WO2023026800A1 - Film de protection, procédé de fabrication d'un film de protection et condensateur céramique - Google Patents

Film de protection, procédé de fabrication d'un film de protection et condensateur céramique Download PDF

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Publication number
WO2023026800A1
WO2023026800A1 PCT/JP2022/029725 JP2022029725W WO2023026800A1 WO 2023026800 A1 WO2023026800 A1 WO 2023026800A1 JP 2022029725 W JP2022029725 W JP 2022029725W WO 2023026800 A1 WO2023026800 A1 WO 2023026800A1
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Prior art keywords
release film
release
particle
polyester
containing layer
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PCT/JP2022/029725
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English (en)
Japanese (ja)
Inventor
一仁 宮宅
竜太 竹上
忠 伊藤
悠樹 豊嶋
泰雄 江夏
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富士フイルム株式会社
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Priority to JP2023543779A priority Critical patent/JPWO2023026800A1/ja
Priority to KR1020247005028A priority patent/KR20240035552A/ko
Publication of WO2023026800A1 publication Critical patent/WO2023026800A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • 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
    • H01G4/30—Stacked capacitors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes

Definitions

  • the present invention relates to a release film, a release film manufacturing method, and a ceramic capacitor.
  • multilayer ceramic capacitors are mounted on substrates in increasing numbers, and there is a strong demand for miniaturization.
  • a ceramic slurry onto a release film having a release layer and dry it to form a ceramic green sheet.
  • a method such as adding particles to the surface of the release film opposite to the release layer. It is also common to provide unevenness by .
  • the release film used for manufacturing the ceramic green sheet there is known a technique for improving the release stability by setting the release layer surface to a specific Si element ratio.
  • a polyester film is used as a substrate, the substrate has a surface layer A that does not substantially contain particles on at least one side, and a release layer is provided on the surface of the surface layer A on at least one side is laminated, the release layer is formed by curing a composition containing a binder component and a silicone-based release agent, and the release layer surface has a specific Si element ratio and maximum protrusion height (P) and area average roughness (Sa) are disclosed.
  • P maximum protrusion height
  • Sa area average roughness
  • the present inventors produced a ceramic green sheet using the release film for producing a ceramic green sheet described in Patent Document 1, and produced a ceramic capacitor using the obtained ceramic green sheet.
  • the peelability of the ceramic capacitor is excellent, when the release film is transported at high speed in the release film manufacturing process such as the release layer coating process or the transport process, defective products with deteriorated electrical characteristics of the resulting ceramic capacitor may occur.
  • the release film is stored for a long period of time and then used to produce a ceramic green sheet, the obtained ceramic green sheet may have uneven defects, and it has been found that there is room for further improvement. .
  • the produced ceramic green sheet has excellent release properties.
  • the present invention provides a ceramic green sheet that is excellent in releasability and is manufactured using the obtained ceramic green sheet even when the ceramic green sheet is manufactured using a release film that is conveyed at high speed.
  • An object of the present invention is to provide a release film capable of suppressing the defect rate of a capacitor and suppressing the occurrence of uneven defects in the obtained ceramic green sheet even when the ceramic green sheet is produced using the release film stored for a long period of time.
  • Another object of the present invention is to provide a release film manufacturing method and a ceramic capacitor.
  • a release film comprising a release layer, a polyester base material, and a particle-containing layer in this order, wherein the particle-containing layer contains particles and a non-polyester resin, the particles contain organic particles, and the release layer comprises silicone A release film containing a compound.
  • the release film according to (1) which is used for producing ceramic green sheets.
  • the surface of the particle-containing layer opposite to the polyester substrate has protrusions, and the proportion of the protrusions formed by the organic particles is 50 to 100% (1) to (3). Release film according to any one of.
  • the surface of the particle-containing layer opposite to the polyester substrate has protrusions, and among the protrusions, the protrusions having the maximum protrusion height Sp are protrusions formed by organic particles, (1) to ( The release film according to any one of 4).
  • the surface free energy of the surface of the release layer opposite to the polyester substrate is 10 to 30 mJ/m 2 and the maximum projection height Sp is 1 to 30 nm, (1) to (5) ), the release film according to any one of (7)
  • the release film according to any one of (1) to (6), wherein the organic particles contain at least one selected from the group consisting of styrene resins, urethane resins, acrylic resins, and divinylbenzene resins.
  • the surface free energy of the surface of the particle-containing layer opposite to the polyester substrate is 25 to 45 mJ/m 2 and the maximum protrusion height Sp is 25 to 1000 nm, (1) to ( The release film according to any one of 7).
  • the release film according to any one of (1) to (10), wherein the particle-containing layer has a thickness of 1 to 500 nm.
  • the defect rate of the ceramic capacitor produced using the obtained ceramic green sheet can be reduced. It is possible to provide a release film that can suppress the occurrence of unevenness defects in the resulting ceramic green sheet even when a ceramic green sheet is produced using the release film that has been stored for a long period of time. Further, according to the present invention, a method for producing a release film and a ceramic capacitor can be provided.
  • a numerical range represented by "to” means a range including the numerical values before and after “to” as lower and upper limits.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the values shown in the examples.
  • the amount of each component in the composition means the total amount of the multiple substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. do.
  • the term "step” includes not only independent steps, but also if the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps. be In this specification, a combination of two or more preferred aspects is a more preferred aspect.
