WO2019039264A1 - セラミックグリーンシート製造用離型フィルム - Google Patents
セラミックグリーンシート製造用離型フィルム Download PDFInfo
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- WO2019039264A1 WO2019039264A1 PCT/JP2018/029567 JP2018029567W WO2019039264A1 WO 2019039264 A1 WO2019039264 A1 WO 2019039264A1 JP 2018029567 W JP2018029567 W JP 2018029567W WO 2019039264 A1 WO2019039264 A1 WO 2019039264A1
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- green sheet
- parts
- ceramic green
- coating layer
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000007883 water-soluble azo polymerization initiator Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/353—Five-membered rings
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
Definitions
- the present invention relates to a release film for producing a ceramic green sheet. More specifically, the present invention relates to a release film for producing a ceramic green sheet which can be provided with all the prevention of pinholes and partial thickness variation and the like and the reduction of unwinding charge even when the ceramic green sheet is made thin.
- the release film for producing a ceramic green sheet is stored in a wound state by relatively roughening the surface roughness of the surface (rear surface) opposite to the surface on which the release agent layer of the substrate film is provided.
- a technique of eliminating defects such as sticking (blocking) of the front and back of the release film for producing a ceramic green sheet when it is made see, for example, Patent Document 1).
- Patent Document 1 such prior art has a problem that pinholes and partial thickness variations occur because the protrusions are large.
- the present invention has been made on the background of the problems of the prior art. That is, it is an object of the present invention to produce an excellent ceramic green sheet capable of preventing pinholes and partial thickness variations, etc., and reducing unrolling charging even when the ceramic green sheet is thinned. It is in providing a release film.
- the present invention has the following constitution.
- An easily slip coating layer based on a polyester film substantially free of inorganic particles, having a release coating layer on one surface of the substrate, and containing particles on the other surface A release film for producing a ceramic green sheet, having a composition having a slippery coating layer containing at least one crosslinking agent selected from an acrylic resin and an oxazoline crosslinking agent or a carbodiimide crosslinking agent.
- the area surface average roughness (Sa) of the easily slip coating layer is 1 nm or more and 25 nm or less
- the maximum projection height (P) is 60 nm or more and 500 nm or less
- the average length (RSm) of the roughness curvilinear element is 10 ⁇ m or less
- a method for producing a ceramic capacitor employing the method for producing a ceramic green sheet according to the sixth or seventh aspect.
- the present invention even when the thickness of the ceramic green sheet is reduced, it is possible to prevent pinholes and partial thickness variations, and to reduce all the charging for unwinding. It becomes possible to provide a film.
- the release film for producing a ceramic green sheet of the present invention (hereinafter sometimes referred to simply as release film) has a release coating layer on one side of a biaxially oriented polyester film which is a base film, and particles on the other side. It is a release film which has an easy-to-slide coating layer containing.
- the present inventors can cope with recent thinning of green sheets by keeping the average length (RSm) of the roughness curvilinear element of the slippery coated surface within a specific range in order to increase the density of protrusions on the slippery surface. Release film is proposed (International Application No. PCT / JP2017 / 017354). According to this technique, it is preferable to increase the density of protrusions, since good winding performance and prevention of pinholes and partial thickness variations can be provided while maintaining the height of protrusions low.
- the easily slipping coating layer since a composition containing an acrylic resin and at least one crosslinking agent selected from an oxazoline crosslinking agent or a carbodiimide crosslinking agent is cured as the easily slipping coating layer, the easily slipping coating layer can be obtained.
- the hardness of the above becomes moderately high, and deformation of the easy-to-slip coating layer when taken up after coating of the release coating layer becomes difficult to occur.
- the contact area between the easily slip coating layer and the release layer will be small, which is preferable because it can suppress unrolling charging when the release film roll is unwound. It is preferable to prevent the charging resistance from being low because this can prevent the quality of the ceramic capacitor from being abnormal due to the adhesion of environmental foreign matter to the releasing surface. In ceramic sheet thinning, which is a trend in recent years, the adhesion of minute environmental foreign matter to the mold release surface, which has not been a problem in the past, is also a problem.
- a release film having a composition is effective, and it is further preferable to add the average length (RSm) of the roughness curvilinear element of the slippery coating layer within a specific range.
- the film preferably used as a substrate in the present invention is a film composed of a polyester resin, and is mainly a polyester film comprising at least one selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and polyethylene naphthalate. preferable.
- it may be a film made of polyester in which a third component monomer is copolymerized as part of the dicarboxylic acid component or diol component of the polyester as described above.
- polyethylene terephthalate films are most preferable in terms of the balance between physical properties and cost.
- the polyester film may be a single layer or multiple layers.
- various additives can be contained in the polyester resin, if necessary, in these layers, as long as the desired effects of the present invention are exhibited.
- the additive include an antioxidant, a light resistant agent, an antigelling agent, an organic wetting agent, an antistatic agent, an ultraviolet light absorber and the like.
- the release film of the present invention has a slippery coating layer on one surface of the polyester base film as described above. It is preferable that at least a binder resin and particles be contained in the easy-to-slide coating layer.
- an acrylic resin is contained as a binder resin which comprises the easily slipping coating layer in this invention.
- the acrylic resin is preferably an acrylic resin having a hydroxyl group and a carboxyl group in the molecule. It is more preferable that the constituent unit having a hydroxyl group is contained in an amount of 20 to 90 mol% in 100 mol% of the total constituent units.
- the water solubility of an acrylic resin can be kept moderate as the structural unit which has a hydroxyl group is 20 mol% or more, and it is preferable. On the other hand, it is preferable that the amount is 90 mol% or less, since the hydroxyl group of the acrylic resin and the particles contained in the slippery coating layer do not extremely interact with each other and the particles are uniformly dispersed.
- a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate or 2-hydroxyethyl
- a copolymerization component a ring-opening adduct of ⁇ -butyrolactone or ⁇ -caprolactone to meta
- 2-hydroxyethyl (meth) acrylate is preferable in that it does not inhibit water solubility.
- the acrylic resin in the present invention includes methacrylic resin.
- the hydroxyl value of the acrylic resin is preferably 2 mg KOH / g or more, more preferably 5 mg KOH / g or more, and still more preferably 10 mg KOH / g or more. If the hydroxyl value of the acrylic resin is 2 mg KOH / g or more, the water solubility of the acrylic resin becomes good, which is preferable.
- the hydroxyl value of the acrylic resin is preferably 250 mg KOH / g or less, more preferably 230 mg KOH / g or less, and still more preferably 200 mg KOH / g or less. If the hydroxyl value of the acrylic resin is 250 mg KOH / g or less, it is preferable that the particles contained in the easily hydroxylated layer of the acrylic resin do not extremely interact with each other and the particles are uniformly dispersed.
- the acrylic resin used in the present invention is preferably a resin having a carboxyl group in addition to the hydroxyl group.
- a carboxyl group By having a carboxyl group, it becomes possible to form a crosslinked structure with a crosslinking agent and to easily impart water solubility.
- carboxy group-containing monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid, and monomers containing an acid anhydride group such as maleic anhydride and itaconic anhydride.
- 4 mol% or more is preferable in 100 mol% of all the structural units of an acrylic resin, and 10 mol% or more of the monomer which has a carboxyl group is more preferable.
- it is 4 mol% or more, it is easy to easily form a crosslinked structure in the easily slip coating layer and to impart water solubility, which is preferable.
- 65 mol% or less is preferable and 50 mol% or less of a monomer which has a carboxyl group is more preferable.
- the Tg of the resulting coating film is not too high relative to the preferred range described later as it is 65 mol% or less, and the film forming property and the stretching suitability in in-line coating are good and preferable.
- ком ⁇ онент In order to develop good water solubility, it is preferable to neutralize the carboxyl group introduced into the acrylic resin by copolymerization of acrylic acid and methacrylic acid.
- basic neutralizing agents include amine compounds such as ammonia, trimethylamine, triethylamine and dimethylaminoethanol, and inorganic basic substances such as potassium hydroxide and sodium hydroxide. Of these, volatilization of the neutralizing agent is included. It is preferable to use an amine compound as a neutralizing agent for ease of formation and ease of formation of a crosslinked structure. Among them, ammonia is most preferable in that aggregation of particles does not occur.
- the neutralization ratio is preferably 30 mol% to 95 mol%, more preferably 40 mol% to 90 mol%.
- the neutralization ratio is 30 mol% or more, the water solubility of the acrylic resin is sufficient, the dissolution of the acrylic resin is easy at the time of preparation of the coating solution, and there is no fear of whitening of the coated film surface after drying. preferable.
- the neutralization ratio is 95 mol% or less, the water solubility is not too high, and mixing of an alcohol or the like is easy in preparation of a coating solution, which is preferable.
- the acid value of the acrylic resin is preferably 40 mg KOH / g or more, more preferably 50 mg KOH / g or more, and still more preferably 60 mg KOH / g or more. If the acid value of the acrylic resin is 40 mg KOH / g or more, the crosslinking point with the oxazoline crosslinking agent or carbodiimide crosslinking agent is increased, and a strong coating film having a higher crosslinking density can be obtained, which is preferable.
- the acid value of the acrylic resin is preferably 400 mg KOH / g or less, more preferably 350 mg KOH / g or less, and still more preferably 300 mg KOH / g or less. If the acid value of the acrylic resin is 400 mg KOH / g or less, the particles contained in the carboxyl group of the acrylic resin and the particles contained in the slippery coating layer do not extremely interact with each other, and the particles are preferably dispersed uniformly. If the dispersibility of the particles is good, coarse projections are not generated on the slippery coated surface, and pinholes of the ceramic sheet are not generated, which is preferable.
- the glass transition temperature (Tg) of an acrylic resin is 50 degreeC or more, More preferably, it is 55 degreeC or more, More preferably, it is 60 degreeC or more.
- Tg glass transition temperature
- the glass transition temperature of the acrylic resin is 50 ° C. or higher, the hardness of the easily slip coating layer is appropriately increased, which is preferable.
- the glass transition temperature (Tg) of an acrylic resin is 110 degrees C or less, More preferably, it is 105 degrees C or less, More preferably, it is 100 degrees C or less. It is preferable that the glass transition temperature of the acrylic resin is 110 ° C. or less, since the coating film is uniformly stretched without cracking in the stretching step after coating the easily slip coating layer.
- a (meth) acrylic monomer or a non-acrylic vinyl monomer can be used as the Tg adjusting monomer to be copolymerized in order to bring the Tg into the above range.
- Specific examples of (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) Acrylate, n-Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as ste
- styrene-based monomers such as styrene, ⁇ -methylstyrene, vinyltoluene (a mixture of m-methylstyrene and p-methylstyrene), chlorostyrene, etc .
- vinyl esters such as vinyl crotonate, vinyl sorbate, vinyl benzoate, and vinyl cinnamate
- vinyl halide monomers such as vinyl chloride and vinylidene chloride.
- One or more species can be used.
- the monomer for Tg adjustment is determined by the following Fox equation.
- the component which reduces surface free energy such as a long chain alkyl group
- the acrylic resin into which a long chain alkyl group is introduced one having an alkyl group having about 8 to 20 carbon atoms in the side chain of the acrylic resin is preferable.
- a copolymer having a (meth) acrylic acid ester as a main repeating unit and containing a long-chain alkyl group having 8 to 20 carbon atoms in a transesterified portion can also be suitably used.
- the monomer having a long chain alkyl group may be 0 mol% as long as the Tg can maintain a suitable range, but if it is 5 mol% or more, the effect of adjusting the Tg of the acrylic resin Becomes clear and preferable.
- the acrylic resin used in the present invention can be obtained by known radical polymerization. Any of emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and the like can be employed. From the viewpoint of handleability, solution polymerization is preferred.
- water-soluble organic solvents that can be used for solution polymerization include ethylene glycol n-butyl ether, isopropanol, ethanol, n-methyl pyrrolidone, tetrahydrofuran, 1,4-dioxane, 1,3-oxolane, methyl solosolve and ethyl sorosolve.
- the polymerization initiator may be any known compound that generates radicals, but for example, a water-soluble azo polymerization initiator such as 2,2-azobis-2-methyl-N-2-hydroxyethyl propionamide is preferable.
- a water-soluble azo polymerization initiator such as 2,2-azobis-2-methyl-N-2-hydroxyethyl propionamide is preferable.
