Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • 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
• • 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
  • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • 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
  • C09D5/02—Emulsion paints including aerosols
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
• • 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
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

• the present invention relates to a silicone release polyester film. More specifically, for example, it has peelability and adhesion suitable for molding from light peeling to heavy peeling in ceramic green sheet molding used in the production of multilayer ceramic capacitors, and does not cause tearing or deformation of the sheets.
• the present invention relates to a silicone release polyester film that can prevent this, and a method for producing the same.
• a release film is used as a carrier film for molding resin sheets and ceramic sheets.
• polyester film is used as the base material of the release film in terms of dimensional stability and heat resistance.
• the carrier film is required to have various properties suitable for the thickness of the slurry.
• the rigidity of the ceramic green sheet decreases when the film is made thinner, and the sheet may break when peeled off, so easy peelability is required.
• a relatively thick green sheet has high rigidity, floating occurs between the sheet and the release film during process transportation, causing deformation of the sheet.
• peeling of the ceramic sheet may require various peeling forces from light peeling to heavy peeling.
• it is not limited to the thickness of the green sheet, but slight repellent defects during ceramic slurry coating can penetrate the sheet, causing pinholes and thickness fluctuations, which can significantly reduce the yield of multilayer ceramic capacitors.
• the coating uniformity of the release layer of the mold film is required.
• an aqueous coating composition containing a silicone containing a Q unit in a predetermined mol% range and a silicone having an Si-H group has been described (see, for example, Patent Document 2), but in particular, the Q unit The optimum molecular weight range of silicone containing 20% is not described.
• the present invention has been developed to provide a film with excellent peelability and adhesion suitable for sheet molding from light peeling to heavy peeling, and which can be suitably used as a carrier film in the production of multilayer ceramic capacitors.
• the purpose of the present invention is to provide a silicone release polyester film, a method for producing the same, and the like.
• the inventors of the present invention have developed a release film that, under certain conditions, has moderate peeling strength from light to heavy peeling even when emulsion-type silicone is used.
• the present inventors have discovered that it is possible to provide the following, and have completed the present invention.
• the present invention provides the following silicone release polyester film (silicone release polyester film).
• a silicone release polyester film having The number average molecular weight of the silicone A is 150,000 or more,
• the content of Si atoms contained in the Q unit is 0.05 mol% or more and 60 mol% or less, Silicone release polyester film.
• the content of the silicone (B) is 3 parts by mass or more and 45 parts by mass or less, when the total content of the silicone (A) and the silicone (B) is 100 parts by mass.
• the present invention also provides the following method for producing a silicone release polyester film.
• a coating layer is formed using a release coating composition containing an aqueous dispersion (2) of silicone (B) having a hydrogen atom directly bonded to an atom, a crosslinking reaction inhibitor, a platinum catalyst, and a nonionic emulsifier.
• a method of manufacturing a silicone release polyester film comprising: The number average molecular weight of the silicone A is 150,000 or more, The content of Si atoms contained in the Q unit is in the range of 0.05 mol% or more and 60 mol% or less, A method for producing a silicone release polyester film.
• the content of the silicone (B) is 3 parts by mass or more and 45 parts by mass or less, when the total content of the silicone (A) and the silicone (B) is 100 parts by mass, according to [6]. Manufacturing method described.
• the silicone mold release polyester film of the present invention has the above-mentioned structure, so that it can be used as a release film for sheet molding, and has a peeling force suitable for sheet molding of a thickness such as a ceramic green sheet, and an appropriate peeling property with little sheet deformation. As a result, it is possible to reduce the defective rate and produce a highly reliable sheet.
• the method for producing a silicone release polyester film of the present invention makes it possible to efficiently and easily obtain a silicone release polyester film having the above characteristics.
• the silicone release polyester film of the present invention is An aqueous dispersion (1) of one or more types of silicone (A) containing an alkenyl group and/or a Q unit represented by SiO 4/2 , Si represented by a Si-H group on at least one side of the polyester film.
• a silicone release polyester film having The number average molecular weight of the silicone A is 150,000 or more,
• the content of Si atoms contained in the Q unit is 0.05 mol% or more and 60 mol% or less.
• polyester film Known polyesters can be used as appropriate for the polyester film of the present invention, and for example, those shown below can be suitably used.