  • the term “longitudinal direction” refers to the longitudinal direction of the release film when the release film is manufactured, and is synonymous with the “conveyance direction” and the “machine direction.”
  • width direction means a direction perpendicular to the longitudinal direction.
  • perpendicular is not limited to strictly perpendicular, but includes substantially perpendicular.
  • substantially orthogonal means intersecting within the range of 90° ⁇ 5°, preferably intersecting within the range of 90° ⁇ 3°, more preferably intersecting within the range of 90° ⁇ 1°. .
  • film width means the distance between both ends of the release film in the width direction.
  • the release film of the present invention (hereinafter also simply referred to as "release film”) comprises a release layer, a polyester base material, and a particle-containing layer in this order, the particle-containing layer containing particles and a non-polyester resin, contains organic particles and the release layer contains a silicone compound.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of a release film.
  • the release film 1 includes a release layer 2, a polyester base material 4, and a particle-containing layer 6 in this order.
  • the surface 21 of the release layer 2 opposite to the polyester substrate 4 (hereinafter also referred to as “release surface”) and the particle-containing layer 6 opposite to the polyester substrate 4 It has two main surfaces consisting of side surfaces 61 (hereinafter also referred to as “conveying surfaces”).
  • the release film of the present invention is not limited to the embodiment shown in FIG.
  • the release film may have intermediate layers, for example, between the release layer 2 and the polyester substrate 4 and/or between the polyester substrate 4 and the particle-containing layer 6 .
  • a feature of the release film of the present invention is that the particle-containing layer contains particles and a non-polyester resin, the particles contain organic particles, and the release layer contains a silicone compound. Since the release film has the above characteristics, the release property of the ceramic green sheet is excellent, and even when the ceramic green sheet is produced using the release film conveyed at high speed, the ceramic produced using the resulting ceramic green sheet It has excellent performance in suppressing the defect rate of capacitors, and also has excellent performance in suppressing the occurrence of uneven defects in the ceramic green sheets obtained even when ceramic green sheets are manufactured using release films that have been stored for a long time. Although the detailed mechanism is not necessarily clear, the present inventors presume as follows.
  • the release layer contains a silicone compound
  • the surface free energy of the release film is lowered, so it is considered that the release property of the ceramic green sheet is excellent.
  • the release film is conveyed under high-speed conditions, the particles forming the projections on the conveying surface may drop off due to the impact caused by contact with the conveying rolls, and adhere to the conveying rolls.
  • the release layer contains a silicone compound
  • the release surface is likely to be charged, so it is conceivable that particles adhering to the transport roll or the like may adhere to the release film.
  • the release film transported at high speed is stored in a roll form, it is conceivable that the particles adhering to the transport surface may adhere to the release surface facing the transport surface.
  • the release film according to the present invention is characterized in that the particles present on the conveying surface of the release film are organic particles.
  • the polyester base material included in the release film contains impurities such as oligomers, and when the release film is stored for a long period of time, precipitates due to the above impurities may be deposited on the transport surface and / or release surface of the release film. May appear.
  • the oligomer is a low-molecular-weight by-product produced during polymerization of the polyester resin, and is a component contained as an impurity in the polyester base material.
  • the release film according to the present invention has a particle-containing layer that constitutes the transport surface containing a non-polyester resin, and a release layer that constitutes the release surface contains a silicone compound. Presumably, this suppresses the precipitation of impurities such as oligomers from the polyester base material onto the conveying surface and/or the release surface of the release film, thereby suppressing the occurrence of uneven defects in the ceramic green sheet formed on the release surface.
  • the effect of the present invention is excellent.
  • the release layer is a layer provided on the side opposite to the side of the polyester base material on which the particle-containing layer is provided, and the ceramic green sheet is formed on the release surface, which is the surface of the release layer opposite to the polyester base material. . That is, a ceramic green sheet is manufactured to be peelable on the peeling surface of the peeling film.
  • the release layer may be provided directly on the surface of the polyester base material, or may be provided on the polyester base material via another layer. It is preferable to provide As a method of forming a release layer having a crosslinked structure, a method of forming a release layer using a release layer-forming composition containing a cross-linking agent can be mentioned, as described later.
  • the release layer contains a silicone compound because of its excellent releasability.
  • the silicone compound contained in the release layer is not particularly limited as long as it is a compound having a siloxane bond in the molecule, but is preferably a silicone resin, more preferably a silicone resin having a crosslinked structure.
  • a silicone resin means a resin having a silicone structure (main chain composed of siloxane bonds) in its molecule.
  • silicone resins include curable silicone resins, silicone graft resins, and modified silicone resins such as alkyl-modified silicone resins, with reactive curable silicone resins being preferred.
  • Examples of reactive curable silicone resins include addition reaction silicone resins, condensation reaction silicone resins, and ultraviolet or electron beam curable silicone resins. Among them, addition reaction type silicone resins having low-temperature curability or UV or electron beam curing type silicone resins are preferable because the release layer can be formed at a low temperature.
  • addition reaction silicone resins include resins obtained by reacting and curing polydimethylsiloxane having a terminal or side chain introduced with a vinyl group and hydrogen siloxane using a platinum catalyst.
  • the condensation reaction silicone resin for example, a three-dimensional polydimethylsiloxane having terminal OH groups and a polydimethylsiloxane having terminal H groups are subjected to a condensation reaction using an organic tin catalyst.