- the temperature, time, etc. of the polymerization are appropriately selected.
- the mass average molecular weight (Mw) of the acrylic resin is preferably about 10,000 to 200,000. A more preferable range is 20,000 to 150,000. When Mw is 10,000 or more, there is no fear of thermal decomposition in a tenter, and it is preferable. When the Mw is 200,000 or less, the viscosity of the coating solution does not significantly increase, and the coatability is favorable, which is preferable.
- binder resins may be used in addition to the acrylic resin.
- binder resins include polyester resins, urethane resins, polyvinyl resins (polyvinyl alcohol and the like), polyalkylene glycols, polyalkyleneimines, methylcellulose, hydroxycellulose, starches and the like.
- the content of the acrylic resin in the easily-slidable coating layer is preferably 20% by mass or more and 95% by mass or less in the total solid content. More preferably, it is 30 mass% or more and 90 mass% or less. If it is 20 mass% or more, since the carboxyl group which is a crosslinking component does not decrease too much and a crosslinking density does not fall, it is preferable. If it is 95 mass% or less, the amount of the crosslinking agent to be crosslinked is not too small, and the crosslinking density is not lowered, which is preferable.
- the easily slip coating layer in order to form a crosslinked structure in the easily slip coating layer, preferably contains at least one crosslinking agent selected from an oxazoline crosslinking agent or a carbodiimide crosslinking agent.
- an oxazoline based crosslinking agent or a carbodiimide based crosslinking agent By containing an oxazoline based crosslinking agent or a carbodiimide based crosslinking agent, the adhesion to the PET substrate is improved, and the crosslinking of the acrylic resin with the carboxyl group is promoted to improve the coating strength of the slippery layer. As a result, it is possible to suppress the unwinding charging when the release film roll is unwound.
- crosslinking agents may be used in combination, and specific crosslinking agents which can be used in combination include urea based, epoxy based, melamine based, isocyanate based and silanol based.
- a catalyst etc. can be used suitably as needed.
- crosslinking agent having an oxazoline group for example, a conventionally known method (for example, solution polymerization, emulsion polymerization, etc.) together with other polymerizable unsaturated monomers, if necessary, a polymerizable unsaturated monomer having an oxazoline group
- a conventionally known method for example, solution polymerization, emulsion polymerization, etc.
- a polymerizable unsaturated monomer having an oxazoline group for example, a conventionally known method (for example, solution polymerization, emulsion polymerization, etc.) together with other polymerizable unsaturated monomers, if necessary, a polymerizable unsaturated monomer having an oxazoline group
- the polymer etc. which have the oxazoline group obtained by copolymerizing with can be mentioned.
- Examples of the polymerizable unsaturated monomer having an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2- Isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like can be mentioned. These may be used alone or in combination of two or more.
- polymerizable unsaturated monomers for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) Alkyl or cycloalkyl ester having 1 to 24 carbon atoms of (meth) acrylic acid such as acrylate, lauryl (meth) acrylate or isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc.
- the other polymerizable unsaturated monomer is a hydrophilic monomer, from the viewpoint of improving compatibility with other resins, wettability, crosslinking reaction efficiency, etc., using the obtained crosslinking agent having an oxazoline group as a water-soluble crosslinking agent. It is preferably a body.
- hydrophilic monomers include monomers having a polyethylene glycol chain such as 2-hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and monoester compounds of (meth) acrylic acid and polyethylene glycol, 2- Aminoethyl (meth) acrylate and salts thereof, (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, (meth) acrylonitrile, sodium styrene sulfonate and the like.
- monomers having a polyethylene glycol chain such as methoxypolyethylene glycol (meth) acrylate having high solubility in water, and monoester compounds of (meth) acrylic acid and polyethylene glycol are preferable.
- the crosslinking agent having an oxazoline group preferably has an oxazoline group content of 3.0 to 9.0 mmol / g. More preferably, it is in the range of 4.0 to 8.0 mmol / g. If it is in the range of 4.0 to 8.0 mmol / g, it is preferable because a suitable crosslinked structure can be formed.
- a monocarbodiimide compound and a polycarbodiimide compound are mentioned.
- monocarbodiimide compounds include dicyclohexyl carbodiimide, diisopropyl carbodiimide, dimethyl carbodiimide, diisobutyl carbodiimide, dioctyl carbodiimide, t-butyl isopropyl carbodiimide, diphenyl carbodiimide, di-t-butyl carbodiimide, di- ⁇ -naphthyl carbodiimide and the like.
- a polycarbodiimide compound what was manufactured by the conventionally well-known method can be used. For example, it can manufacture by synthesize
- diisocyanates that can be used to synthesize polycarbodiimide compounds include isomers of toluylene diisocyanate, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate, and the like. And alicyclic diisocyanates such as 2,4-dicyclohexylmethane diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane; aliphatic diisocyanates such as hexamethylene diisocyanate; and 2,2,4-trimethylhexamethylene diisocyanate. From the problem of yellowing, aromatic aliphatic diisocyanates, alicyclic diisocyanates and aliphatic diisocyanates are preferred.
- the above diisocyanate may be used by controlling the molecule to an appropriate degree of polymerization using a compound which reacts with terminal isocyanate such as monoisocyanate.
- monoisocyanate for sealing the end of polycarbodiimide and controlling the degree of polymerization thereof include phenylisocyanate, toluyleneisocyanate, dimethylphenylisocyanate, cyclohexylisocyanate, butylisocyanate, and naphthylisocyanate.
- compounds having an OH group, -NH 2 group, COOH group, SO 3 H group can be used as an end capping agent.
- the condensation reaction involving the carbon dioxide removal of the diisocyanate proceeds in the presence of a carbodiimidization catalyst.
- a catalyst for example, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2 -Phospholene-1-oxide, and phosphorene oxides such as 3-phospholene isomers thereof, and the like, and 3-methyl-1-phenyl-2-phospholene-1-oxide is preferable in terms of reactivity.
- the usage-amount of the said catalyst can be made into a catalytic amount.
- the above-mentioned mono- or polycarbodiimide compound is kept in a uniform dispersion state when formulated into an aqueous paint, for this purpose it is emulsion-processed using an appropriate emulsifier and used as an emulsion, or polycarbodiimide It is preferable to add a hydrophilic segment to the molecular structure of the compound and to add it to the paint in the form of a self-emulsified product or in the form of a self-dissolved product.
- the carbodiimide type crosslinking agent used in the present invention includes water dispersibility and water solubility.
- Water solubility is preferred because it has good compatibility with other water-soluble resins and improves the crosslinking reaction efficiency of the slippery coating layer.
- a carbodiimide compound water-soluble after synthesizing an isocyanate-terminated polycarbodiimide by condensation reaction involving decarbon dioxide of an isocyanate, adding a hydrophilic site having a functional group having reactivity with an isocyanate group. It can be manufactured by
- hydrophilic portion (1) quaternary ammonium salt of dialkylamino alcohol, quaternary ammonium salt of dialkylaminoalkylamine, etc. (2) alkyl sulfonate having at least one reactive hydroxyl group, etc., (3) Examples thereof include poly (ethylene oxide) end-capped with an alkoxy group, and a mixture of poly (ethylene oxide) and poly (propylene oxide).
- the carbodiimide compound becomes (1) cationic, (2) anionic, and (3) nonionic when the above-mentioned hydrophilic site is introduced. Among them, nonionicity that is compatible is preferable regardless of the ionicity of the other water-soluble resin.
- the content of the crosslinking agent in the slippery coating layer is preferably 5% by mass to 80% by mass in the total solid content. More preferably, it is 10% by mass or more and 70% by mass or less. If it is 5 mass% or more, it is preferable from the crosslink density of resin of an application layer not falling. If it is 80 mass% or less, the amount of carboxyl groups of the acrylic resin to be crosslinked is not too small, and the crosslinking density is not lowered, which is preferable.
- 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 / Iso
- 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
- small particles with an average particle diameter of about 10 to 270 nm and large particles with an average particle diameter of about 300 to 1000 nm the area surface average roughness (Sa) described below, and the maximum projection height ( P is preferably kept small, and the average length (RSm) of the roughness curvilinear element is made small to achieve both slipperiness and smoothness, and particularly preferably small particles of 30 to 250 nm and average particles. It is to use large particles having a diameter of 350 to 600 nm in combination.
- small particles and large particles it is preferable to make the mass content of small particles larger than the mass content of large particles with respect to the total solid content of the coating layer.
- organic particles it is also particularly preferable to use organic particles in order to prevent the particles from falling off the slip coating layer.
- the organic particles By using the organic particles, the interaction with the binder of the easily sliding coating layer and the crosslinker component becomes strong, and it is easy to prevent dropping off, which is preferable.
- acrylic resin particles and / or methacrylic resin particles whose chemical structure is similar to that of the acrylic resin present in the slippery coating layer are particularly preferable in preventing the particles from coming off from the slippery coating layer.
- These organic particles are preferably contained as particles having a relatively large average particle diameter, in which the detachment of the particles from the slippery coating layer tends to be a problem, for example, containing as particles having an average particle diameter of 300 to 1000 nm. Is preferred. More preferably, it is contained as particles having an average particle diameter of 350 to 600 nm.
- the organic particles having the above average particle diameter are acrylic resin particles and / or methacrylic resin particles.
- the method of measuring the average particle diameter of the particles is to observe the particles of the cross section of the film after processing with a transmission electron microscope or a scanning electron microscope, observe 100 non-aggregated particles, and find the average value of the average particles. It was done by the method to make it the diameter.
- 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 ⁇ , calculating the square root and doubling it.
- the ratio of the particles to the total solid content of the easily-slidable coating layer is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. If the ratio of the particles to the total solid content of the easily-slidable coating layer is 50% by mass or less, transparency is maintained and the particles are not significantly separated from the easily-slidable coating layer, which is preferable.
- the ratio of the particles to the total solid content of the easily-slidable coating layer is preferably 1% by mass or more, more preferably 1.5% by mass or more, and still more preferably 2% by mass or more. If the ratio of the particles to the total solid content of the easily slip coating layer is 1% by mass or more, slipperiness can be secured, which is preferable.
- the following method can be used.
- the easily slip coating layer provided on the processed film is extracted from the processed film using a solvent or the like and dried to obtain the easily slip coating layer.
- heat is applied to the obtained easy-to-slip coating layer, and the organic components contained in the easy-sliding coating layer are burned and distilled off by heat to obtain only the inorganic component.
- the mass% of the particles contained in the easy-to-slide coating layer can be measured.
- the ratio of the above-mentioned particles in the total solid content of the easily-slidable coating layer means the ratio of the total amount of the plurality of types of particles, when there are a plurality of types of particles.
- additives in slippery coating layer In order to impart other functionality to the easily slip coating layer, various additives may be contained to such an extent that the coating appearance is not impaired.
- the additive include fluorescent dyes, fluorescent whitening agents, plasticizers, ultraviolet light absorbers, pigment dispersants, foam inhibitors, antifoaming agents, preservatives and the like.
- a surfactant can also be incorporated into the easy-to-slip coating layer for the purpose of improving the leveling property at the time of coating and degassing the coating solution.
- the surfactant may be any of cationic, anionic and nonionic surfactants, but is preferably silicone, acetylene glycol or fluorosurfactant. It is preferable that these surfactants be contained in the coating layer in such a range that an abnormality in the coating appearance does not occur by the excessive addition.
- any of so-called in-line coating method of simultaneously applying at the time of film formation of polyester base film and so-called off-line coating method of separately applying with a coater after film formation of polyester base film can be applied. Is efficient and more preferable.
- any known method can be used.
- reverse roll coating method gravure coating method, kiss coating method, die coating method, roll brush method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, pipe doctor method, impregnation coating method, curtain coating method, etc. It can be mentioned. These methods are applied alone or in combination.
- a method of providing a slippery coating layer on a polyester film there may be mentioned a method in which a coating solution containing a solvent, particles and a resin is applied to the polyester film and dried.
- the solvent include an organic solvent such as toluene, water, or a mixed system of water and a water-soluble organic solvent, preferably a so-called water-based system in which water alone or a water-soluble organic solvent is mixed from the viewpoint of environmental problems. Solvents are preferred.