• polyester The polyester constituting the polyester film used as the base film (hereinafter sometimes referred to as "base material") in the present invention is not particularly limited, and polyesters commonly used as base materials for release films can be used.
• a film molded product can be used.
• a polyester film formed from polyethylene terephthalate is particularly suitable.
• the repeating units of ethylene terephthalate are preferably 90 mol% or more, more preferably 95 mol% or more, and a small amount of other dicarboxylic acid components and diol components may be copolymerized.
• the polyester film is preferably a biaxially oriented polyester film for reasons such as high elastic modulus in both directions.
• the intrinsic viscosity of the polyester film is preferably 0.50 dl/g or more and 0.70 dl/g or less, more preferably 0.52 dl/g or more and 0.65 dl/g or less.
• the intrinsic viscosity is 0.50 dl/g or more, it is preferable because many breaks do not occur during the stretching process.
• it is 0.70 dl/g or less it is preferable because the cutting properties are good when cutting into a predetermined product width and dimensional defects do not occur. Further, it is preferable that the raw material pellets be sufficiently vacuum dried.
• polyester film when it is simply described as a "polyester film", it means a polyester film having (laminated) a surface layer A and a surface layer B.
• the method for producing the polyester film in the present invention is not particularly limited, and conventionally commonly used methods can be used.
• it can be obtained by melting the polyester in an extruder, extruding it into a film, cooling it in a rotating cooling drum to obtain an unstretched film, and then biaxially stretching the unstretched film.
• a biaxially stretched film can be obtained by sequentially biaxially stretching a uniaxially stretched film in the longitudinal or transverse direction in the transverse or longitudinal direction, or by simultaneously biaxially stretching an unstretched film in the longitudinal and transverse directions. can.
• the stretching temperature during stretching of the polyester film is preferably at least the secondary transition point (Tg) of the polyester. It is preferable to stretch the film by a factor of 1 to 8 times, particularly 2 times to 6 times, in both the longitudinal and transverse directions.
• the thickness of the polyester film is preferably 12 ⁇ m or more and 100 ⁇ m or less, more preferably 16 ⁇ m or more and 50 ⁇ m or less, and even more preferably 19 ⁇ m or more and 33 ⁇ m or less. If the thickness of the film is 12 ⁇ m or more, there is no risk of deformation due to heat during film production, processing, and molding, which is preferable. On the other hand, if the thickness of the film is 100 ⁇ m or less, the amount of film to be discarded after use will not be excessively large, which is preferable in terms of reducing environmental burden.
• the polyester film base material may be a single layer or a multilayer of two or more layers.
• the base film may be a polyester film having a surface layer A that does not substantially contain particles having a particle size of 1.0 ⁇ m or more and a surface layer B that contains particles.
• surface layer A does not substantially contain inorganic particles having a particle size of 1.0 ⁇ m or more.
• particles having a particle size of less than 1.0 ⁇ m and 1 nm or more may be present in the surface layer A. Since the surface layer A does not substantially contain particles having a particle size of 1.0 ⁇ m or more, for example, inorganic particles, it is possible to reduce problems caused by transfer of the shape of particles in the base material to the resin sheet.
• the surface layer A does not contain particles with a particle size of less than 1.0 ⁇ m, so that problems caused by transfer of the particle shape in the base material to the resin sheet can be more effectively suppressed.
• the polyester film base material is preferably a laminated film having a surface layer A substantially free of inorganic particles on at least one side. Thereby, it is possible to more effectively suppress the transfer of the particle shape in the base material to the resin sheet and the occurrence of defects.
• the surface layer A that does not substantially contain particles with a particle size of less than 1.0 ⁇ m also substantially does not contain particles with a particle size of 1.0 ⁇ m or more.
• substantially no particles means, for example, in the case of inorganic particles of less than 1.0 ⁇ m, the amount of inorganic elements determined by fluorescent X-ray analysis is 50 ppm or less, preferably 10 ppm. Hereinafter, it most preferably means a content that is below the detection limit. Even if particles are not actively added to the film, contaminants derived from foreign substances or dirt attached to the raw resin or the line or equipment in the film manufacturing process are peeled off and mixed into the film. This is because there is. Moreover, "substantially not containing particles with a particle size of 1.0 ⁇ m or more” means that particles with a particle size of 1.0 ⁇ m or more are not included.