  • examples thereof include resins having a crosslinked structure.
  • Ultraviolet or electron beam curing silicone resins include those that utilize the same radical reaction as silicone rubber cross-linking, those that are photocured by introducing unsaturated groups, and those that decompose onium salts with ultraviolet rays or electron beams to generate strong acids.
  • One of the silicone resins contained in the release layer may be used alone, or two or more of them may be used.
  • the content of the silicone resin in the release layer is preferably 0.1 to 99.9% by mass, more preferably 0.5 to 99.5% by mass, based on the total mass of the release layer.
  • the release layer may contain a resin other than the silicone compound (hereinafter also referred to as "another resin").
  • Other resins contained in the release layer are not particularly limited, but from the point of view of further improving release properties, it is preferable that the release layer further contains fluorine resins, alkyd resins, acrylic resins, various waxes, and aliphatic olefins.
  • unsaturated polyester resins, melamine resins, epoxy resins, phenol resins, urethane resins, and the like may be used in combination.
  • the release layer may be used singly or in combination of two or more.
  • the content of the other resin in the release layer is preferably 50 to 99% by mass, more preferably 60 to 98% by mass, based on the total mass of the release layer.
  • the rest of the release layer excluding the silicone resin and other resins is the additives described later, and the solvent, polymerization initiator, catalyst, etc. contained in the release layer forming composition (described later) used to form the release layer. It may be at least one of the residues.
  • the release layer may contain additives in addition to the above resins.
  • additives such as light release additives and heavy release additives for adjusting the release force, adhesion improvers, and antistatic agents may be added.
  • the thickness of the release layer may be set according to the purpose of use, and is not particularly limited, but is preferably 5 to 2000 nm, more preferably 10 to 1000 nm, in terms of excellent balance between release performance and smoothness of the release surface. 30 to 300 nm is more preferred, and 50 to 200 nm is particularly preferred.
  • the thickness of the release layer is determined by preparing a section having a cross section perpendicular to the main surface of the release film and using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Arithmetic mean value of 5 thicknesses of the section measured.
  • the surface free energy of the surface (release surface) of the release layer on the side opposite to the polyester substrate side is preferably 30 mJ/m 2 or less, more preferably 10 to 30 mJ/m 2 , in terms of better release properties of the ceramic green sheet.
  • 10 to 24 mJ/m 2 is more preferable, and 10 to 20 mJ/m 2 is particularly preferable.
  • the surface free energy of the release surface can be adjusted by the type of resin forming the release layer and additives. In particular, since the release layer of the release film of the present invention contains a silicone compound, the surface free energy is small and the release property of the ceramic green sheet is excellent.
  • the surface free energy of the peeled surface was measured using a contact angle meter (for example, "DROPMASTER-501" manufactured by Kyowa Interface Science Co., Ltd.) at 25 ° C. on the peeled surface with purified water, methylene iodide and ethylene. It is obtained by dropping a droplet of glycol, measuring the contact angle one second after the droplet adheres to the surface, and calculating from each obtained contact angle according to the method of Kitazaki and Hata.
  • the "surface free energy” obtained by the above method is the sum of the polar component and the hydrogen bond component of the surface free energy.
  • the release surface is preferably as smooth as possible in order to smooth the functional layer such as a ceramic green sheet formed on the release layer.
  • the maximum protrusion height Sp of the peeled surface is preferably 1 to 60 nm, more preferably 1 to 40 nm, and even more preferably 1 to 30 nm.
  • the surface average roughness Sa of the peeled surface is preferably 0 to 10 nm, more preferably 0 to 5 nm, still more preferably 0 to 2 nm, and particularly preferably 0 to 1 nm.
  • the maximum protrusion height Sp and surface average roughness Sa of the release surface are determined, for example, by not putting particles in the release layer when providing the release layer, and by selecting the resin and additives that form the release layer. Adjustable. In particular, by providing a release layer containing a silicone compound on a polyester base material that does not substantially contain particles, smoothness is improved and Sp and Sa can be reduced.
  • the maximum projection height Sp and the surface average roughness Sa of the peeled surface are measured using an optical interferometer ("Vertscan R3300G Lite" manufactured by Hitachi High-Tech Co., Ltd.) under the following conditions. It is obtained by analyzing with the data analysis software provided. In the measurement of the maximum projection height Sp, the measurement position is changed and measured five times, and the maximum value of the obtained measurement values is taken as the measurement value of the maximum projection height Sp (indicated as P in the built-in data analysis software) ). In addition, in the measurement of the surface average roughness Sa, the measurement position is changed and the measurement is performed five times, and the average value of the obtained measurement values is used as the measurement value of the surface average roughness Sa. Specific measurement conditions are as follows. Measurement mode: WAVE mode Objective lens: 50x Measurement area: 186 ⁇ m ⁇ 155 ⁇ m
  • a polyester substrate is a film-like body containing a polyester resin as the main polymer component.
  • the "main polymer component” means the polymer with the highest content (mass) among all polymers contained in the film-like substance.
  • the polyester base material may contain a single polyester resin, or may contain two or more polyester resins.
  • a polyester resin is a polymer having an ester bond in its main chain.
  • a polyester resin is usually formed by polycondensing a dicarboxylic acid compound and a diol compound, which will be described later.
  • the polyester resin is not particularly limited, and known polyester resins can be used.