- the solid content concentration of the slippery coating solution depends on the type of the binder resin, the type of the solvent, and the like, but is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
- the solid content concentration of the coating solution is preferably 35% by mass or less, more preferably 20% by mass or less.
- the drying temperature after application also depends on the type of binder resin, the type of solvent, the presence or absence of a crosslinking agent, the solid content concentration, etc., but is preferably 70 ° C. or higher, and preferably 250 ° C. or lower.
- the polyester film to be a base film can be produced according to a general polyester film production method.
- a polyester resin is melted, and a non-oriented polyester extruded into a sheet is stretched in the longitudinal direction at a temperature higher than the glass transition temperature using a roll speed difference and then stretched in the transverse direction by a tenter.
- the method of heat-processing is mentioned.
- the method of biaxially stretching simultaneously in all directions in a tenter is also mentioned.
- the polyester film to be the base film may be a uniaxially stretched film or a biaxially stretched film, but is preferably a biaxially stretched film.
- the thickness of the polyester film substrate is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and still more preferably 15 ⁇ m or more. When the thickness is 5 ⁇ m or more, it is preferable that wrinkles hardly occur when the film is transported.
- the thickness of the polyester film substrate is preferably 50 ⁇ m or less, more preferably 45 ⁇ m or less, and still more preferably 40 ⁇ m or less. When the thickness is 40 ⁇ m or less, the cost per unit area is reduced, which is preferable.
- in-line coating it may be coated on an unstretched film before stretching in the longitudinal direction or may be coated on a uniaxially stretched film before stretching in the transverse direction after stretching in the longitudinal direction.
- coating before stretching in the longitudinal direction it is preferable to provide a drying step before roll stretching.
- the film heating process in the tenter can also serve as the drying process, so it is not necessary to separately provide a drying process. The same applies to simultaneous biaxial stretching.
- the thickness of the easily slip coating layer is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, still more preferably 0.02 ⁇ m or more, and particularly preferably 0.03 ⁇ m or more.
- the film thickness of the coating layer is 0.001 ⁇ m or more, the film forming property of the coating film is maintained, and a uniform coating film is obtained, which is preferable.
- the thickness of the easily slip coating layer is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, still more preferably 0.8 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less.
- the film thickness of the coating layer is 2 ⁇ m or less, there is no possibility that blocking will occur, which is preferable.
- the ceramic green sheet to be coated and molded on a release coating layer described later is rolled up with a release film after coating and molding. At this time, the easy-sliding coating layer of the release film is in contact with the surface of the ceramic green sheet, and is wound.
- the outer surface of the slippery coated layer (the slippery coated layer surface of the whole coated film not in contact with the polyester film) needs to be appropriately flat in order to prevent the occurrence of defects on the surface of the ceramic green sheet. It is preferable that the surface average roughness (Sa) is 1 nm or more and 25 nm or less, and the maximum projection height (P) is 60 nm or more and 500 nm or less.
- the slippery coated surface is not too smooth and adequate slipperiness is maintained It is preferable because it can be done. If the area surface average roughness (Sa) is 25 nm or less and the maximum projection height (P) is 500 nm or less, the easily-smooth coated surface is not too rough and defects in the ceramic green sheet due to the projections are not generated.
- the average length (RSm) of the roughness curvilinear element is preferably 10 ⁇ m or less.
- the average length (RSm) of the roughness curvilinear element is more preferably 5 ⁇ m or less, still more preferably 3 ⁇ m or less.
- the average length (RSm) of the roughness curvilinear element is too small is related to the fact that the content of particles in the slippery coating layer is too high, etc., and the area surface average roughness (Sa) increases.
- the maximum protrusion height (P) is also related to the increase, it is preferably 0.1 ⁇ m or more, and may be 0.5 ⁇ m or more, or 1 ⁇ m or more.
- the average particle size of the particles contained in the slippery coating layer is 1000 nm or less. More preferably, it is 800 nm or less, still more preferably 600 nm or less. If the particle diameter is 1000 nm or less, the distance between particles does not become too large, and RSm is preferably adjusted within a predetermined range.
- the surface free energy of the slipperiness coating layer is preferably 45 mJ / m 2 or less, more preferably 40 mJ / m 2 or less.
- the resin constituting the release coating layer in the present invention is not particularly limited, and silicone resin, fluorine resin, alkyd resin, various waxes, aliphatic olefins, etc. can be used, and each resin may be used alone or in combination of two or more kinds. You can also
- silicone resin is a resin having a silicone structure in the molecule, and curing silicone, silicone graft resin, modified silicone resin such as alkyl modified, etc. may be mentioned. It is preferable to use a reactive cured silicone resin from the viewpoint of properties and the like.
- the reactive cured silicone resin those of addition reaction type, those of condensation reaction type, those of ultraviolet ray or electron beam hardening type, etc. can be used. More preferred are low-temperature curable addition reaction systems that can be processed at low temperatures, and ultraviolet or electron beam curing systems.
- silicone resin of the addition reaction system for example, one in which polydimethylsiloxane having a vinyl group introduced at a terminal or a side chain and hydrogen siloxane are reacted and cured using a platinum catalyst can be mentioned. At this time, it is more preferable to use a resin which can be cured at 120 ° C. within 30 seconds, because processing at a low temperature is possible.
- Examples include low temperature addition cures from Toray Dow Corning (LTC 1006 L, LTC 1056 L, LTC 300 B, LTC 303 E, LTC 310, LTC 314 G, LTC 450 A, LTC 371 G, LTC 750 A, LTC 750 A, LTC 755, LTC 760 A etc.) and thermal UV cure (LTC 851, BY24 -510, BY24-561, BY24-562, etc.), solvent addition + UV curing type (X62-5040, X62-5065, X62-5072T, KS5508 etc.) manufactured by Shin-Etsu Chemical Co., Ltd., dual cure curing type (X62-2835, X62 -2834, X62-1980, etc.).
- Toray Dow Corning LTC 1006 L, LTC 1056 L, LTC 300 B, LTC 303 E, LTC 310, LTC 314 G, LTC 450 A, LTC 371 G, LTC 750 A, LTC
- a silicone resin of a condensation reaction system for example, a polydimethylsiloxane having an OH group at the end and a polydimethylsiloxane having an H group at the end are condensation reacted using an organotin catalyst to form a three-dimensional crosslinked structure It can be mentioned.
- UV curable silicone resin for example, one that utilizes the same radical reaction as conventional silicone rubber crosslinking as the most basic type, one that is photocured by introducing an unsaturated group, and an onium salt is decomposed by ultraviolet light Those which generate a strong acid and thereby cleave an epoxy group to crosslink, and those which crosslink by an addition reaction of a thiol to a vinyl siloxane and the like can be mentioned.
- an electron beam can also be used instead of the said ultraviolet-ray. Electron beams are stronger in energy than ultraviolet rays, and it is possible to carry out a crosslinking reaction by radicals even without using an initiator as in the case of ultraviolet curing.
- Examples of resins used include UV curable silicones (X62-7028A / B, X62-7052, X62-7205, X62-7622, X62-7629, X62-7660, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Momentive Performance ⁇ UV curable silicones manufactured by Materials (TPR6502, TPR6501, TPR6500, UV9300, UV9315, XS56-A2982, UV9430, etc.), UV cured silicones manufactured by Arakawa Chemical (Silycose UV POLY 200, POLY 215, POLY 201, KF-UV 265 AM, etc.) Can be mentioned.
- UV curable silicones X62-7028A / B, X62-7052, X62-7205, X62-7622, X62-7629, X62-7660, etc.
- Momentive Performance ⁇ UV curable silicones manufactured by Materials TPR6502, TPR6501, TPR6500, UV9300
- acrylate modified or glycidoxy modified polydimethylsiloxane can also be used.
- modified polydimethylsiloxanes can be mixed with a polyfunctional acrylate resin, an epoxy resin or the like and used in the presence of an initiator to provide good mold release performance.
- alkyd resins or acrylic resins which are stearyl-modified, lauryl-modified or the like, alkyd-based resins obtained by reaction of methylated melamine, acrylic resins and the like are also suitable.
- Examples of the amino alkyd resin obtained by the reaction of methylated melamine include Tess Fine 303, Tess Fine 305, Tess Fine 314, etc. manufactured by Hitachi Chemical Co., Ltd.
- As an amino acrylic resin obtained by reaction of methylated melamine etc. Tes fine 322 made by Hitachi Chemical Co., Ltd. etc. may be mentioned.
- the release coating layer in the present invention can contain particles having a particle diameter of 1 ⁇ m or less, but from the viewpoint of pinhole generation, it is preferable not to substantially contain those forming protrusions such as particles.
- an adhesion improver an additive such as an antistatic agent, or the like may be added to the release coating layer in the present invention. 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 coating layer may be set according to the purpose of use, and is not particularly limited.
- the thickness of the release coating layer after curing is 0.005 to 2.0 ⁇ m. The range is good.
- a peeling performance is maintained as the thickness of a mold release application layer is 0.005 micrometer or more, and it is preferable.
- the thickness of the release coating layer is 2.0 ⁇ m or less, the curing time does not become too long, and the thickness unevenness of the ceramic green sheet due to the decrease in the flatness of the release film is not likely to occur, which is preferable.
- the curing time does not become too long, there is no possibility that the resin constituting the release coating layer is aggregated, and there is no possibility of forming projections, so that pinhole defects of the ceramic green sheet are less likely to occur, which is preferable.
- the outer surface of the film on which the release coating layer is formed (the release coating layer surface of the entire applied film not in contact with the polyester film) is flat so as not to cause defects in the ceramic green sheet to be applied and molded thereon. It is desirable that the area surface average roughness (Sa) is 5 nm or less and the maximum projection height (P) is 30 nm or less. Furthermore, the region surface average roughness of 5 nm or less and the maximum projection height of 20 nm or less are more preferable. If the area surface roughness is 5 nm or less and the maximum projection height is 30 nm or less, defects such as pinholes do not occur at the time of forming the ceramic green sheet, which is preferable because the yield is good.
- the PET film contains substantially no inorganic particles.
- substantially free of inorganic particles means 50 ppm or less when the element derived from the particles is quantitatively analyzed by fluorescent X-ray analysis for both the substrate film and the release coating layer. It is defined by a certain thing, Preferably it is 10 ppm or less, Most preferably, it is less than a detection limit. This is because, even if the particles are not actively added to the base film, contamination components derived from extraneous foreign matter, lines attached to the line or apparatus in the manufacturing process of the raw resin or film, and contamination are mixed in the film. Because it is
- the method for forming the release coating layer is not particularly limited, and a coating liquid in which a releasable resin is dissolved or dispersed is spread on one surface of the polyester film of the substrate by coating etc.
- a method of heat drying, heat curing or ultraviolet curing is used.
- the drying temperature at the time of solvent drying and heat curing is preferably 180 ° C. or less, more preferably 150 ° C. or less, and most preferably 120 ° C. or less.
- the heating time is preferably 30 seconds or less, more preferably 20 seconds or less. When the temperature is 180 ° C.
- the flatness of the film is maintained, and the possibility of causing thickness unevenness of the ceramic green sheet is small, which is preferable. It can process without impairing the planarity of a film as it is 120 degrees C or less, and since the possibility of causing thickness nonuniformity of a ceramic green sheet will fall further, it is especially preferable.
- the surface tension of the coating liquid when the release coating layer is applied is not particularly limited, but is preferably 30 mN / m or less.
- the coating liquid for applying the release coating layer is not particularly limited, but it is preferable to add a solvent having a boiling point of 90 ° C. or more.
- a solvent having a boiling point of 90 ° C. or more By adding a solvent having a boiling point of 90 ° C. or more, bumping during drying can be prevented, the coating film can be leveled, and the smoothness of the surface of the coating film after drying can be improved.
- the addition amount thereof is preferably about 10 to 80% by mass with respect to the entire coating solution.
- 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.
- a laminated ceramic capacitor has a rectangular parallelepiped ceramic body. Inside the ceramic body, first internal electrodes and second internal electrodes are alternately provided along the thickness direction. The first inner electrode is exposed at the first end face of the ceramic body. A first external electrode is provided on the first end face. The first inner electrode is electrically connected to the first outer electrode at the first end face. The second inner electrode is exposed at the second end face of the ceramic body. A second external electrode is provided on the second end face. The second inner electrode is electrically connected to the second outer electrode at the second end face.