• the layer on the side to which the release layer is applied is layer A
• the layer on the opposite side is layer B
• the other core layer is layer C
• the layer structure in the thickness direction is release layer/A/ B, or a laminated structure such as release layer/A/C/B.
• the C layer may have a plurality of layers.
• the surface layer B may not contain inorganic particles. In that case, it is preferable to provide a coating layer containing at least inorganic particles and a binder on the surface layer B in order to provide slipperiness for winding up the film into a roll.
• the surface layer B forming the opposite surface to the surface to which the release layer is applied preferably contains inorganic particles from the viewpoint of the slipperiness of the film and the ease with which air can escape.
• inorganic particles from the viewpoint of the slipperiness of the film and the ease with which air can escape.
• silica particles and/or calcium carbonate particles it is preferable to use silica particles and/or calcium carbonate particles.
• the total amount of inorganic particles contained in the surface layer B is preferably 5,000 ppm or more and 15,000 ppm or less.
• the area surface average roughness (Sa) of the film of the surface layer B is preferably in the range of 1 nm or more and 40 nm or less. More preferably, the range is 5 nm or more and 35 nm or less.
• the total amount of silica particles and/or calcium carbonate particles is 5000 ppm or more and Sa is 1 nm or more, air can be released uniformly when the film is rolled up, resulting in a good rolled shape and good flatness. , it is suitable for producing ultra-thin ceramic green sheets.
• the lubricant is less likely to aggregate and coarse protrusions are not formed, resulting in stable quality when producing ultra-thin ceramic green sheets. It is preferable.
• inert inorganic particles and/or heat-resistant organic particles can also be used as particles contained in layer B, but from the viewpoint of transparency and cost, silica particles and/or More preferably, calcium carbonate particles are used.
• other inorganic particles that can be used include alumina-silica composite oxide particles and hydroxyapatite particles.
• heat-resistant organic particles include crosslinked polyacrylic particles, crosslinked polystyrene particles, and benzoguanamine particles.
• porous colloidal silica is preferable, and when using calcium carbonate particles, light calcium carbonate whose surface is treated with a polyacrylic acid-based polymer compound is preferable from the viewpoint of preventing the lubricant from falling off. .
• the average particle diameter of the inorganic particles added to the surface layer B is preferably 0.1 ⁇ m or more and 2.0 ⁇ m or less, particularly preferably 0.3 ⁇ m or more and 1.0 ⁇ m or less. It is preferable that the average particle diameter of the inorganic particles is 0.1 ⁇ m or more because the release film has good slip properties. Further, if the average particle diameter is 2.0 ⁇ m or less, there is no risk of adversely affecting the smoothness of the surface of the mold release layer, so there is no risk of pinholes occurring in the ceramic green sheet, which is preferable.
• a film may be applied to the surface of surface layer A and/or surface layer B before or after uniaxial stretching during the film forming process.
• a coating layer may be provided on the substrate, and a corona treatment or the like may be applied.
• the silicone release polyester film of the present invention can have a peeling force of 20 g/25 mm width or more and 400 g/25 mm width or less after being attached to a polyester adhesive tape.
• the lower limit of the above peeling force is, for example, 30g/25mm width or more, 40g/25mm width or more, 50g/25mm width or more, 70g/25mm width or more, 100g/25mm width or more, 120g/25mm width or more, 150g/25mm width or more , 180g/25mm width or more.
• the upper limit of the above peeling force is, for example, 380g/25mm width or less, 350g/25mm width or less, 330g/25mm width or less, 300g/25mm width or less, 280g/25mm width or less, 250g/25mm width or less, 230g/25mm
• the width may be less than or equal to 200 g/25 mm width, etc.
• the peel strength is preferably 20 g/25 mm or more and 400 g/25 mm or less. Since the silicone release polyester film of the present invention has the above structure, for example, by introducing a silicone resin (Q unit resin) into the silicone base material (silicone A), it can be used for sheet formation even when the amount of crosslinking agent is small. As a release film, it is possible to control the release force from light release to heavy release by adjusting the amount of crosslinking agent added while providing adhesion, such as release with appropriate hardness, and its industrial value is extremely high. .
