥後の離型層膜厚が1.0μmになるように塗工した点を除いては、実施例1と同様にして、離型フィルムを得た。得られた離型フィルムについて、離型層厚み、領域表面粗さSa、最大突起高さRp、セラミックグリーンシートのピンホール評価、セラミックグリーンシートへのダメージ評価、静摩擦係数、動摩擦係数の評価を行った。
(塗布液4)
化合物(I) 100.00質量部
(ジペンタエリスリトールヘキサアクリレート、新中村化学工業社製 A-DPH、固形分濃度100%)
離型剤(III) 1.00質量部
(アクリロイル基含有ポリエーテル変性ポリジメチルシロキサン BYK UV-3500、ビッグケミー・ジャパン社製 固形分濃度100%))
光重合開始剤 5.00質量部
(OMNIRAD(登録商標)907、IGM Japan GK社製 固形分濃度100質量%)
希釈溶剤(IPA/MEK=3/1) 424.25質量部 (Comparative example 1)
Compared with Example 1, the resin (II) is not contained, and the release agent (III) is an acryloyl group-containing polyether-modified polydimethylsiloxane (BYK UV-3500, 100% solid concentration by Big Chemie Japan) The following coating solution 4 was used in which the amount of addition was increased and the dilution solvent was changed. A release film was obtained in the same manner as in Example 1 except that the coating solution 4 was used and the coating was performed so that the thickness of the release layer after drying was 1.0 μm. The release film thickness, area surface roughness Sa, maximum protrusion height Rp, pinhole evaluation of ceramic green sheet, damage evaluation to ceramic green sheet, static friction coefficient, dynamic friction coefficient are evaluated for the obtained release film. The
(Coating solution 4)
Compound (I) 100.00 parts by mass (Dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd. A-DPH, solid content concentration 100%)
Releasing agent (III) 1.00 parts by mass (Acryloyl group-containing polyether-modified polydimethylsiloxane BYK UV-3500, 100% solid concentration by Big Chemie Japan)
Photopolymerization initiator 5.00 parts by mass (OMNIRAD (registered trademark) 907, IGM Japan GK company solid content concentration 100 mass%)
Diluted solvent (IPA / MEK = 3/1) 424.25 parts by mass
Claims (7)
- ポリエステルフィルムの少なくとも片面に直接又は他の層を介して0.2~3.5μmの離型層が積層された離型フィルムであって、前記離型層表面の領域表面粗さ(Sa)が5~40nm、最大山高さ(Rp)が60nm以下であるセラミックグリーンシート製造用離型フィルム。 A release film in which a release layer of 0.2 to 3.5 μm is laminated on at least one surface of a polyester film directly or through another layer, and the area surface roughness (Sa) of the release layer surface is A release film for producing a ceramic green sheet, having a maximum peak height (Rp) of 60 nm or less and 5 to 40 nm.
- 離型層が、1分子内に3以上の反応性基を有するエネルギー線硬化型化合物(I)と、前記エネルギー線硬化型化合物(I)を海成分とし、前記エネルギー線硬化型化合物(I)と非相溶であり島成分となる樹脂(II)と、離型成分(III)を少なくとも含む塗膜が硬化されてなる請求項1に記載のセラミックグリーンシート製造用離型フィルム。 An energy ray-curable compound (I), wherein the releasing layer has three or more reactive groups in one molecule, and the energy ray-curable compound (I) as a sea component, the energy ray-curable compound (I) The release film for producing a ceramic green sheet according to claim 1, wherein the coating film containing at least the resin (II) which is incompatible with the resin and which becomes the island component and the release component (III) is cured.
- 離型層が実質的に無機粒子を含有しない請求項1又は2に記載のセラミックグリーンシート製造用離型フィルム。 The release film for producing a ceramic green sheet according to claim 1 or 2, wherein the release layer contains substantially no inorganic particles.
- ポリエステルフィルムが、少なくとも表面層Aと、前記表面層Aとは反対側の表面層Bを含む2層以上からなる積層ポリエステルフィルムであって、前記表面層A上に離型層が積層されており、表面層Aには実質的に無機粒子が含有されていない請求項1~3のいずれかに記載のセラミックグリーンシート製造用離型フィルム。 The polyester film is a laminated polyester film comprising at least a surface layer A and two or more layers including a surface layer B opposite to the surface layer A, and a release layer is laminated on the surface layer A. 4. The release film for producing a ceramic green sheet according to any one of claims 1 to 3, wherein the surface layer A is substantially free of inorganic particles.