- the release film for producing a ceramic green sheet of the present invention is used to produce such a multilayer ceramic capacitor.
- it is manufactured as follows. First, using the release film of the present invention as a carrier film, a ceramic slurry for forming a ceramic body is applied and dried. A conductive layer for forming a first or second internal electrode is printed on the coated and dried ceramic green sheet. The ceramic green sheet, the ceramic green sheet on which the conductive layer for forming the first internal electrode is printed, and the ceramic green sheet on which the conductive layer for forming the second internal electrode is printed are appropriately laminated and pressed. Thus, a mother laminate is obtained. The mother laminate is divided into a plurality of pieces to prepare a green ceramic body. A ceramic body is obtained by firing a green ceramic body. Thereafter, the laminated ceramic capacitor can be completed by forming the first and second external electrodes.
- Tg of each acrylic polyol was determined from the composition ratio of the copolymerization component determined by the above-mentioned NMR measurement and the equation of Fox described above.
- the sample was hand-set and set in a drawing apparatus (made by Toyobo Engineering Co., Ltd.), placed in a hot air circulating oven at 100 ° C., and subjected to a drawing operation slowly.
- the drawing operation was performed until the length was 4 times the length before drawing, and the drawing apparatus was removed from the hot air circulation oven.
- stretching was observed with the optical microscope (magnification: 200 times), and the presence or absence of the cracking by extending
- the contact angle data of water, diiodomethane and ethylene glycol obtained by the above method are calculated from “Kitazaki-Hata” theory to determine the dispersion component ⁇ sd of the surface free energy of the release film, the polar component ⁇ sp and the hydrogen bond component ⁇ sh The sum of each component was taken as the surface free energy ⁇ s. This calculation was performed using calculation software in the contact angle meter software (FAMAS).
- the release film for producing a green sheet obtained in each of the Examples and the Comparative Examples was wound into a roll having a width of 400 mm and a length of 5000 m to obtain a release film roll.
- the release film roll was stored for 30 days in an environment of 40 ° C. and a humidity of 50% or less, and the charge amount at the time of rewinding at 100 m / min was measured using “KSD-0103” manufactured by Kasuga Denki.
- the charge amount was measured every 500 M of the unwinding length at a portion of 100 mm immediately after the unwinding, and the average value was calculated.
- the release film was peeled off to obtain a ceramic green sheet.
- 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. :: No occurrence of pinholes, thickness variation in particular ⁇ ⁇ : No occurrence of pinholes, no thickness variation in particular ⁇ : Occurrence of pinholes is very slight, and thickness variations are slightly visible. X: There are a few pinholes and a slight thickness variation.
- PET (I) Preparation of polyethylene terephthalate pellets (PET (I))
- 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 by an average pressure of 5 passes and an average particle with 1% by mass of ammonium salt of polyacrylic acid attached per calcium carbonate 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 (I)) .
- PET (I) intrinsic viscosity of 0.60 dl / g
- PET (II) Preparation of polyethylene terephthalate pellets (PET (II))
- PET (II) a PET chip having an intrinsic viscosity of 0.62 dl / g which does not contain any particles such as calcium carbonate and silica was obtained (hereinafter referred to as PET (II)).
- PET chips 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 ⁇ m stainless steel fibers, 95% cut diameter
- Two stages of filtration of a sintered filter of 15 ⁇ m stainless steel particles are carried out to merge in a feed block, and PET (I) becomes an anti-mold surface side layer and PET (II) becomes a release surface side layer It is laminated and extruded (casting) in sheet form at a speed of 45 m / min, electrostatically adhered and cooled on a casting drum at 30 ° C.
- the Sa of the release surface side layer of the obtained film Z was 2 nm, and the Sa of the anti-release surface side layer was 28 nm.
- compositional ratio is MMA, St (styrene), SMA (stearyl methacrylate), l-1, l-2, l-3 (unit), HEMA m (unit), MAA, AA (acrylic acid) Is expressed as n (unit).
- the temperature was raised to 255 ° C., and the reaction system was gradually depressurized, and then reacted under a reduced pressure of 30 Pa for 1 hour and 30 minutes to obtain a copolyester resin (B0-1).
- the obtained copolyester resin (B0-1) was pale yellow and transparent.
- the reduced viscosity of the copolyester resin (B0-1) was measured to be 0.60 dl / g.
- the glass transition temperature by DSC was 65.degree.
- polyester water dispersion B-1 (Production of polyester water dispersion B-1)
- a reactor equipped with a stirrer, a thermometer and a reflux apparatus 30 parts by mass of polyester resin (B0-1) and 15 parts by mass of ethylene glycol-n-butyl ether were added, and the mixture was heated and stirred at 110 ° C. to dissolve the resin. After the resin was completely dissolved, 55 parts by weight of water was gradually added to the polyester solution while stirring. After the addition, the solution was cooled to room temperature with stirring to prepare a milky white polyester water dispersion (B-1) with a solid content of 30% by mass.
- polyester water dispersion B-2 (Production of polyester water dispersion B-2) Then, 60 parts by mass of this copolyester resin (B0-2), 45 parts by mass of methyl ethyl ketone and 15 parts by mass of isopropyl alcohol are added to a reactor equipped with a stirrer for producing graft resin, a thermometer, a refluxing device and a fixed amount dropping device. Then, the mixture was heated at 65 ° C. and stirred to dissolve the resin. After the resin was completely dissolved, 24 parts by mass of maleic anhydride was added to the polyester solution.
- polyester graft copolymer dispersion (B-2) was prepared.
- the glass transition temperature of the obtained polyester graft copolymer was 68 ° C.
- a monomer mixture consisting of 126 parts of methyl methacrylate, 210 parts of 2-isopropenyl-2-oxazoline and 84 parts of methoxypolyethylene glycol acrylate prepared in advance and a polymerization initiator, 2,2'-azobis
- An initiator solution consisting of 21 parts of (2-methylbutyronitrile) ("ABN-E” manufactured by Nippon Hydrazine Industry Co., Ltd.) and 189 parts of isopropyl alcohol is added dropwise from the dropping funnel over 2 hours, and reacted, After completion, the reaction was continued for 5 hours. During the reaction, nitrogen gas was kept flowing to keep the temperature in the flask at 80 ⁇ 1 ° C.
- the reaction solution was cooled to obtain a resin (D-1) having an oxazoline group with a solid concentration of 25%.
- the amount of oxazoline groups of the obtained resin (D-1) having an oxazoline group was 4.3 mmol / g, and the number average molecular weight measured by GPC (gel permeation chromatography) was 20000.
- the infrared spectrum of the reaction solution was measured, and it was confirmed that the absorption at a wavelength of 2200 to 2300 cm -1 disappeared.
- the mixture was allowed to cool to 60 ° C., and 567 parts by mass of ion exchange water was added to obtain a carbodiimide water-soluble resin (E-1) having a solid content of 40% by mass.
- Isocyanate Crosslinker F-1 100 parts by mass of polyisocyanate compound having isocyanurate structure (Duranate TPA, manufactured by Asahi Kasei Chemicals Co., Ltd., manufactured by Asahi Kasei Chemicals, Inc.), 55 parts by mass of propylene glycol monomethyl ether acetate, having a stirrer, a thermometer, and a reflux condenser 30 parts by mass of polyethylene glycol monomethyl ether (average molecular weight 750) was charged, and maintained at 70 ° C. for 4 hours under a nitrogen atmosphere. Thereafter, the reaction solution temperature was lowered to 50 ° C., and 47 parts by mass of methyl ethyl ketoxime was dropped. The infrared spectrum of the reaction solution was measured to confirm that the absorption of the isocyanate group disappeared, and a block polyisocyanate water dispersion (F-1) having a solid content of 75% by mass was obtained.
- Duranate TPA manufactured by Asahi
- Acrylic particles G-5 Acrylic particle water dispersion (manufactured by Nippon Shokubai, trade name MX 100 W, average particle diameter 150 nm, solid content concentration 10% by mass)
- Acrylic particles G-6 Acrylic particle water dispersion (manufactured by Nippon Shokubai, trade name MX 200 W, average particle diameter 350 nm, solid content concentration 10 mass%)
- Acrylic particles G-7) Acrylic particle water dispersion (manufactured by Nippon Shokubai, trade name MX 300 W, average particle diameter 450 nm, solid content concentration 10 mass%)
- the solution was diluted to prepare a 2% by mass solid content mold release solution.
- Example 1 Adjustment of slippery coating solution 1 A slippery coating solution 1 having the following composition was prepared.
- (Easy slip coating solution 1) Water 41.86 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-1 16.57 parts by mass (solid content concentration 20% by mass) Oxazoline based crosslinking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
- Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%) 0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration 10% by mass)
- the unstretched PET sheet was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a peripheral speed difference to obtain a uniaxially stretched PET film.
- the above easy-to-slip coating solution was applied to one side of a PET film with a bar coater, and then dried at 80 ° C. for 15 seconds. In addition, it adjusted so that the coating amount after final extending
- a release agent solution X-1 is applied to the surface of the inline coated polyester film obtained above on the surface opposite to the surface on which the lubricant layer is laminated, in a reverse gravure coater in a thickness of 0.1 ⁇ m after drying, and then A mold release coating layer was formed by drying with hot air at 130 ° C. for 30 seconds to obtain a mold release film for producing an ultrathin ceramic green sheet.
- the rollability, process passability, and handleability were excellent without any particular problems. After being wound up as a roll, the winding charge when winding it back again for ceramic sheet coating is low, adhesion of environmental foreign matter can be suppressed, and a ceramic capacitor of good quality is made without lowering the yield of the ceramic capacitor. I was able to.
- Example 2 is the same as Example 1 except that the easy-to-use coating liquid 2 in which the cross-linking agent in the easy-to-use coating liquid 1 used in Example 1 is changed to the carbodiimide crosslinking agent E-1 (solid content 40% by mass) is used. Thus, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 3 is the same as Example 1 except that the easy-to-use coating liquid 3 in which the crosslinking agent in the easy-to-use coating liquid 1 used in Example 1 is changed to the oxazoline crosslinking agent D-2 (solid content concentration 10% by mass) is used. Thus, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 4 A polyester film was obtained in the same manner as in Example 1 except that the easy-sliding coating solution 1 was changed to the following easy-sliding coating solution 4.
- (Easy slip coating solution 4) Water 43.28 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-1 9.47 parts by mass (solid content concentration 20% by mass)
- Oxazoline based crosslinking agent D-1 11.36 parts by mass (solid content concentration 25% by mass)
- Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%) 0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration 10% by mass)
- Example 5 A polyester film was obtained in the same manner as in Example 1 except that the easy sliding coating solution 1 was changed to the following easy sliding coating solution 5.
- (Easy slip coating solution 5) Water 41.15 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-1 20.12 parts by mass (solid content concentration 20% by mass)
- Oxazoline based crosslinking agent D-1 2.84 parts by mass (solid content concentration 25% by mass)
- Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%) 0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration 10% by mass)
- Example 6 The procedure of Example 1 was repeated except that the acrylic polyol A-1 (solid content concentration of 20% by mass) in the slippery coating solution 1 used in Example 1 was changed to acrylic polyol A-2 (solid content concentration of 20% by mass). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 7 Example 1 was repeated except that the acrylic polyol A-1 (solid content concentration 20 mass%) in the slippery coating solution 1 used in Example 1 was changed to acrylic polyol A-3 (solid content concentration 20 mass%). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 8 The procedure of Example 1 was repeated except that the acrylic polyol A-1 (solid content concentration of 20% by mass) in the slippery coating solution 1 used in Example 1 was changed to acrylic polyol A-4 (solid content concentration of 20% by mass). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 1 is the same as Example 1 except that the acrylic polyol A-1 (solid content concentration 20% by mass) in the slippery coating solution 1 used in Example 1 is changed to acrylic polyol A-5 (solid content concentration 20% by mass). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 10 The procedure of Example 1 was repeated except that the acrylic polyol A-1 (solid content concentration of 20% by mass) in the slippery coating solution 1 used in Example 1 was changed to acrylic polyol A-6 (solid content concentration of 20% by mass). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 11 The procedure of Example 1 was repeated except that the acrylic polyol A-1 (solid content concentration of 20% by mass) in the slippery coating solution 1 used in Example 1 was changed to acrylic polyol A-7 (solid content concentration of 20% by mass). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 12 The procedure of Example 1 was repeated except that the acrylic polyol A-1 (solid content concentration of 20% by mass) in the slippery coating solution 1 used in Example 1 was changed to acrylic polyol A-8 (solid content concentration of 20% by mass). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 13 The procedure of Example 1 was repeated except that the acrylic polyol A-1 (solid content concentration of 20% by mass) in the slippery coating solution 1 used in Example 1 was changed to acrylic polyol A-9 (solid content concentration of 20% by mass). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 14 The procedure of Example 1 was repeated except that the acrylic polyol A-1 (solid content concentration of 20% by mass) in the slippery coating solution 1 used in Example 1 was changed to acrylic polyol A-10 (solid content concentration of 20% by mass). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 15 The procedure of Example 1 was repeated except that the acrylic polyol A-1 (solid content concentration of 20% by mass) in the slippery coating solution 1 used in Example 1 was changed to acrylic polyol A-11 (solid content concentration of 20% by mass). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 16 The procedure of Example 1 was repeated except that the acrylic polyol A-1 (solid content concentration of 20% by mass) in the slippery coating solution 1 used in Example 1 was changed to acrylic polyol A-12 (solid content concentration of 20% by mass). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 17 A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy sliding coating solution 1 was changed to the following easy sliding coating solution 17.