• the above-mentioned adhesive tape peel strength is determined by laminating a polyester adhesive tape (manufactured by Nitto Denko Corporation, No. 31B) on the surface of the coating layer (mold release layer) of a release film, and pressing it with a 5 kg pressure roller for 30 minutes. After being left to stand as described above, the peel strength between the release layer and the adhesive tape (peel angle: 180 degrees, peel speed: 300 mm/min, unit: g/25 mm width) is measured using a peel strength tester.
• the mold release coating composition of the present invention comprises an aqueous dispersion (1) of one or more silicones (A) containing an alkenyl group and/or a Q unit represented by SiO 4/2 , an Si-H group It contains an aqueous dispersion (2) of silicone (B) having a hydrogen atom directly bonded to the represented Si atom, a crosslinking reaction inhibitor, a platinum catalyst, and a nonionic emulsifier.
• silicone (A) containing an alkenyl group and/or a Q unit represented by SiO 4/2 has the following general formula (I).
• An example is organopolysiloxane (hereinafter sometimes referred to as "silicone (A)").
• R 1 a R 2 b SiO (4-ab)/2 ...(I) (In formula (I), R 1 is an alkenyl group having 2 to 8 carbon atoms, R 2 is a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms selected from an alkyl group or an aryl group, and a represents an integer from 0 to 3, b represents an integer from 0 to 3, and satisfies a+b ⁇ 3.)
• Examples of the alkenyl group having 2 to 8 carbon atoms represented by R 1 include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and among these, a vinyl group is particularly preferred.
• Examples of the alkyl group represented by R 2 include a methyl group, ethyl group, propyl group, butyl group, and examples of the aryl group include a phenyl group and tolyl group. Among these, for example, it is preferable that 50 mol % or more of the substituents of R 2 be methyl groups from the viewpoint of easy releasability.
• the silicone (A) containing an alkenyl group and/or a Q unit needs to contain a Q unit.
• a plurality of silicones (A) containing an alkenyl group and/or a Q unit it is sufficient that any one of them contains a Q unit.
• the coating hardness of the silicone-based release layer increases and viscosity loss when peeling the sheet can be suppressed, leading to easy release.
• the silicone containing Q units is included in the alkenyl group-containing silicone, wettability is also improved, so pinhole defects can be suppressed during sheet coating.
• the content of Si atoms contained in the Q unit is 0.05 mol% or more and 60 mol%, preferably 0.05 mol% or more, based on the total Si atoms in the silicone (A) containing the alkenyl group and/or the Q unit.
• the content is 1 mol% or more and 55 mol% or less, more preferably 1.0 mol% or more and 50 mol% or less.
• the number average molecular weight of the silicone (A) containing an alkenyl group and/or a Q unit is preferably 150,000 or more, for example, 180,000 or more, 200,000 or more, 220,000 or more, etc. Further, the number average molecular weight of the silicone (A) containing an alkenyl group and/or a Q unit can be, for example, 1,000,000 or less, 900,000 or less, 800,000 or less, 700,000 or less, 600,000 or less, 500,000 or less, 400,000 or less, etc. And you can get.
• crosslinking agent is less than 150,000, crosslinking of the release coating will be insufficient, and viscosity loss during peeling of the sheet cannot be suppressed, resulting in excessively heavy peeling and causing damage to the adherend.
• the amount of silicone transferred also increases.
• the silicone (A) containing an alkenyl group and/or a Q unit in the present invention can be produced by a known method. Further, the silicone (A) containing an alkenyl group and/or a Q unit in the present invention is preferably contained in the composition in the form of an aqueous dispersion (aqueous dispersion (1)).
• the silicone (A) containing the alkenyl group and/or Q unit is made into an aqueous dispersion (water dispersion (1))
• the silicone containing the alkenyl group and/or Q unit in the aqueous dispersion (1) is The mass% of the silicone (A) can be, for example, 1% by mass or more and 50% by mass or less, 3% by mass or more and 40% by mass or less, 5% by mass or more and 30% by mass, 10% by mass or more and 20% by mass, etc. There may be.
• silicone (B) having a hydrogen atom directly bonded to a Si atom represented by a Si-H group silicone (B) having a hydrogen atom directly bonded to an Si atom represented by a Si-H group (hereinafter referred to as "silicone (B)" or "Si-H group-containing silicone (B)”)
• Si-H group-containing silicone (B) An example of the organohydrogenpolysiloxane having a structure represented by the following general formula (II) is exemplified.