- 表面層Bが粒子を含有し、前記粒子がシリカ粒子及び/又は炭酸カルシウム粒子であり、合計の粒子の含有量が表面層Bの総質量に対して5000~15000ppmである請求項4に記載のセラミックグリーンシート製造用離型フィルム。 The surface layer B contains particles, the particles are silica particles and / or calcium carbonate particles, and the total content of particles is 5,000 to 15,000 ppm with respect to the total mass of the surface layer B. Release film for ceramic green sheet production.
- ポリエステルフィルムが実質的に無機粒子を含有しておらず、ポリエステルフィルムの離型層が積層されていない側に粒子を含むコーティング層が積層されている請求項1~3のいずれかに記載のセラミックグリーンシート製造用離型フィルム。 The ceramic according to any one of claims 1 to 3, wherein the polyester film is substantially free of inorganic particles, and the coating layer containing the particles is laminated on the side of the polyester film on which the release layer is not laminated. Release film for green sheet production.
- 請求項1~6のいずれかに記載のセラミックグリーンシート製造用離型フィルムを用いてセラミックグリーンシートを成型するセラミックグリーンシートの製造方法であって、成型されたセラミックグリーンシートが0.2μm~1.0μmの厚みであることを特徴とするセラミックグリーンシートの製造方法。 A method for producing a ceramic green sheet, wherein the ceramic green sheet is molded using the mold release film for producing a ceramic green sheet according to any one of claims 1 to 6, wherein the molded ceramic green sheet has a thickness of 0.2 μm to 1 A method of producing a ceramic green sheet having a thickness of 0 μm.
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SG11202005633XA SG11202005633XA (en) | 2017-12-27 | 2018-12-20 | Release film for production of ceramic green sheet |
JP2019502113A JP6822549B2 (en) | 2017-12-27 | 2018-12-20 | Release film for manufacturing ceramic green sheets |
MYPI2020003262A MY192990A (en) | 2017-12-27 | 2018-12-20 | Mold release film for production of ceramic green sheet |
KR1020207021350A KR102518776B1 (en) | 2017-12-27 | 2018-12-20 | Release Film for Ceramic Green Sheet Manufacturing |
CN201880083606.2A CN111527136B (en) | 2017-12-27 | 2018-12-20 | Release film for producing ceramic green sheet |
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KR (1) | KR102518776B1 (en) |
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JP2020049803A (en) * | 2018-09-27 | 2020-04-02 | 東洋紡株式会社 | Release film for producing ceramic green sheet and method for evaluating the same |
JP2021024926A (en) * | 2019-08-02 | 2021-02-22 | 三菱ケミカル株式会社 | Hardened film, method for producing the same, and laminate |
JP2021054079A (en) * | 2019-09-30 | 2021-04-08 | 太陽インキ製造株式会社 | Laminate structure |
WO2023276892A1 (en) * | 2021-06-30 | 2023-01-05 | 東洋紡株式会社 | Release film for molding resin sheets |
WO2023032793A1 (en) * | 2021-08-31 | 2023-03-09 | 東洋紡株式会社 | Mold release film for resin sheet molding |
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SG11202102850UA (en) * | 2018-09-27 | 2021-04-29 | Toyo Boseki | Release film for production of ceramic green sheet |
WO2022085531A1 (en) * | 2020-10-22 | 2022-04-28 | 東洋紡株式会社 | Mold release film for resin sheet molding |
CN114393904B (en) * | 2022-01-20 | 2022-10-28 | 宁波勤邦新材料科技有限公司 | Base film of release film for multilayer ceramic capacitor |
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SG11202005633XA (en) | 2020-07-29 |
JPWO2019131449A1 (en) | 2020-01-16 |
MY192990A (en) | 2022-09-20 |
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JP6822549B2 (en) | 2021-01-27 |
KR20200098678A (en) | 2020-08-20 |
CN111527136A (en) | 2020-08-11 |
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KR102518776B1 (en) | 2023-04-10 |
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