- (Easy slip coating solution 17) Water 41.74 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-10 16.57 parts by mass (solid content concentration 20% by mass) Oxazoline based crosslinking agent D-1 5.68 parts by mass (solid content concentration 25% by mass) Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%) Silica particle G-4 0.12 mass parts (average particle diameter 450 nm, solid content concentration 40 mass%) 0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration 10% by mass)
- Example 18 A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy sliding coating solution 1 was changed to the following easy sliding coating solution 18.
- Easy slip coating solution 18 Water 41.15 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-10 16.57 parts by mass (solid content concentration 20% by mass) Oxazoline based crosslinking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
- Silica particle G-2 1.18 mass parts (average particle diameter 40 nm, solid content concentration 40 mass%)
- Silica particle G-4 0.12 mass parts (average particle diameter 450 nm, solid content concentration 40 mass%) 0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration 10% by mass)
- Example 19 A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy sliding coating solution 1 was changed to the following easy sliding coating solution 19.
- Easy slip coating solution 19 Water 41.27 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-10 16.57 parts by mass (solid content concentration 20% by mass) Oxazoline based crosslinking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
- Silica particle G-3 1.18 mass parts (average particle diameter 100 nm, solid content concentration 40 mass%) 0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration 10% by mass)
- Example 20 A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy-sliding coating solution 1 was changed to the following easy-sliding coating solution 20.
- (Easy slip coating solution 20) Water 40.09 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-10 16.57 parts by mass (solid content concentration 20% by mass) Oxazoline based crosslinking agent D-1 5.68 parts by mass (solid content concentration 25% by mass) Acrylic particles G-5 2.37 parts by mass (average particle size 150 nm, solid content concentration 10% by mass) 0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration 10% by mass)
- Example 21 A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the formation of the release coating layer was performed as follows.
- the release agent solution X-2 was applied to the obtained in-line coated polyester film with a reverse gravure coater so as to have a thickness after drying of 0.1 ⁇ m, and then dried with a hot air of 90 ° C. for 30 seconds.
- Ultraviolet irradiation 300 mJ / cm 2
- an electrode lamp H bulb manufactured by Heraeus Co., Ltd.
- Example 1 is the same as Example 1 except that the acrylic polyol A-1 (solid content concentration of 20% by mass) in the slippery coating solution 1 used in Example 1 is changed to acrylic polyol A-13 (solid content concentration of 20% by mass). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
- Example 23 A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy-sliding coating solution 1 was changed to the following easy-sliding coating solution 22.
- (Easy slip coating solution 22) Water 41.39 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-13 16.57 parts by mass (solid content concentration 20% by mass) Oxazoline based crosslinking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
- Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%)
- Acrylic particle G-6 0.47 mass parts (average particle diameter 350 nm, solid content concentration 10 mass%) 0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration 10% by mass)
- Example 24 A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy sliding coating solution 1 was changed to the following easy sliding coating solution 23.
- Easy slip coating solution 23 Water 41.39 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-13 16.57 parts by mass (solid content concentration 20% by mass) Oxazoline based crosslinking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
- Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%)
- Acrylic particles G-7 0.47 parts by mass (average particle diameter 450 nm, solid content concentration 10% by mass) 0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration 10% by mass)
- Example 25 A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy-sliding coating solution 1 was changed to the following easy-sliding coating solution 24.
- (Easy slip coating solution 24) Water 39.62 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-13 16.57 parts by mass (solid content concentration 20% by mass) Oxazoline based crosslinking agent D-1 5.68 parts by mass (solid content concentration 25% by mass) Acrylic particles G-5 2.37 parts by mass (average particle size 150 nm, solid content concentration 10% by mass) Acrylic particles G-7 0.47 parts by mass (average particle diameter 450 nm, solid content concentration 10% by mass) 0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration 10% by mass)
- Example 1 A polyester film was obtained in the same manner as in Example 1 except that the easy sliding coating solution 1 was changed to the following easy sliding coating solution 25.
- Easy slip coating solution 25 Water 48.33 parts by mass Isopropyl alcohol 35.00 parts by mass Polyester water dispersion B-1 15.78 parts by mass (solid content concentration 30% by mass) Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%) Surfactant (fluorine-based, solid content 10% by mass) 0.30 parts by mass
- Example 2 A polyester film was obtained in the same manner as in Example 1 except that the easy-sliding coating solution 1 was changed to the following easy-sliding coating solution 26.
- Easy slip coating solution 26 Water 45.18 parts by mass Isopropyl alcohol 35.00 parts by mass Polyester water dispersion B-2 18.93 parts by mass (solid content concentration 25% by mass) Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%) Surfactant (fluorine-based, solid content 10% by mass) 0.30 parts by mass
- Example 3 A polyester film was obtained in the same manner as in Example 1 except that the easy sliding coating solution 1 was changed to the following easy sliding coating solution 27.
- Easy slip coating solution 27 Water 51.32 parts by mass Isopropyl alcohol 35.00 parts by mass Polyurethane resin water dispersion C-1 12.79 parts by mass (solid content concentration 37% by mass) Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%) Surfactant (fluorine-based, solid content 10% by mass) 0.30 parts by mass
- Example 4 A polyester film was obtained in the same manner as in Example 1 except that the easy sliding coating solution 1 was changed to the following easy sliding coating solution 28.
- Easy slip coating solution 28 Water 47.39 parts by mass Isopropyl alcohol 35.00 parts by mass Polyester water dispersion B-1 11.04 parts by mass (solid content concentration 30% by mass) Oxazoline based crosslinking agent D-1 5.68 parts by mass (solid content concentration 25% by mass) Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%) Surfactant (fluorine-based, solid content 10% by mass) 0.30 parts by mass
- Example 5 A polyester film was obtained in the same manner as in Example 1 except that the easy sliding coating solution 1 was changed to the following easy sliding coating solution 29.
- Easy slip coating solution 29 Water 49.51 parts by mass Isopropyl alcohol 35.00 parts by mass Polyester water dispersion B-1 11.04 parts by mass (solid content concentration 30% by mass) Carbodiimide based crosslinking agent E-1 3.55 parts by mass (solid content concentration 40% by mass) Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%) Surfactant (fluorine-based, solid content 10% by mass) 0.30 parts by mass
- Example 6 A polyester film was obtained in the same manner as in Example 1 except that the easy-sliding coating solution 1 was changed to the following easy-sliding coating solution 30.
- Easy slip coating solution 30 Water 40.44 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-1 23.67 parts by mass (solid content concentration 20% by mass) Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%) 0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration 10% by mass)
- Example 7 A polyester film was obtained in the same manner as in Example 1 except that the easy sliding coating solution 1 was changed to the following easy sliding coating solution 31.
- Easy slip coating solution 31 Water 45.65 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-1 16.57 parts by mass (solid content concentration 20% by mass) Isocyanate crosslinker F-1 1.89 parts by mass (solid content concentration 75% by mass) Silica particle G-1 0.59 mass parts (average particle diameter 200 nm, solid content concentration 40 mass%) 0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration 10% by mass)
- Example 8 As a film for forming a release coating layer, it was changed to E5000-25 ⁇ m (made by Toyobo Co., Ltd.) and used instead of the inline coating film having a slippery coating layer on one surface prepared in Example 1 A release film for producing a ceramic green sheet was obtained in the same manner as in Example 1. E5000 contained particles inside the film, and the Sa on both surfaces was both 0.031 ⁇ m.
- Example 9 Similar to Example 1 except that instead of the inline coating film having a slippery coating layer on one surface prepared in Example 1 as a film for forming a release coating layer, the laminated film Z is changed and used.
- a release film for producing a ceramic green sheet was obtained by the following method. A release coating layer was provided on the surface (layer containing no particles) of the laminated film Z from which the PET (II) pellets of the laminated film Z were discharged.
- the composition of each of the resin, the crosslinking agent, the particles, and the surfactant in the slippery coating liquid is described as a solid part by mass, and the resin and the crosslinker present in the slippery coating liquid
- the total of parts by mass of solid components of particles and surfactant becomes part by mass of total solid content of the slippery coating layer, and the parts by mass of each solid component of resin, crosslinking agent, particles and surfactant are easily slipped
- the weight percentage of the resin, the crosslinking agent, the particles, and the total solid content in the slip coating layer of the surfactant can be determined by dividing by the mass part of the total solid content of the coating layer.
- a ceramic capacitor of good quality is formed without lowering the yield of the ceramic capacitor.
- a release film a polyester film substantially free of inorganic particles is used as a substrate, a release coating layer is provided on one surface of the substrate, and particles are contained on the other surface.
- a slippery coating layer the slippery coating layer being formed by curing a composition containing an acrylic resin and at least one crosslinker selected from an oxazoline crosslinker or a carbodiimide crosslinker; The crosslink density of the coating layer is high, and the amount of deformation of the easy-to-slip coating layer is small.
- a slippery coating formed by curing a composition containing the acrylic resin specified in the present invention and at least one crosslinking agent selected from an oxazoline crosslinking agent or a carbodiimide crosslinking agent. Since the layer is not a layer, the crosslink density of the easily slip coating layer is lowered, and the deformation amount of the easily slip coating layer is increased. Since the contact area is increased when the release layer and the slippery layer are separated when the release-treated film roll is unwound, it is considered that the unwinding charging is increased. Further, in Comparative Examples 8 and 9, although the unwinding charge is low, the easily slip coating layer defined in the present invention is not provided, and the surface roughness of the slippery surface is large. did.
- the present invention even when the thickness of the ceramic green sheet is reduced, mold release for manufacturing the ceramic green sheet can be achieved simultaneously with preventing pinholes and partial thickness variations and preventing adhesion of environmental foreign matter due to charging. It becomes possible to provide a film. Moreover, by using the release film for producing a ceramic green sheet of the present invention, a ceramic green sheet of an extremely thin film can be obtained, and a minute ceramic capacitor can be efficiently produced.