  • polyester resins include polyethylene terephthalate (PET), polyethylene-2,6-naphthalate (PEN), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), and copolymers thereof. At least one selected from the group consisting of PET, PEN, and copolymers thereof is preferred, and PET is more preferred.
  • the intrinsic viscosity of the polyester resin is preferably 0.50 dl/g or more and less than 0.80 dl/g, more preferably 0.55 dl/g or more and less than 0.70 dl/g.
  • the melting point (Tm) of the polyester resin is preferably 220 to 270°C, more preferably 245 to 265°C.
  • the glass transition temperature (Tg) of the polyester resin is preferably 65-90°C, more preferably 70-85°C.
  • the method for producing the polyester resin is not particularly limited, and known methods can be used.
  • a polyester resin can be produced by polycondensing at least one dicarboxylic acid compound and at least one diol compound in the presence of a catalyst.
  • the materials used for the production of polyester and the production conditions are described below.
  • dicarboxylic acid compound examples include dicarboxylic acids such as aliphatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds, and aromatic dicarboxylic acid compounds, and dicarboxylic acids such as methyl ester compounds and ethyl ester compounds of these dicarboxylic acids. esters. Among them, aromatic dicarboxylic acid or methyl aromatic dicarboxylate is preferable.
  • aliphatic dicarboxylic acid compounds include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid.
  • Alicyclic dicarboxylic acid compounds include, for example, adamantanedicarboxylic acid, norbornenedicarboxylic acid, cyclohexanedicarboxylic acid, and decalinedicarboxylic acid.
  • aromatic dicarboxylic acid compounds include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 1,8-naphthalenedicarboxylic acid.
  • terephthalic acid or 2,6-naphthalenedicarboxylic acid is preferable, and terephthalic acid is more preferable.
  • dicarboxylic acid compound Only one type of dicarboxylic acid compound may be used, or two or more types may be used in combination.
  • terephthalic acid When terephthalic acid is used as the dicarboxylic acid compound, terephthalic acid may be used alone, or may be copolymerized with another aromatic dicarboxylic acid such as isophthalic acid, or an aliphatic dicarboxylic acid.
  • diol compound examples include aliphatic diol compounds, alicyclic diol compounds, and aromatic diol compounds, with aliphatic diol compounds being preferred.
  • aliphatic diol compounds examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, and neo Pentyl glycol may be mentioned, with ethylene glycol being preferred.
  • Alicyclic diol compounds include, for example, cyclohexanedimethanol, spiroglycol, and isosorbide.
  • aromatic diol compounds include bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, and 9,9′-bis(4-hydroxyphenyl)fluorene. Only one kind of diol compound may be used, or two or more kinds thereof may be used in combination.
  • the catalyst used for producing the polyester resin is not particularly limited, and any known catalyst that can be used for synthesizing the polyester resin can be used.
  • catalysts include alkali metal compounds (e.g., potassium compounds, sodium compounds), alkaline earth metal compounds (e.g., calcium compounds, magnesium compounds), zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony. compounds, titanium compounds, germanium compounds, and phosphorus compounds.
  • alkali metal compounds e.g., potassium compounds, sodium compounds
  • alkaline earth metal compounds e.g., calcium compounds, magnesium compounds
  • zinc compounds e.g., lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony.
  • titanium compounds are preferable from the viewpoint of catalytic activity and cost. Only one kind of catalyst may be used, or two or more kinds thereof may be used in combination.
  • At least one metal catalyst selected from potassium compounds, sodium compounds, calcium compounds, magnesium compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, and germanium compounds; It is preferable to use a compound together, and it is more preferable to use a titanium compound and a phosphorus compound together.
  • an organic chelate titanium complex is preferred.
  • An organic chelate titanium complex is a titanium compound having an organic acid as a ligand.
  • Organic acids include, for example, citric acid, lactic acid, trimellitic acid, and malic acid.
  • titanium compounds described in [0049] to [0053] of Japanese Patent No. 5575671 can also be used, and the contents of the above publications are incorporated herein.
  • Terminal blocking agent In the production of the polyester resin, if necessary, a terminal blocker may be used. By using the terminal blocking agent, a structure derived from the terminal blocking agent is introduced to the terminal of the polyester resin.
  • the terminal blocking agent is not limited, and known terminal blocking agents can be used. Examples of terminal blocking agents include oxazoline-based compounds, carbodiimide-based compounds, and epoxy-based compounds.
  • the end blocking agent the content described in [0055] to [0064] of JP-A-2014-189002 can also be referred to, and the content of the above publication is incorporated herein.
  • the reaction temperature for producing the polyester resin is not limited, and may be appropriately set according to the raw materials.
  • the reaction temperature is preferably 260-300°C, more preferably 275-285°C.
  • the pressure in producing the polyester resin is not limited, and may be appropriately set according to the raw material.
  • the pressure is preferably 1.33 ⁇ 10 ⁇ 3 to 1.33 ⁇ 10 ⁇ 5 MPa, more preferably 6.67 ⁇ 10 ⁇ 4 to 6.67 ⁇ 10 ⁇ 5 MPa.
  • the content of the polyester resin in the polyester base is preferably 85% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 98% by mass with respect to the total mass of the polymer in the polyester base. % or more is particularly preferred.
  • the upper limit of the content of the polyester resin is not particularly limited, and can be appropriately set, for example, within a range of 100% by mass or less with respect to the total mass of the polymer in the polyester base material.