• R 3 c H d SiO (4-c-d)/2 ...(II)
• R 3 is a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms selected from an alkyl group or an aryl group, c is 0 to 2, d is 1 to 3, and Each represents an integer that satisfies c+d ⁇ 3.
• Examples of the alkyl group represented by R 3 include a methyl group, ethyl group, propyl group, butyl group, and examples of the aryl group include a phenyl group and tolyl group. Among these, it is preferable that 50 mol % or more of the substituents of R 3 be methyl groups from the viewpoint of easy releasability.
• the Si--H group-containing silicone (B) preferably has at least 3, preferably 5 or more hydrogen atoms bonded to Si atoms in one silicone molecule.
• the Si--H group-containing silicone (B) can be produced by a known method. Further, the Si--H group-containing silicone (B) in the present invention is preferably contained in the composition in the form of an aqueous dispersion (aqueous dispersion (2)).
• the mass % of the Si-H group-containing silicone (B) in the aqueous dispersion (2) is as follows:
• the content may be 1% by mass or more and 50% by mass or less, 3% by mass or more and 40% by mass or less, 5% by mass or more and 30% by mass, 10% by mass or more and 20% by mass, or the like.
• the content of the Si-H group-containing silicone (B) is the content of the silicone (A) containing an alkenyl group and/or a Q unit represented by SiO 4/2 and the Si-H group-containing silicone (B).
• the total amount is 100 parts by mass, it is preferably 1 part by mass or more and 60 parts by mass or less, more preferably 2 parts by mass or more and 50 parts by mass or less, and 3 parts by mass or more and 45 parts by mass or less. It is more preferable. If the above content is less than 1 part by mass, the curing reaction will be difficult to proceed and sufficient coating hardness may not be obtained. If the above content exceeds 60 parts by mass, Si-H will be excessively It precipitates on the green sheet and adheres strongly to the green sheet, which may result in heavy peeling.
• silicone (A) containing an alkenyl group and/or a Q unit represented by SiO 4/2 and a Si-H group based on the solid content mass of the composition are provided.
• the total amount of silicone (B) solid content is preferably 70% by mass or more.
• the more preferable content of each silicone solid content is 80% by mass or more and 97% by mass or less.
• the silicone solid content refers to the amount excluding the aqueous solvent
• the solid content mass of the composition refers to the total amount of solid content of each additive. If the total amount of silicone solid content is less than the lower limit, the area covered with silicone on the film surface on which the coating film is formed will decrease, the peeling force will become heavy, and the peeling force may become uneven. There is.
• aqueous solvent Water is preferably used as the aqueous solvent for forming each silicone aqueous dispersion of the present invention.
• a silicone mold release layer can be formed without using explosion-proof equipment and organic solvent recovery equipment that are required for organic solvents during the process of manufacturing a mold release film.
• Nonionic emulsifier Each water dispersion is prepared using a nonionic emulsifier to increase the stability and shear resistance of the water dispersion.
• the emulsifier must be a nonionic emulsifier in order to prevent aggregation of the respective water dispersions and to not affect the curing reaction of silicone. found.
• Cationic emulsifiers affect the curing reaction of silicone, and are localized in the coating film, for example, bleed out to the surface, affecting mold releasability and causing heavy peeling. Further, although the details are unknown, when a cationic emulsifier is used, silicone-based water dispersions tend to aggregate with each other.
• the nonionic emulsifier preferably has an HLB value in the range of 6 to 18, and includes, for example, alkylene oxide adducts of higher alcohols or higher fatty acids, esters of alkylene oxide adducts of higher fatty acids and alcohols, and alkylene alkanolamides. At least one type selected from alkylene oxide adducts such as oxide adducts, alkylene oxide adducts of sorbitan esters, and alkylene oxide adducts of higher fatty acid glycerides is mentioned. These may be used alone or in combination of two or more.
• the HLB value is a value calculated using the Griffin calculation formula.
• the alkylene oxide examples include ethylene oxide, propylene oxide, and butylene oxide, and one or more of these may be used.
• the HLB value is preferably in the range of 6 or more and 18 or less, and more preferably in the range of 10 or more and 15 or less, although it does not matter whether the addition format is block or random.