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Abstract
Description
1. 無機粒子を実質的に含有していないポリエステルフィルムを基材とし、前記基材の一方の表面上に離型塗布層を有し、かつ、もう一方の表面上に粒子を含有する易滑塗布層を有し、易滑塗布層がアクリル樹脂、及びオキサゾリン系架橋剤またはカルボジイミド系架橋剤から選ばれる少なくとも1種の架橋剤を含有する組成物が硬化されてなるセラミックグリーンシート製造用離型フィルム。
2. アクリル樹脂のガラス転移温度が50℃以上110℃以下である上記第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. アクリル樹脂の酸価が40mgKOH/g以上400mgKOH/g以下である上記第1または第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. 易滑塗布層の領域表面平均粗さ(Sa)が1nm以上25nm以下、最大突起高さ(P)が60nm以上500nm以下、かつ粗さ曲線要素の平均長さ(RSm)が10μm以下である上記第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。
5. 易滑塗布層の厚みが0.001μm以上2μm以下である上記第1~第4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。
6. 上記第1~第5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るセラミックグリーンシートの製造方法。
7. 製造するセラミックグリーンシートの厚みが、0.2μm以上2.0μm以下である上記第6に記載のセラミックグリーンシートの製造方法。
8. 上記第6または第7に記載のセラミックグリーンシートの製造方法を採用するセラミックコンデンサの製造方法。
本発明のセラミックグリーンシート製造用離型フィルム(以下、単に離型フィルムということがある)は、基材フィルムである二軸配向ポリエステルフィルムの片面に離型塗布層、もう一方の面に粒子を含む易滑塗布層を有する離型フィルムである。
本発明において好ましく基材として用いられるフィルムとしては、ポリエステル樹脂より構成されるフィルムであり、主に、ポリエチレンテレフタレート、ポリプロピレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートから選ばれる少なくとも1種を含むポリエステルフィルムが好ましい。また、前記のようなポリエステルのジカルボン酸成分、又は、ジオール成分の一部として、第三成分モノマーが共重合されたポリエステルからなるフィルムであってもよい。これらのポリエステルフィルムの中でも、物性とコストのバランスからポリエチレンテレフタレートフィルムが最も好ましい。
本発明の離型フィルムは、上記のようなポリエステル製の基材フィルムの一方の表面上に易滑塗布層を有するものである。易滑塗布層中には、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。
本発明における易滑塗布層を構成するバインダー樹脂としてはアクリル樹脂が含まれていることが好ましい。アクリル樹脂は、分子中に水酸基、及びカルボキシル基を有するアクリル樹脂であることが好ましい。水酸基を有する構成ユニットは、全構成ユニット100モル%中、20~90モル%含まれていることが更に好ましい。水酸基を有する構成ユニットが20モル%以上であると、アクリル樹脂の水溶性を適度に保つことができ好ましい。一方、90モル%以下であると、アクリル樹脂の水酸基と易滑塗布層中に含まれる粒子が極端に相互作用を引き起こさず粒子が均一に分散され好ましい。
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、易滑塗布層はオキサゾリン系架橋剤またはカルボジイミド系架橋剤から選ばれる少なくとも1種の架橋剤を含有していることが好ましい。オキサゾリン系架橋剤またはカルボジイミド系架橋剤を含有させることにより、PET基材との密着性を向上させること、及びアクリル樹脂のカルボキシル基との架橋を促進させることにより易滑層の塗膜強度を向上させることができ、結果として離型フィルムロールを巻きだした時の巻出し帯電を抑制することができる。また他の架橋剤を併用してもよく、併用でき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、シラノール系等が挙げられる。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。
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。塗布層に適度な滑り性を与えるためには、シリカが特に好ましく使用される。
易滑塗布層に他の機能性を付与するために、塗布外観を損なわない程度の範囲で、各種の添加剤を含有させても構わない。前記添加剤としては、例えば、蛍光染料、蛍光増白剤、可塑剤、紫外線吸収剤、顔料分散剤、抑泡剤、消泡剤、防腐剤等が挙げられる。
本発明において、基材フィルムとなるポリエステルフィルムは、一般的なポリエステルフィルムの製造方法に従って製造することができる。例えば、ポリエステル樹脂を溶融し、シート状に押出し成形された無配向ポリエステルをガラス転移温度以上の温度において、ロールの速度差を利用して縦方向に延伸した後、テンターにより横方向に延伸し、熱処理を施す方法が挙げられる。また、テンター内で縦横同時に二軸延伸する方法も挙げられる。
本発明における離型塗布層を構成する樹脂には特に限定はなく、シリコーン樹脂、フッ素樹脂、アルキド樹脂、各種ワックス、脂肪族オレフィンなどを用いることができ、各樹脂を単独もしくは、2種類以上併用することもできる。
一般に、積層セラミックコンデンサは、直方体状のセラミック素体を有する。セラミック素体の内部には、第1の内部電極と第2の内部電極とが厚み方向に沿って交互に設けられている。第1の内部電極は、セラミック素体の第1の端面に露出している。第1の端面の上には第1の外部電極が設けられている。第1の内部電極は、第1の端面において第1の外部電極と電気的に接続されている。第2の内部電極は、セラミック素体の第2の端面に露出している。第2の端面の上には第2の外部電極が設けられている。第2の内部電極は、第2の端面において第2の外部電極と電気的に接続されている。
アクリルポリオール中に導入された共重合成分の比率は、核磁気共鳴分光法(1H-N
MR、13C-NMR:Varian Unity 400、Agilent社製)を用いて確認した。測定は、合成したアクリルポリオール中の溶媒を真空乾燥機にて除去した後、乾固物を重クロロフォルムに溶解させて行った。得られたNMRスペクトルから、各基の部位に帰属される化学シフトδ(ppm)のピークを同定した。得られた各ピークの積分強度を求め、各基の部位の水素数と積分強度から、アクリルポリオールに導入された共重合成分の組成比率(mol%)を確認した。
上記NMR測定で求めた共重合成分の組成比率と、前記したFoxの式から各アクリルポリオールのTgを求めた。
アクリルポリオール自体の延伸適性を評価するため、合成したアクリルポリオール(1)~(13)を、固形分濃度が12質量%となるように、イソプロパノール30質量%と水70質量%の混合溶媒(25℃)中に投入して、アクリルポリオール単体の溶解液を調製した後、縦延伸のみを行ったポリエステルフィルムの表面に、溶解液をメイヤーバー#5で塗布した。次いで、塗布層(厚み6.5μm)を形成したフィルムサンプルを、温度60℃に設定した熱風循環オーブン中に30秒間静置した後、フィルムサンプルをオーブンから取り出してプレ乾燥を行った。次いで、サンプルを手廻し延伸装置(東洋紡エンジニアリング社製)にセットして、100℃の熱風循環オーブン中に入れ、ゆっくりと延伸操作を行った。延伸前の長さの4倍の長さになるまで延伸操作を行い、延伸装置を熱風循環オーブンから取り出した。その後、延伸後の塗膜を光学顕微鏡(倍率:200倍)にて観察し、下記の基準に従って、延伸によるクラッキングの有無を判断した。
○:クラックが全く見られない。
△:クラックがやや見られる(1本~4本)。
×:5本以上のクラック、もしくは全面にクラックが見られる。
非接触表面形状計測システム(VertScan R550H-M100)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)、粗さ曲線要素の平均長さ(RSm)は、5回測定の平均値を採用し、最大突起高さ(P)は5回測定の最大値を採用した。
(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
・測定面積 187×139μm (Sa,P測定)
・測定長さ(Lr:基準長さ):187μm(RSm測定)
上記(1)で測定した最大突起高さ(P)の値で下記のような基準で判断した。
○: 最大突起高さ(P)が0.2μm以下
○△: 最大突起高さ(P)が0.2μmより大きく、0.3μmより小さい。
△: 最大突起高さ(P)が0.3μm以上
暗室にて目視でLEDライト(LED LENSER社製、LED LENSER P5R.2)を用いて、A4サイズのグリーンシート製造用剥離フィルムを4枚観察し、白く視認できる粒子凝集物にマーキングを行い、下記のような基準で判断した。
◎: 粒子凝集物無し
○: 粒子凝集物が1個から3個。
△: 粒子凝集物が4個以上。
摩擦堅牢度試験機(大栄科学精器製作所製、RT-200)にグリーンシート製造用剥離フィルム(3cm(フィルム幅方向)×20cm(フィルム長手方向))を易滑塗布層が上になるように取り付け、荷重ヘッド部(2cmx2cm、200g)と試料フィルムの接触部にアルミ箔(厚さ80μm、算術的平均表面粗さ0.03μm)を用い、10cmの距離を1往復2秒の速度で10往復させた。黒台紙の上に得られたフィルムをのせ、粉落ちしているか目視で確認した。
○:黒台紙上で粉落ちが確認できない。
△:黒台紙上で全体的にわずかな粉落ちが確認できる。
25℃、50%RHの条件下で接触角計(協和界面科学株式会社製: 全自動接触角計 DM-701)を用いて離型フィルムの離型面に水(液滴量1.8μL)、ジヨードメタン(液適量0.9μL)、エチレングリコール(液適量0.9μL)の液滴を作成しその接触角を測定した。接触角は、各液を離型フィルムに滴下後10秒後の接触角を採用した。前記方法で得られた、水、ジヨードメタン、エチレングリコールの接触角データを「北崎-畑」理論より計算し離型フィルムの表面自由エネルギーの分散成分γsd、極性成分γsp、水素結合成分γshを求め、各成分を合計したものを表面自由エネルギーγsとした。本計算には、本接触角計ソフトウェア(FAMAS)内の計算ソフトを用いて行った。
各実施例および各比較例で得られたグリーンシート製造用剥離フィルムを、幅400mm、長さ5000mのロール状に巻き上げ、剥離フィルムロールを得た。この剥離フィルムロールを40℃、湿度50%以下の環境下に30日間保管した後、100m/minで巻き返す際の帯電量を春日電機社製「KSD-0103」を用いて測定した。帯電量は、巻出し直後100mmの箇所について、巻出し長さ500M毎に測定し、その平均値を算出した。
○:±3kV未満
○△:±3kV以上、5kV未満
△:±5kV以上、10kV未満
×:±10kV以上
下記、材料からなる組成物を攪拌混合し、2.0mmのガラスビーズを分散媒とするペイントシェーカーを用いて2時間分散し、セラミックスラリーを得た。
トルエン 22.5質量%
エタノール 22.5質量%
チタン酸バリウム 50 質量%
(富士チタン社製 HPBT-1)
ポリビニルブチラール 5 質量%
(積水化学社製 エスレックBH-3)
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スラリーが0.5μmの厚みになるように塗布し90℃で1分乾燥後、スラリー面と平滑化塗布層面を重ね合わせ、10分間、1kg/cm2の加重を掛けたあと、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。
◎:ピンホールの発生なし、厚みばらつき特に良好
○:ピンホールの発生なし、厚みばらつき特に問題なし
△:ピンホールの発生がごくわずかにあり、厚みばらつきが若干見える。
×:ピンホールの発生が少しあり、及び、厚みばらつきが少し目立つ。
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(I)と略す)。PETチップ中の滑剤含有量は0.6質量%であった。
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(II)と略す。)。
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させ、PET(I)を反離型面側層、PET(II)を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(キャステイング)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(I)/(II)=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Zを得た。得られたフィルムZの離型面側層のSaは2nm、反離型面側層のSaは28nmであった。
撹拌機、還流式冷却器、温度計および窒素吹き込み管を備えた4つ口フラスコに、メチルメタクリレート(MMA)77質量部、ヒドロキシエチルメタクリレート(HEMA)100質量部、メタクリル酸(MAA)33質量部およびイソプロピルアルコール(IPA)490質量部を仕込み、撹拌を行いながら80℃までフラスコ内を昇温した。フラスコ内を80℃に維持したまま3時間の撹拌を行い、その後、2,2-アゾビス-2―メチル-N-2-ヒドロキシエチルプロピオンアミドを0.5質量部フラスコに添加した。フラスコ内を120℃に昇温しながら窒素置換を行った後、120℃で混合物を2時間撹拌した。
次いで、120℃で1.5kPaの減圧操作を行い、未反応の原材料と溶媒を除去し、アクリルポリオールを得た。フラスコ内を大気圧に戻して室温まで冷却し、IPA水溶液(水含量50質量%)840質量部を添加混合した。その後、撹拌しながら滴下ロートを用いて、トリエチルアミンを加え、溶液のpHが5.5~7.5の範囲になるまでアクリルポリオールの中和処理を行い、固形分濃度が20質量%のアクリルポリオール(A-1)を得た。アクリルポリオール(A-1)のNMR測定による組成比率、Tg、延伸適性、酸価を表1に併記した。
表1に示したように、MMA、St、SMA、HEMA、MAA、AA、仕込み時IPA、希釈時IPA水溶液の量、及び中和剤を変更した以外はアクリルポリオール1の製造と同様にして、固形分濃度が20質量%のアクリルポリオール(A-2)~(A-13)を得た。アクリルポリオール(A-2)~(A-13)のNMR測定による組成比率、Tg、延伸適性、酸価を表1に併記した。なお、組成比率は、MMA、St(スチレン)、SMA(ステアリルメタクリレート)、を各々l-1、l-2、l-3(単位)、HEMAをm(単位)、MAA、AA(アクリル酸)をn(単位)として表した。