  • the polyester base material contains polyethylene terephthalate
  • the content of polyethylene terephthalate is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, based on the total mass of the polyester resin in the polyester base material. 100% by mass is more preferred, and 100% by mass is particularly preferred.
  • the polyester base material may contain components other than the polyester resin (eg, catalyst, unreacted raw material components, particles, water, etc.). From the viewpoint of improving the smoothness of the release film, it is preferable that the polyester base material does not substantially contain particles.
  • the particles include particles contained in the particle-containing layer described below. "Substantially free of particles” means that the content of particles is 50 mass with respect to the total mass of the polyester base material when quantitatively analyzing the elements derived from the particles by fluorescent X-ray analysis for the polyester base material. It is defined as ppm or less, preferably 10 mass ppm or less, more preferably detection limit or less.
  • the polyester substrate is a biaxially oriented polyester substrate.
  • "Biaxial orientation” means the property of having molecular orientation in two axial directions. The molecular orientation is measured using a microwave transmission type molecular orientation meter (for example, MOA-6004, manufactured by Oji Scientific Instruments Co., Ltd.). The angle formed by the two axial directions is preferably within the range of 90° ⁇ 5°, more preferably within the range of 90° ⁇ 3°, and still more preferably within the range of 90° ⁇ 1°.
  • the biaxially oriented polyester substrate in the release film of the present invention preferably has molecular orientation in the longitudinal direction and the width direction. A biaxially oriented polyester substrate can be produced by the method described later.
  • the density of the polyester base material is preferably 1.39 to 1.41 g/cm 3 , more preferably 1.395 to 1.405 g/cm 3 and even more preferably 1.398 to 1.400 g/cm 3 .
  • the density of the polyester base material can be measured using an electronic hydrometer (product name “SD-200L”, manufactured by Alpha Mirage).
  • the thickness of the polyester base material is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 40 ⁇ m or less, from the viewpoint of being able to control the releasability.
  • the lower limit of the thickness is not particularly limited, it is preferably 3 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 20 ⁇ m or more in terms of improving strength and workability.
  • the thickness of the polyester base material should be measured using a continuous stylus type film thickness meter. Specifically, the thickness of the polyester base material is measured over 10 m along the longitudinal direction with a continuous stylus film thickness gauge. This measurement is performed at five different positions in the width direction. Let the arithmetic average value of the obtained measured value be thickness.
  • a particle-containing layer refers to a layer containing particles.
  • the particle-containing layer is a layer provided on the surface of the polyester substrate opposite to the side on which the release layer is provided, and can improve the transportability of the release film. Specifically, the winding quality can be improved (blocking can be suppressed), the occurrence of scratches and defects during transportation can be suppressed, and wrinkles during high-speed transportation can be reduced.
  • the particle-containing layer may be provided directly on the surface of the polyester base material, or may be provided on the surface of the polyester base material via another layer. It is preferable to provide
  • the particle-containing layer preferably contains a binder, and may further contain an additive.
  • the particles, binders and additives are described below.
  • the particle-containing layer contains organic particles as particles. Thereby, the defect rate of the ceramic capacitor can be suppressed.
  • the particle-containing layer may also contain inorganic particles, but when manufacturing a ceramic capacitor using a ceramic green sheet formed on the peeling surface, it reduces the number of particles that do not burn and fall off, and is excellent in suppressing the defect rate of the ceramic capacitor. In addition, the smaller the number of inorganic particles, the better.
  • the transport surface which is the surface of the particle-containing layer opposite to the polyester base material, has protrusions, and among the protrusions observed on this transport surface, the proportion of protrusions formed by organic particles is the number of protrusions. The ratio is preferably 50 to 100%, more preferably 70 to 100%.
  • the particles forming the protrusions are analyzed by observing the transport surface with a scanning electron microscope (SEM, "S-4800", manufactured by Hitachi High-Tech Co., Ltd.). Specifically, the conveying surface is observed with an SEM at a magnification such that 15 to 20 protrusions are within the observation field (however, 20,000 times is the upper limit magnification, and if there are 15 or more protrusions, Arbitrary 15 particles are discriminated between organic particles and inorganic particles). At this time, even if dust and/or coarsely aggregated particles of 1 ⁇ m or more are present, the dusts and coarsely aggregated particles are not counted.
  • SEM scanning electron microscope
  • EDS Electronic Dispersive X-ray Spectroscopy, energy dispersive X-ray
  • analysis equipment is used to analyze the elements that form each particle, and determine whether it is an organic particle or an inorganic particle. do.
  • the ratio of the number of organic particles to the total number of particles observed in the above measurement area is calculated, this is performed for 10 fields of view, and the arithmetic average value is taken as the ratio of protrusions formed by organic particles.
  • the particles are determined to be organic particles.
  • the transport surface has protrusions, and among the protrusions observed on the transport surface, the protrusions having the maximum protrusion height Sp are formed of organic particles. It is preferable that the projection is A method for determining whether or not the protrusions having the maximum protrusion height Sp on the conveying surface of the release film are protrusions formed of organic particles will be described in detail in Examples described later.
  • Resin particles are preferable as the organic particles contained in the particle-containing layer.
  • the resin constituting the resin particles include acrylic resins such as polymethyl methacrylate resin (PMMA), polyester resins, silicone resins, and styrene-acrylic resins.
  • the resin particles may have a crosslinked structure.