• preferred examples include polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether. If a nonionic emulsifier with an HLB value outside the above range is used as an emulsifier for a silicone aqueous dispersion, the emulsifying dispersion power and stability of the aqueous dispersion may decrease.
• the nonionic emulsifier is preferably used in a range of 0.1% by mass or more and 20% by mass or less, more preferably 0.2% by mass or more and 15% by mass or less, based on the total solid content, and Preferably it is in the range of 0.5% by mass or more and 10% by mass or less. If it is below this range, emulsification tends to be poor, and if it is above this range, heavy exfoliation may occur.
• Platinum-based catalyst In the mold release coating composition constituting the coating layer of the present invention, one or more silicones (A) containing an alkenyl group and/or Q unit are subjected to an addition reaction with a Si-H group-containing silicone (B). Therefore, it is necessary to use a platinum-based catalyst.
• platinum-based catalysts can be used, such as platinum chloride and chloroplatinic acid.
• the above platinum-based catalyst may be a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex (Karstedt catalyst) in consideration of its dispersibility in silicone. Uniform dispersibility can be ensured by dispersing at the same time. These may be used alone or in combination of two or more.
• the amount of platinum-based catalyst is determined by an aqueous dispersion (1) of one or more types of silicone (A) containing an alkenyl group and/or a Q unit, and an aqueous dispersion (2) of an Si-H group-containing silicone (B). It is preferable that the mass of the platinum element is contained in a range of 10 ppm or more and 800 ppm or less with respect to 100 parts by mass of the total amount. By setting it as the said range, silicone can be fully hardened. Moreover, the generation of silicone aggregates can be suppressed, and a release polyester film with excellent surface properties can be obtained.
• the amount of platinum-based catalyst is more preferably 600 ppm or less, still more preferably 500 ppm or less, particularly preferably 200 ppm or less, and very preferably 150 ppm or less. Furthermore, if the mass ratio of the platinum element is below the lower limit, the addition reaction does not proceed, which tends to cause poor curing of silicone. From the above viewpoint, the amount of platinum catalyst is more preferably 15 ppm or more, still more preferably 20 ppm or more, particularly preferably 25 ppm or more, and most preferably 40 ppm or more.
• the aqueous coating composition contains a crosslinking reaction inhibitor.
• the crosslinking reaction inhibitor is preferably a crosslinking reaction inhibitor having an alkynyl group.
• the crosslinking reaction inhibitor having an alkynyl group is not particularly limited as long as it has an alkynyl group, but specifically, 1-ethynyl-1-cyclohexanol, 4-ethyl-1-octyn-3-ol, 3-Methyl-1-dodecyn-3-ol, 3,7,11-trimethyl-1-dodecyn-3-ol, 1,1-diphenyl-2-propyn-3-ol, 3-ethyl-6-ethyl- Examples include 1-nonyn-3-ol, 3-methyl-1-pentadecyn-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, and 3-phenyl-1-butyn-3-ol.
• Ru These may be used alone or in combination of two or more. Since the present invention employs an aqueous emulsion coating composition, a crosslinking reaction inhibitor having an alkynyl group and a hydroxyl group as exemplified may be used in view of the balance between affinity and solubility in water, coordination ability to platinum, and boiling point. is preferred.
• the content of the crosslinking reaction inhibitor is preferably 5 ppm or more and 1000 ppm or less, more preferably 10 ppm or more and 700 ppm or less, and even more preferably 20 ppm or more and 500 ppm or less, based on the amount of the aqueous coating composition used to form the release layer.
• the content of the crosslinking reaction inhibitor is at least the lower limit, the pot life becomes long, the addition curing reaction of silicone is difficult to proceed at room temperature, and silicone aggregates tend to be difficult to generate.
• silicone will be difficult to transfer to the other material after the other material is peeled off, and the amount of reaction inhibitor that evaporates during heat treatment will decrease, resulting in contamination inside the oven. is less likely to occur.
• the release coating composition of the present invention may further contain, for example, an adhesion imparting agent to a substrate, a coloring agent, an ultraviolet absorber, particles, an antistatic agent, etc., within a range that does not impair the objects of the present invention. May be added.
• each silicone aqueous dispersion of the present invention a method of emulsifying the silicone component, an aqueous solvent, and an emulsifier described above may be mentioned.