攪拌機、温度計、および部分還流式冷却器を具備するステンレススチール製オートクレーブに、ジメチルテレフタレート194.2質量部、ジメチルイソフタレート184.5質量部、ジメチルー5-ナトリウムスルホイソフタレート14.8質量部、エチレングリコール185.1質量部、ネオペンチルグリコール185.1質量部、およびテトラ-n-ブチルチタネート0.2質量部を仕込み、160℃から220℃の温度で4時間かけてエステル交換反応を行なった。次いで255℃まで昇温し、反応系を徐々に減圧した後、30Paの減圧下で1時間30分反応させ、共重合ポリエステル樹脂(B0-1)を得た。得られた共重合ポリエステル樹脂(B0-1)は、淡黄色透明であった。共重合ポリエステル樹脂(B0-1)の還元粘度を測定したところ,0.60dl/gであった。DSCによるガラス転移温度は65℃であった。
攪拌機、温度計と還流装置を備えた反応器に、ポリエステル樹脂(B0-1)30質量部、エチレングリコール-n-ブチルエーテル15質量部を入れ、110℃で加熱、攪拌し樹脂を溶解した。樹脂が完全に溶解した後、水55質量部をポリエステル溶液に攪拌しつつ徐々に添加した。添加後、液を攪拌しつつ室温まで冷却して、固形分30質量%の乳白色のポリエステル水分散体(B-1)を作製した。
撹拌機、温度計、および部分還流式冷却器を具備したステンレススチール製オートクレーブに、ジメチルテレフタレート163質量部、ジメチルイソフタレート163質量部、1,4ブタンジオール169質量部、エチレングリコール324質量部、およびテトラ-n-ブチルチタネート0.5質量部を仕込み、160℃から220℃まで、4時間かけてエステル交換反応を行った。
次いで、フマル酸14質量部およびセバシン酸203質量部を加え、200℃から220℃まで1時間かけて昇温し、エステル化反応を行った。次いで、255℃まで昇温し、反応系を徐々に減圧した後、29Paの減圧下で1時間30分反応させ、疎水性共重合ポリエステル樹脂(B0-2)を得た。得られた疎水性共重合ポリエステル樹脂(B0-2)は、淡黄色透明であった。
次いで、グラフト樹脂の製造撹拌機、温度計、還流装置と定量滴下装置を備えた反応器に、この共重合ポリエステル樹脂(B0-2)60質量部、メチルエチルケトン45質量部およびイソプロピルアルコール15質量部を入れ、65℃で加熱、撹拌し、樹脂を溶解した。樹脂が完全に溶解した後、無水マレイン酸24質量部をポリエステル溶液に添加した。
次いで、スチレン16質量部、およびアゾビスジメチルバレロニトリル1.5質量部をメチルエチルケトン19質量部に溶解した溶液を、0.1ml/分でポリエステル溶液中に滴下し、さらに2時間撹拌を続けた。反応溶液から分析用のサンプリングを行った後、メタノール8質量部を添加した。次いで、水300質量部とトリエチルアミン24質量部を反応溶液に加え、1時間撹拌した。
その後、反応器の内温を100℃に上げ、メチルエチルケトン、イソプロピルアルコール、過剰のトリエチルアミンを蒸留により留去し、淡黄色透明のポリエステル系樹脂を得、固形分濃度25質量%の均一な水分散性ポリエステル系グラフト共重合体分散液(B-2)を調製した。得られたポリエステル系グラフト共重合体のガラス転移温度は68℃であった。
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、4,4-ジシクロヘキシルメタンジイソシアネート43.75質量部、ジメチロールブタン酸12.85質量部、数平均分子量2000のポリヘキサメチレンカーボネートジオール153.41質量部、ジブチルスズジラウレート0.03質量部、及び溶剤としてアセトン84.00質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン8.77質量部を添加し、ポリウレタンプレポリマー溶液を得た。次に、高速攪拌可能なホモディスパーを備えた反応容器に、水450gを添加して、25℃に調整して、2000min-1で攪拌混合しながら、ポリウレタンプレポリマー溶液を添加して水分散した。その後、減圧下で、アセトンおよび水の一部を除去することにより、固形分37質量%の水溶性ポリウレタン樹脂溶液C-1を調製した。得られたポリウレタン樹脂のガラス転移点温度は-30℃であった。
撹拌機、還流冷却器、窒素導入管および温度計を備えたフラスコに、イソプロピルアルコール460.6部を仕込み、緩やかに窒素ガスを流しながら80℃に加熱した。そこへ予め調製しておいたメタクリル酸メチル126部、2-イソプロペニル-2-オキサゾリン210部およびメトキシポリエチレングリコールアクリレート84部からなる単量体混合物と、重合開始剤である2,2’-アゾビス(2-メチルブチロニトリル)(日本ヒドラジン工業株式会社製「ABN-E」)21部およびイソプロピルアルコール189部からなる開始剤溶液を、それぞれ滴下漏斗から2時間かけて滴下して反応させ、滴下終了後も引き続き5時間反応させた。反応中は窒素ガスを流し続け、フラスコ内の温度を80±1℃に保った。その後、反応液を冷却し、固形分濃度25%のオキサゾリン基を有する樹脂(D-1)を得た。得られたオキサゾリン基を有する樹脂(D-1)のオキサゾリン基量は4.3mmol/gであり、GPC(ゲルパーミエーションクロマトグラフィ)により測定した数平均分子量は20000であった。
上記オキサゾリン基を有する樹脂(D-1)の合成と同様の方法で、組成(オキサゾリン基量および分子量)の異なる固形分濃度10%のオキサゾリン基を有する樹脂(D-2)を得た。得られたオキサゾリン基を有する樹脂(D-2)のオキサゾリン基量は7.7mmol/gであり、GPCにより測定した数平均分子量は40000であった。
撹拌機、温度計、還流冷却管を備えたフラスコにヘキサメチレンジイソシアネート168質量部とポリエチレングリコールモノメチルエーテル(M400、平均分子量400)220質量部を仕込み、120℃で1時間、撹拌し、更に4,4’-ジシクロヘキシルメタンジイソシアネート26質量部とカルボジイミド化触媒として3-メチル-1-フェニル-2-フォスフォレン-1-オキシド3.8質量部(全イソシイアネートに対し2質量%)を加え、窒素気流下185℃で更に5時間撹拌した。反応液の赤外スペクトルを測定し、波長2200~2300cm-1の吸収が消失したことを確認した。60℃まで放冷し、イオン交換水を567質量部加え、固形分40質量%のカルボジイミド水溶性樹脂(E-1)を得た。
撹拌機、温度計、還流冷却管を備えたフラスコにヘキサメチレンジイソシアネートを原料としたイソシアヌレート構造を有するポリイソシアネート化合物(旭化成ケミカルズ製、デュラネートTPA)100質量部、プロピレングリコールモノメチルエーテルアセテート55質量部、ポリエチレングリコールモノメチルエーテル(平均分子量750)30質量部を仕込み、窒素雰囲気下、70℃で4時間保持した。その後、反応液温度を50℃に下げ、メチルエチルケトオキシム47質量部を滴下した。反応液の赤外スペクトルを測定し、イソシアネート基の吸収が消失したことを確認し、固形分75質量%のブロックポリイソシアネート水分散液(F-1)を得た。
コロイダルシリカ(日産化学製、商品名MP2040、平均粒径200nm、固形分濃度40質量%)
コロイダルシリカ(日産化学製、商品名スノーテックスXL、平均粒径40nm、固形分濃度40質量%)
コロイダルシリカ(日産化学製、商品名スノーテックスZL、平均粒径100nm、固形分濃度40質量%)
コロイダルシリカ(日産化学製、商品名MP4540M、平均粒径450nm、固形分濃度40質量%)
アクリル粒子水分散体(日本触媒製、商品名MX100W、平均粒径150nm、固形分濃度10質量%)
アクリル粒子水分散体(日本触媒製、商品名MX200W、平均粒径350nm、固形分濃度10質量%)
アクリル粒子水分散体(日本触媒製、商品名MX300W、平均粒径450nm、固形分濃度10質量%)
熱硬化型アミノアルキド樹脂(日立化成社製 テスファイン314、固形分60質量%)100質量部と硬化触媒としてp-トルエンスルホン酸(日立化成社製、ドライヤー900、固形分50質量%)1.2質量部を、トルエン/メチルエチルケトン/ヘプタン(=3:5:2)溶液で希釈し、固形分2質量%の離型剤溶液を調製した。
UV硬化型シリコーン樹脂(モメンティブ社製 UV9300、固形分濃度100質量%)100質量部と硬化触媒ビス(アルキルフェニル)ヨードニウムヘキサフルオロアンチモネート1質量部を、トルエン/メチルエチルケトン/ヘプタン(=3:5:2)溶液で希釈し、固形分2質量%の離型剤溶液を調製した。
(易滑塗布液1の調整)
下記の組成の易滑塗布液1を調整した。
(易滑塗布液1)
水 41.86質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-1 16.57質量部
(固形分濃度20質量%)
オキサゾリン系架橋剤D-1 5.68質量部
(固形分濃度25質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
フィルム原料ポリマーとして、固有粘度(溶媒:フェノール/テトラクロロエタン=60/40)が0.62dl/gで、かつ粒子を実質的に含有していないPET樹脂ペレット(PET(II))を、133Paの減圧下、135℃で6時間乾燥した。その後、押し出し機に供給し、約280℃でシート状に溶融押し出しして、表面温度20℃に保った回転冷却金属ロール上で急冷密着固化させ、未延伸PETシートを得た。
上記で得たインラインコーティングポリエステルフィルムに離型剤溶液X-1を易滑塗布層積層面とは反対表面に、乾燥後の厚みで0.1μmとなるようにリバースグラビアコーターにて塗布し、次いで、130℃の熱風で30秒間乾燥することで離型塗布層を形成し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。巻き取り性等、工程通過性、ハンドリング性は特に問題なく優秀であった。ロールとして巻き取った後に、セラミックシート塗工のために再度巻きだした時の巻出し帯電も低く、環境異物の付着が抑制できセラミックコンデンサの歩留まりを落とすことなく、品質の良いセラミックコンデンサを作成することができた。
実施例1で使用した易滑塗布液1中の架橋剤をカルボジイミド系架橋剤E-1(固形分濃度40質量%)に変更した易滑塗布液2を使用した以外は、実施例1と同様にして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。
(易滑塗布液2)
水 43.99質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-1 16.57質量部
(固形分濃度20質量%)
カルボジイミド系架橋剤E-1 3.55質量部
(固形分濃度40質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
実施例1で使用した易滑塗布液1中の架橋剤をオキサゾリン系架橋剤D-2(固形分濃度10質量%)に変更した易滑塗布液3を使用した以外は、実施例1と同様にして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。
(易滑塗布液3)
水 33.34質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-1 16.57質量部
(固形分濃度20質量%)
オキサゾリン系架橋剤D-2 14.20質量部
(固形分濃度10質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
易滑塗布液1を、下記の易滑塗布液4に変更した以外は、実施例1と同様にしてポリエステルフィルムを得た。
(易滑塗布液4)
水 43.28質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-1 9.47質量部
(固形分濃度20質量%)
オキサゾリン系架橋剤D-1 11.36質量部
(固形分濃度25質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
易滑塗布液1を、下記の易滑塗布液5に変更した以外は、実施例1と同様にしてポリエステルフィルムを得た。
(易滑塗布液5)
水 41.15質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-1 20.12質量部
(固形分濃度20質量%)
オキサゾリン系架橋剤D-1 2.84質量部
(固形分濃度25質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
実施例1で使用した易滑塗布液1中のアクリルポリオールA-1(固形分濃度20質量%)をアクリルポリオールA-2(固形分濃度20質量%)に変更した以外は、実施例1と同様にして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。
実施例1で使用した易滑塗布液1中のアクリルポリオールA-1(固形分濃度20質量%)をアクリルポリオールA-3(固形分濃度20質量%)に変更した以外は、実施例1と同様にして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。
実施例1で使用した易滑塗布液1中のアクリルポリオールA-1(固形分濃度20質量%)をアクリルポリオールA-4(固形分濃度20質量%)に変更した以外は、実施例1と同様にして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。
実施例1で使用した易滑塗布液1中のアクリルポリオールA-1(固形分濃度20質量%)をアクリルポリオールA-5(固形分濃度20質量%)に変更した以外は、実施例1と同様にして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。
実施例1で使用した易滑塗布液1中のアクリルポリオールA-1(固形分濃度20質量%)をアクリルポリオールA-6(固形分濃度20質量%)に変更した以外は、実施例1と同様にして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。
実施例1で使用した易滑塗布液1中のアクリルポリオールA-1(固形分濃度20質量%)をアクリルポリオールA-7(固形分濃度20質量%)に変更した以外は、実施例1と同様にして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。
実施例1で使用した易滑塗布液1中のアクリルポリオールA-1(固形分濃度20質量%)をアクリルポリオールA-8(固形分濃度20質量%)に変更した以外は、実施例1と同様にして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。
実施例1で使用した易滑塗布液1中のアクリルポリオールA-1(固形分濃度20質量%)をアクリルポリオールA-9(固形分濃度20質量%)に変更した以外は、実施例1と同様にして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。
実施例1で使用した易滑塗布液1中のアクリルポリオールA-1(固形分濃度20質量%)をアクリルポリオールA-10(固形分濃度20質量%)に変更した以外は、実施例1と同様にして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。
実施例1で使用した易滑塗布液1中のアクリルポリオールA-1(固形分濃度20質量%)をアクリルポリオールA-11(固形分濃度20質量%)に変更した以外は、実施例1と同様にして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。
実施例1で使用した易滑塗布液1中のアクリルポリオールA-1(固形分濃度20質量%)をアクリルポリオールA-12(固形分濃度20質量%)に変更した以外は、実施例1と同様にして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。