  • resin particles having a crosslinked structure include urethane crosslinked particles, acrylic crosslinked particles, and divinylbenzene crosslinked particles.
  • the organic particles preferably contain at least one selected from the group consisting of styrene resins, urethane resins, acrylic resins, and divinylbenzene resins, and are selected from the group consisting of styrene resins, urethane resins, and acrylic resins. It is more preferred to include at least one
  • an acrylic resin means a resin containing structural units derived from acrylate or methacrylate.
  • acrylic resin particles examples include Eposter (registered trademark) MX020W, MX030W, MX050W, MX100W, MX200W, and MX300W (manufactured by Nippon Shokubai Co., Ltd.), and Techpolymer (registered trademark) series (Sekisui Plastics Co., Ltd.). manufactured by Kogyo Co., Ltd.).
  • examples of commercially available styrene resin particles examples include Nipol (registered trademark) UFN1008 (manufactured by Nippon Zeon Co., Ltd.).
  • examples of commercial products of urethane resin particles examples include Artpearl (registered trademark) C-1000T and MM110SMA (manufactured by Negami Kogyo Co., Ltd.).
  • the average particle size of the organic particles contained in the particle-containing layer is not particularly limited, and is preferably 1 nm to 3 ⁇ m, more preferably 40 nm to 2 ⁇ m, and more preferably 50 nm to 1 ⁇ m.
  • the shape of the particles is not particularly limited, and examples thereof include rice grain-like, spherical, cubic, spindle-like, scale-like, aggregated, and irregular shapes. Aggregate means a state in which primary particles are aggregated. Although the shape of the aggregated particles is not limited, spherical or irregular shapes are preferred.
  • the particles contained in the particle-containing layer may be used singly, or two or more kinds of particles may be used.
  • the particle-containing layer preferably contains at least one kind of particles having an average particle diameter within the above range, and two or more kinds of particles having different particle diameters. More preferably, all of the particles have an average particle size within the above range.
  • the content of the particles in the particle-containing layer is preferably 0.1 to 30% by mass, preferably 1 to 25% by mass, based on the total mass of the particle-containing layer, from the viewpoints of transportability and coating properties of the release layer. More preferably, 1 to 15% by mass is even more preferable. Also, the content of the particles is preferably 0.0001 to 0.01% by mass, more preferably 0.0005 to 0.005% by mass, relative to the total mass of the polyester base material.
  • Non-polyester resin (binder) The particle-containing layer contains a non-polyester resin.
  • the non-polyester resin contained in the particle-containing layer functions as a binder.
  • Non-polyester resins are not particularly limited as long as they are resins other than polyester resins, and include acrylic resins, urethane resins, olefin resins, polyvinyl alcohol resins, and acrylonitrile-butadiene resins. , an acrylic resin, a urethane resin, or an olefin resin is preferable.
  • non-polyester resins (especially acrylic resins, urethane resins and olefin resins) and polyester resins have different solubility parameters (SP values).
  • the compatibility between the polyester resin and the acrylic resin, urethane resin, and olefin resin is insufficient, so that impurities such as oligomers are less likely to deposit on the conveying surface from the polyester base material via the particle-containing layer. It is speculated that this makes it difficult for projections due to impurities contained in the polyester base material to occur on the conveying surface.
  • Non-polyester resins such as acrylic resins, urethane resins, and olefin resins are not particularly limited, and known resins can be used.
  • the non-polyester resin may be an acid-modified resin.
  • the particle-containing layer may contain a polyester resin.
  • the acrylic resin is a resin containing structural units derived from (meth)acrylate, and may be copolymerized with a vinyl monomer such as styrene.
  • the acrylic resin is not particularly limited, it preferably contains a structural unit derived from a (meth)acrylate having an alkyl group having 1 to 12 carbon atoms, and a (meth)acrylate having an alkyl group having 1 to 8 carbon atoms. It is more preferable to contain structural units derived from.
  • the acrylic resin may have an acid-modified component.
  • the acrylic resin may contain a structural unit derived from (meth)acrylic acid as an acid-modified component.
  • (meth)acrylic acid may form an acid anhydride, or may be neutralized with at least one selected from alkali metals, organic amines and ammonia.
  • the acid value of the acrylic resin is preferably 30 mgKOH/g or less, more preferably 20 mgKOH/g or less.
  • the lower limit of the acid value is not particularly limited, and is, for example, 0 mgKOH/g, but is preferably 2 mgKOH/g or more from the viewpoint of coating as an aqueous dispersion.
  • the olefin resin may be any resin containing a structural unit derived from an olefin in its main chain.
  • a structural unit derived from an olefin in the main chain it is possible to make the resin difficult to be compatible with the polyester resin, and the deposition of impurities such as oligomers contained in the polyester base material in the particle-containing layer is suppressed. Defects in ceramic green sheets can be suppressed.
  • the olefin is not particularly limited, but is preferably an alkene having 2 to 6 carbon atoms, more preferably ethylene, propylene or hexene, and still more preferably ethylene.
  • the olefin-derived structural units of the polyolefin are preferably 50 to 99 mol %, more preferably 60 to 98%, of all the structural units of the polyolefin.
  • an acid-modified olefin resin is preferable.
  • acid-modified olefin resins include copolymers obtained by modifying the above olefin resins with an acid-modifying component such as an unsaturated carboxylic acid or an anhydride thereof.