• These components can be emulsified using a known method.
• silicone and emulsifier prepared in advance, and other components as necessary, are mixed using a stirring device such as a homogenizer, ajihomo mixer, or an ultra planetary mixer. Examples include a method of mechanical emulsification in an aqueous medium.
• the particle size of the aqueous dispersion can be adjusted by adjusting the size of the stirring blade, stirring speed, and stirring time.
• the average particle size of each silicone aqueous dispersion of the present invention is preferably 200 nm or less, more preferably 100 nm or more and 200 nm or less.
• a coating layer is formed on at least one surface of a polyester film using the release coating composition of the present invention.
• the coating layer (release layer) of the present invention is formed by applying the coating composition for mold release onto the polyester film, followed by drying.
• the thickness of the coating layer after drying is preferably 5 nm or more and 70 nm or less. If the thickness of the coating layer is less than the lower limit, the release properties may be insufficient, and if it exceeds the upper limit, the peel strength will increase, and it may be necessary to increase the concentration of the coating liquid or increase the amount of coating. Therefore, it tends to be difficult to apply.
• an aqueous coating solution containing the above composition is prepared, and the solid content concentration of the aqueous coating solution is 20% by mass or less based on the mass of the above coating solution.
• the content is preferably 1% by mass or more and 10% by mass or less. If the solid content concentration in the aqueous coating liquid is less than the lower limit, the coating properties on the polyester film may be insufficient. Furthermore, if the solid content concentration exceeds the upper limit, the stability of the coating liquid and the appearance of the coating layer may deteriorate. Water is preferably used as the aqueous solvent to adjust the solid content concentration.
• the aqueous coating solution can be applied to the polyester film at any stage, it is preferable to apply it during the manufacturing process of the polyester film. is preferred.
• the polyester film before the completion of crystal orientation refers to an unstretched film, an unstretched film in the longitudinal direction (hereinafter sometimes referred to as continuous film forming direction, longitudinal direction, MD direction) or transverse direction (hereinafter referred to as continuous film forming direction, longitudinal direction, MD direction). , a direction perpendicular to the machine direction, a width direction, or a TD direction), and a film oriented by low-magnification stretching in two directions, the machine direction and the transverse direction (sometimes called the TD direction).
• in-line coating in which an aqueous coating solution of the above composition is applied to an unstretched film or a uniaxially stretched film oriented in one direction, and the film is directly subjected to longitudinal stretching and/or transverse stretching and heat setting.
• the coated layer may be dried by a stretching process or a heat setting process after coating, and a drying process may be added if necessary.
• the curing can be performed by a stretching process or a heat setting process, but a curing process may be added as necessary.
• the film surface is subjected to physical treatment such as corona surface treatment, flame treatment, plasma treatment, etc. as a preliminary treatment to improve coating properties, or the above-mentioned composition is applied together with the composition. It is preferable to use an emulsifier as a wetting agent.
• any known coating method can be used as the coating method.
• a roll coating method, a gravure coating method, a roll brushing method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, etc. can be used alone or in combination.
• the method for producing a silicone release polyester film of the present invention includes: An aqueous dispersion (1) of one or more types of silicone (A) containing an alkenyl group and/or a Q unit represented by SiO 4/2 , Si represented by a Si-H group on at least one side of the polyester film.
• a coating layer is formed using a release coating composition containing an aqueous dispersion (2) of silicone (B) having a hydrogen atom directly bonded to an atom, a crosslinking reaction inhibitor, a platinum catalyst, and a nonionic emulsifier.
• a method of manufacturing a silicone release polyester film comprising:
• the number average molecular weight of the silicone A is 150,000 or more,
• the content of Si atoms contained in the Q unit is in the range of 0.05 mol% or more and 60 mol% or less.
• the method for producing a silicone release polyester film of the present invention makes it possible to efficiently and easily obtain a silicone release polyester film having the above characteristics. Note that the manufacturing method shown here is an example, and the present invention is not limited thereto.
• the step of forming a coating layer using an aqueous dispersion mold release coating composition may be a method of forming a coating layer on a film using an aqueous dispersion mold release coating composition.
• a known method can be used as appropriate.