易滑塗布液1を下記の易滑塗布液17に変更した以外は、実施例1と同様にして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。
(易滑塗布液17)
水 41.74質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-10 16.57質量部
(固形分濃度20質量%)
オキサゾリン系架橋剤D-1 5.68質量部
(固形分濃度25質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
シリカ粒子G-4 0.12質量部
(平均粒径450nm、固形分濃度40質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
易滑塗布液1を下記の易滑塗布液18に変更した以外は、実施例1と同様にして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。
(易滑塗布液18)
水 41.15質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-10 16.57質量部
(固形分濃度20質量%)
オキサゾリン系架橋剤D-1 5.68質量部
(固形分濃度25質量%)
シリカ粒子G-2 1.18質量部
(平均粒径40nm、固形分濃度40質量%)
シリカ粒子G-4 0.12質量部
(平均粒径450nm、固形分濃度40質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
易滑塗布液1を下記の易滑塗布液19に変更した以外は、実施例1と同様にして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。
(易滑塗布液19)
水 41.27質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-10 16.57質量部
(固形分濃度20質量%)
オキサゾリン系架橋剤D-1 5.68質量部
(固形分濃度25質量%)
シリカ粒子G-3 1.18質量部
(平均粒径100nm、固形分濃度40質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
易滑塗布液1を下記の易滑塗布液20に変更した以外は、実施例1と同様にして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。
(易滑塗布液20)
水 40.09質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-10 16.57質量部
(固形分濃度20質量%)
オキサゾリン系架橋剤D-1 5.68質量部
(固形分濃度25質量%)
アクリル粒子G-5 2.37質量部
(平均粒径150nm、固形分濃度10質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
離型塗布層の形成を下記のように実施した以外は、実施例1と同様にして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。
(離型塗布層の形成)
得たインラインコーティングポリエステルフィルムに離型剤溶液X-2を乾燥後の厚みで0.1μmとなるようにリバースグラビアコーターにて塗布し、次いで、90℃の熱風で30秒間乾燥した後、直ちに無電極ランプ(ヘレウス株式会社製Hバルブ)にて紫外線照射(300mJ/cm2)を行い、離型塗布層を形成し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。
実施例1で使用した易滑塗布液1中のアクリルポリオールA-1(固形分濃度20質量%)をアクリルポリオールA-13(固形分濃度20質量%)に変更した以外は、実施例1と同様にして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。
易滑塗布液1を下記の易滑塗布液22に変更した以外は、実施例1と同様にして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。
(易滑塗布液22)
水 41.39質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-13 16.57質量部
(固形分濃度20質量%)
オキサゾリン系架橋剤D-1 5.68質量部
(固形分濃度25質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
アクリル粒子G-6 0.47質量部
(平均粒径350nm、固形分濃度10質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
易滑塗布液1を下記の易滑塗布液23に変更した以外は、実施例1と同様にして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。
(易滑塗布液23)
水 41.39質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-13 16.57質量部
(固形分濃度20質量%)
オキサゾリン系架橋剤D-1 5.68質量部
(固形分濃度25質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
アクリル粒子G-7 0.47質量部
(平均粒径450nm、固形分濃度10質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
易滑塗布液1を下記の易滑塗布液24に変更した以外は、実施例1と同様にして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。
(易滑塗布液24)
水 39.62質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-13 16.57質量部
(固形分濃度20質量%)
オキサゾリン系架橋剤D-1 5.68質量部
(固形分濃度25質量%)
アクリル粒子G-5 2.37質量部
(平均粒径150nm、固形分濃度10質量%)
アクリル粒子G-7 0.47質量部
(平均粒径450nm、固形分濃度10質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
易滑塗布液1を、下記の易滑塗布液25に変更した以外は、実施例1と同様にしてポリエステルフィルムを得た。
(易滑塗布液25)
水 48.33質量部
イソプロピルアルコール 35.00質量部
ポリエステル水分散体B-1 15.78質量部
(固形分濃度30質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
界面活性剤(フッ素系、固形分濃度10質量%) 0.30質量部
易滑塗布液1を、下記の易滑塗布液26に変更した以外は、実施例1と同様にしてポリエステルフィルムを得た。
(易滑塗布液26)
水 45.18質量部
イソプロピルアルコール 35.00質量部
ポリエステル水分散体B-2 18.93質量部
(固形分濃度25質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
界面活性剤(フッ素系、固形分濃度10質量%) 0.30質量部
易滑塗布液1を、下記の易滑塗布液27に変更した以外は、実施例1と同様にしてポリエステルフィルムを得た。
(易滑塗布液27)
水 51.32質量部
イソプロピルアルコール 35.00質量部
ポリウレタン樹脂水分散体C-1 12.79質量部
(固形分濃度37質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
界面活性剤(フッ素系、固形分濃度10質量%) 0.30質量部
易滑塗布液1を、下記の易滑塗布液28に変更した以外は、実施例1と同様にしてポリエステルフィルムを得た。
(易滑塗布液28)
水 47.39質量部
イソプロピルアルコール 35.00質量部
ポリエステル水分散体B-1 11.04質量部
(固形分濃度30質量%)
オキサゾリン系架橋剤D-1 5.68質量部
(固形分濃度25質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
界面活性剤(フッ素系、固形分濃度10質量%) 0.30質量部
易滑塗布液1を、下記の易滑塗布液29に変更した以外は、実施例1と同様にしてポリエステルフィルムを得た。
(易滑塗布液29)
水 49.51質量部
イソプロピルアルコール 35.00質量部
ポリエステル水分散体B-1 11.04質量部
(固形分濃度30質量%)
カルボジイミド系架橋剤E-1 3.55質量部
(固形分濃度40質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
界面活性剤(フッ素系、固形分濃度10質量%) 0.30質量部
易滑塗布液1を、下記の易滑塗布液30に変更した以外は、実施例1と同様にしてポリエステルフィルムを得た。
(易滑塗布液30)
水 40.44質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-1 23.67質量部
(固形分濃度20質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
易滑塗布液1を、下記の易滑塗布液31に変更した以外は、実施例1と同様にしてポリエステルフィルムを得た。
(易滑塗布液31)
水 45.65質量部
イソプロピルアルコール 35.00質量部
アクリルポリオール樹脂A-1 16.57質量部
(固形分濃度20質量%)
イソシアネート架橋剤F-1 1.89質量部
(固形分濃度75質量%)
シリカ粒子G-1 0.59質量部
(平均粒径200nm、固形分濃度40質量%)
界面活性剤H-1(フッ素系、固形分濃度10質量%)0.30質量部
離型塗布層を形成するフィルムとして、実施例1で作成した一方の表面に易滑塗布層を有するインラインコーティングフィルムの代わりに、E5000-25μm(東洋紡製)に変更して使用した以外は、実施例1と同様の方法でセラミックグリーンシート製造用離型フィルムを得た。E5000はフィルム内部に粒子を含有しており、両表面のSaがともに0.031μmであった。
離型塗布層を形成するフィルムとして、実施例1で作成した一方の表面に易滑塗布層を有するインラインコーティングフィルムの代わりに、積層フィルムZに変更して使用した以外は、実施例1と同様の方法でセラミックグリーンシート製造用離型フィルムを得た。積層フィルムZのPET(II)ペレットを吐出した面(粒子を含有しない層)に離型塗布層を設けた。
一方、比較例1~7においては、本発明で規定するアクリル樹脂、及びオキサゾリン系架橋剤またはカルボジイミド系架橋剤から選ばれる少なくとも1種の架橋剤を含有する組成物が硬化されてなる易滑塗布層ではないため、易滑塗布層の架橋密度が低くなり、易滑塗布層の変形量が大きくなる。離型加工済のフィルムロールを巻きだす際の離型層と易滑層の剥離時に、接触面積が大きくなるため、巻出し帯電が大きくなったと考えられる。また、比較例8、9においては巻出し帯電は低いものの、本発明で規定する易滑塗布層を有しておらず、易滑面の表面粗さが大きいため、セラミックシートにピンホールが発生した。
Claims (8)
- 無機粒子を実質的に含有していないポリエステルフィルムを基材とし、前記基材の一方の表面上に離型塗布層を有し、かつ、もう一方の表面上に粒子を含有する易滑塗布層を有し、易滑塗布層がアクリル樹脂、及びオキサゾリン系架橋剤またはカルボジイミド系架橋剤から選ばれる少なくとも1種の架橋剤を含有する組成物が硬化されてなるセラミックグリーンシート製造用離型フィルム。
- アクリル樹脂のガラス転移温度が50℃以上110℃以下である請求項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。
- アクリル樹脂の酸価が40mgKOH/g以上400mgKOH/g以下である請求項1または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。
- 易滑塗布層の領域表面平均粗さ(Sa)が1nm以上25nm以下、最大突起高さ(P)が60nm以上500nm以下、かつ粗さ曲線要素の平均長さ(RSm)が10μm以下である請求項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。
- 易滑塗布層の厚みが0.001μm以上2μm以下である請求項1~4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。
- 請求項1~5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るセラミックグリーンシートの製造方法。
- 製造するセラミックグリーンシートの厚みが、0.2μm以上2.0μm以下である請求項6に記載のセラミックグリーンシートの製造方法。
- 請求項6または7に記載のセラミックグリーンシートの製造方法を採用するセラミックコンデンサの製造方法。
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WO2021192896A1 (ja) * | 2020-03-27 | 2021-09-30 | 東洋紡株式会社 | 離型フィルム及びその製造方法 |
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WO2023282232A1 (ja) * | 2021-07-05 | 2023-01-12 | 東洋紡株式会社 | 帯電防止フィルムおよび保護フィルム |
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KR20240022660A (ko) | 2021-08-26 | 2024-02-20 | 후지필름 가부시키가이샤 | 폴리에스터 필름, 폴리에스터 필름의 제조 방법, 박리 필름 |
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PH12020500227A1 (en) | 2020-11-09 |
JP2020100148A (ja) | 2020-07-02 |
JP6593506B2 (ja) | 2019-10-23 |
JP6992827B2 (ja) | 2022-01-13 |
JP6780734B2 (ja) | 2020-11-04 |
MY193296A (en) | 2022-10-03 |
JPWO2019039264A1 (ja) | 2019-11-07 |
JP2020001406A (ja) | 2020-01-09 |
JP2019171872A (ja) | 2019-10-10 |
CN110944840A (zh) | 2020-03-31 |
JP2019069594A (ja) | 2019-05-09 |
KR20200022015A (ko) | 2020-03-02 |
JP6477989B1 (ja) | 2019-03-06 |
CN110944840B (zh) | 2022-04-01 |
JP6791329B2 (ja) | 2020-11-25 |
KR102337032B1 (ko) | 2021-12-08 |
SG11202000848PA (en) | 2020-03-30 |
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