  • Acid-modified olefin resins include, for example, Zaixen (registered trademark) series such as Zaixen AC, A, L, NC and N (manufactured by Sumitomo Seika Co., Ltd.), Chempearl S100, S120, S200, S300, S650.
  • the urethane resin is not limited as long as it is a polymer having a urethane bond, and known urethane resins such as reaction products of isocyanate compounds and polyol compounds can be used.
  • the urethane resin is preferably a urethane resin having an acidic group, or a form containing a urethane resin and a dispersing agent, since it is easy to form a film by coating.
  • a carboxyl group etc. are mentioned as an acidic group.
  • Urethane resin for example, by adjusting the structure and hydrophobicity (hydrophilicity) of each of the polyol compound and / or isocyanate compound as a raw material, it can be a resin that is difficult to be compatible with the polyester resin, the polyester base material Precipitation of impurities such as oligomers contained in is suppressed in the particle-containing layer, and defects in the ceramic green sheet can be suppressed.
  • the urethane resin preferably contains a polyester structure in that defect suppression can be further improved.
  • urethane resins include, for example, Hydran (registered trademark) AP-20, AP-40N and AP-201 (manufactured by DIC Corporation), Takelac (registered trademark) W-605, W-5030 and W-5920. (above, manufactured by Mitsui Chemicals), Superflex (registered trademark) 210 and 130, and Elastron (registered trademark) H-3-DF, E-37 and H-15 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) mentioned.
  • the non-polyester resin contained in the particle-containing layer may have a crosslinked structure. That is, the particle-containing layer may be a crosslinked film.
  • a method of forming a particle-containing layer using a particle-containing layer-forming composition containing a crosslinking agent can be used, as described later.
  • the particle-containing layer may contain a single binder, or may contain two or more binders. Moreover, the particle-containing layer may contain a single non-polyester resin, or may contain two or more non-polyester resins. From the viewpoint of suppressing defects, the content of the binder (preferably non-polyester resin) is preferably 30 to 99.8% by mass, more preferably 50 to 99.5% by mass, based on the total mass of the particle-containing layer. .
  • the particle-containing layer may contain additives other than the particles and binder described above.
  • Additives contained in the particle-containing layer include, for example, surfactants, waxes, antioxidants, ultraviolet absorbers, colorants, reinforcing agents, plasticizers, antistatic agents, flame retardants, rust inhibitors, and anti-rust agents. Examples include fungicides.
  • the particle-containing layer preferably contains a surfactant from the viewpoint of improving the smoothness of areas other than areas where protrusions formed by particles exist on the conveying surface.
  • the surfactant is not particularly limited, and includes silicone-based surfactants, fluorine-based surfactants, and hydrocarbon-based surfactants, among which hydrocarbon-based surfactants are preferred.
  • the silicone-based surfactant is not particularly limited as long as it has a silicon-containing group as a hydrophobic group, and examples thereof include polydimethylsiloxane, polyether-modified polydimethylsiloxane, and polymethylalkylsiloxane.
  • silicone surfactants examples include BYK (registered trademark)-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, and , BYK-349 (manufactured by BYK), and KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the fluorosurfactant is not particularly limited as long as it has a fluorine-containing group as a hydrophobic group, and examples thereof include perfluorooctane sulfonic acid and perfluorocarboxylic acid.
  • fluorosurfactants include, for example, Megafac (registered trademark) F-114, F-410, F-440, F-447, F-553, and F-556 (manufactured by DIC Corporation).
  • the fluorine-based surfactant has a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). It is preferred to use surfactants derived from substitute materials for the compounds.
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctane sulfonic acid
  • hydrocarbon surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
  • Anionic surfactants include, for example, alkyl sulfates, alkylbenzene sulfonates, alkyl phosphates, and fatty acid salts.
  • nonionic surfactants include polyalkylene glycol mono- or dialkyl ethers, polyalkylene glycol mono- or dialkyl esters, and polyalkylene glycol mono- or dialkyl esters/monoalkyl ethers.
  • Cationic surfactants include primary to tertiary alkylamine salts and quaternary ammonium compounds.
  • Amphoteric surfactants include surfactants having both an anionic site and a cationic site in the molecule.
  • anionic surfactants examples include RAPISOL (registered trademark) A-90, A-80, BW-30, B-90, and C-70 (manufactured by NOF Corporation), NIKKOL (registered trademark) OTP-100 (manufactured by Nikko Chemical Co., Ltd.), Kohakul (registered trademark) ON, L-40, and Phosphanol (registered trademark) 702 (manufactured by Toho Chemical Industry Co., Ltd.) ), and Viewlite (registered trademark) A-5000 and SSS (manufactured by Sanyo Chemical Industries Co., Ltd.).
  • nonionic surfactants include, for example, Naloacty (registered trademark) CL-95 and HN-100 (trade name: manufactured by Sanyo Chemical Industries, Ltd.), Resolex BW400 (trade name: KOKYU ALCOHOL KOGYO Co., Ltd.), EMALEX (registered trademark) ET-2020 (manufactured by Nippon Emulsion Co., Ltd.), and Surfynol (registered trademark) 104E, 420, 440, 465, and Dynol (registered trademark) 604, 607 (manufactured by Nissin Chemical Industry Co., Ltd.).
  • anionic surfactants and/or nonionic surfactants are preferred, and anionic surfactants are more preferred.