• Adhesive tape peel strength is measured by laminating a polyester adhesive tape (manufactured by Nitto Denko Corporation, No. 31B) on the surface of the coating layer (mold release layer) of a release film and pressing it with a 5 kg pressure roller. This is the strength obtained by measuring the peel strength between the release layer and the adhesive tape (peel angle 180 degrees, peel speed 300 mm/min, unit: g/25 mm width) with a peel strength tester after standing for 30 minutes or more. .
• the silicone release polyester film of the present invention preferably has a peel strength of 20 g/25 mm or more and 400 g/25 mm or less.
• the peeling angle was 180 degrees and the peeling speed was 300 mm/min.
• Residual adhesion rate (%) (f) / (f0) x 100
• the residual adhesion rate is preferably 90% or more, indicating a high silicone crosslinking density. Moreover, when it is less than 90%, it shows that crosslinking is insufficient.
• this coated film was dried at 115°C for about 5 seconds, stretched 4.5 times in the transverse direction at 145°C, and further heat-set at 230°C for about 5 seconds to form a 25um coated film having the coated layer shown in Table 1.
• a biaxially stretched polyester film was obtained.
• the composition of silicone (1-a) is that in formula (I), R 1 is a vinyl group, R 2 is a methyl group, and silicon to which a vinyl group is directly bonded has only one vinyl group.
• R 1 is a vinyl group
• R 2 is a methyl group
• silicon to which a vinyl group is directly bonded has only one vinyl group.
• R 1 a R 2 b SiO (4-ab)/2 ...(I) (In formula (I), R 1 is an alkenyl group having 2 to 8 carbon atoms, R 2 is a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms selected from an alkyl group or an aryl group, and a represents an integer from 0 to 3, b represents an integer from 0 to 3, and satisfies a+b ⁇ 3.)
• composition of silicone (1-b) is that in formula (I), R 1 is a vinyl group, R 2 is a methyl group, and silicon to which a vinyl group is directly bonded has only one vinyl group.
• the vinyl group is bonded to the terminal silicon atom, and the vinyl group is bonded to a silicon atom with a repeating number of 3 and a dimethylsiloxane constituent unit (both ends are vinyl groups), and the latter
• the number average molecular weight was adjusted to 40,000 by the number of repeating structural units.
• R 3 c H d SiO (4-c-d)/2 ...(II) (In formula (II), R 3 is a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms selected from an alkyl group or an aryl group, c is 0 to 2, d is 1 to 3, and Each represents an integer that satisfies c+d ⁇ 3.)
• the hydrogen atom is not bonded to the terminal silicon atom, and the number of repetitions of the constituent unit with the silicon atom to which the hydrogen group is directly bonded is 30, and the constituent unit of dimethylsiloxane (both terminals are methyl
• the number average molecular weight was adjusted to 5,000 depending on the number of repeats of the latter structural unit.
• aqueous coating composition As the aqueous coating composition (coating composition for mold release), an aqueous dispersion of silicone (1-a) or an aqueous dispersion of silicone (1-b) and silicone (2) having an Si-H group are used. , 40 ppm of the following platinum-based catalyst based on the total coating liquid weight of silicone (1-a) and silicone (2) and the coating weight were added to the silicone aqueous dispersion mixed so as to have the solid proportion shown in Table 1.
• a coating solution was prepared by mixing 200 ppm of the following crosslinking reaction inhibitor with the sample and diluting the solid content concentration of the coating solution with water so that the dry coating thickness was 40 nm.
• Platinum-based catalyst emulsion manufactured by Shin-Etsu Chemical Co., Ltd., product name "CAT-PM-10A"
• CAT-PM-10A ⁇ Crosslinking reaction inhibitor: 1-ethynylcyclohexanol (manufactured by Alfa Lancaster)
• the films of Examples of the present invention were excellent in releasability and residual adhesion. This is because by using a specific composition containing very high molecular weight silicone, a film with excellent residual adhesive strength as well as various releasability properties can be obtained.
• Comparative Example 1 insufficient crosslinking resulted in heavy peeling.
• Comparative Example 2 the number of SiH residues in silicone (2) increased, resulting in an increase in transfer and a decrease in the residual adhesion rate.
• crosslinking was insufficient, the transfer of the base resin increased, and the residual adhesion rate also decreased.
• Comparative Example 4 the number of SiH residues in silicone (2) increased, resulting in an increase in transfer and a decrease in the residual adhesion rate.

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