  • the anionic hydrocarbon-based surfactant preferably has a plurality of hydrophobic terminal groups in terms of further improving smoothness.
  • the hydrophobic end group may be part of the hydrocarbon group of the hydrocarbon surfactant.
  • a hydrocarbon surfactant terminated with a hydrocarbon group having a branched chain structure will have a plurality of hydrophobic end groups.
  • anionic hydrocarbon surfactants having multiple hydrophobic terminal groups include di-2-ethylhexyl sodium sulfosuccinate (having four hydrophobic terminal groups), di-2-ethyloctyl sodium sulfosuccinate ( 4 hydrophobic end groups) and branched alkyl benzene sulfonates (2 hydrophobic end groups).
  • One type of surfactant may be used, or two or more types may be used in combination.
  • the content of the surfactant is preferably 0.1 to 10% by mass with respect to the total mass of the particle-containing layer. ⁇ 5% by mass is more preferred, and 0.5 to 2% by mass is even more preferred.
  • the wax is not particularly limited, and may be natural wax or synthetic wax. Natural waxes include carnauba wax, candelilla wax, beeswax, montan wax, paraffin wax, and petroleum wax. In addition, a slipping agent described in [0087] of International Publication No. 2017/169844 can also be used.
  • the wax content is preferably 0 to 10% by mass with respect to the total mass of the particle-containing layer.
  • the particle-containing layer is formed, for example, by coating a composition containing organic particles and a non-polyester resin on one surface of the polyester substrate, and often has a thickness of 1 ⁇ m or less. Further, the polyester base material and the particle-containing layer, which will be described later, may be formed by co-extrusion molding, in which case the thickness of the particle-containing layer is often 1 to 10 ⁇ m.
  • the thickness of the particle-containing layer is preferably 1 nm to 3 ⁇ m, and when it is produced by coating, it is preferably 1 to 500 nm, more preferably 1 to 250 nm, even more preferably 10 to 100 nm, from the viewpoint of production suitability and haze reduction.
  • the thickness of the particle-containing layer is measured using a scanning electron microscope (SEM) or a transmission electron microscope (TEM) by preparing a section having a cross section perpendicular to the main surface of the release film. Arithmetic mean value of thickness at 5 locations.
  • the surface free energy of the surface (conveying surface) of the particle-containing layer opposite to the polyester substrate is preferably 25 to 60 mJ/m 2 , more preferably 25 to 45 mJ/m 2 , and further preferably 30 to 45 mJ/m 2 . preferable.
  • the surface free energy on the conveying surface is within the above range, deposition of impurities such as oligomers contained in the polyester base material on the conveying surface can be further suppressed, and defects in the ceramic green sheet can be further suppressed.
  • the maximum protrusion height Sp on the transport surface is preferably 10 to 5000 nm, the release film is excellent in high-speed transportability, and defects in the ceramic green sheet can be further suppressed, and the release film is transported at high speed.
  • the thickness is more preferably 25 to 1000 nm, still more preferably 25 to 600 nm, and particularly preferably 30 to 500 nm.
  • the average surface roughness Sa on the conveying surface is preferably 0 to 10 nm, more preferably 0 to 5 nm, even more preferably 1 to 3 nm.
  • the method for measuring the maximum projection height Sp and the average surface roughness Sa of the conveying surface is the same as the method for measuring the maximum projection height Sp and the average surface roughness Sa of the peeling surface described above.
  • the thickness of the release film is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 40 ⁇ m or less, in terms of better releasability. Moreover, the thickness of the release film is preferably 3 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 20 ⁇ m or more, in order to improve strength and workability.
  • a method for manufacturing a release film will be described.
  • the method for producing the release film is not particularly limited as long as the release film having the properties described above can be obtained, and known methods can be used.
  • the preferred method for producing a release film is the following in that the release film can be produced with high productivity.
  • An extrusion molding step of forming an unstretched polyester base material by extrusion A first stretching step of stretching an unstretched polyester substrate in one of the transport direction and the width direction to form a uniaxially oriented polyester substrate, and a uniaxially oriented polyester substrate in the transport direction and a stretching step in which a second stretching step of stretching in the other width direction to form a biaxially oriented polyester substrate is performed stepwise or simultaneously, Between the extrusion molding step and the stretching step, between the first stretching step and the second stretching step, or after the stretching step, the particle-containing layer-forming composition is applied to one surface side of the polyester base material.
  • a particle-containing layer forming step of forming a particle-containing layer Between the extrusion molding step and the stretching step, between the first stretching step and the second stretching step, or after the stretching step, the release layer forming composition is applied to the other surface side of the polyester base material and peeled. and a release layer forming step of forming a layer.
  • the extrusion molding step is a step of forming an unstretched polyester base material by extrusion molding. More specifically, it is a step of extruding a molten resin containing a raw material polyester resin into a film to form an unstretched polyester base material.
  • the raw material polyester resin is synonymous with the polyester resin described in the item (polyester resin) above.
  • polyester pellets that do not contain particles at the time of extrusion molding.
  • the extrusion molding method is, for example, a method of molding a raw material resin into a desired shape by extruding a melt of the raw material resin using an extruder.
  • the melt extruded from the extrusion die is cooled to form a film.
  • the melt can be formed into a film by contacting the melt with a casting roll and cooling and solidifying the melt on the casting roll. In cooling the melt, it is preferable to blow air (preferably cool air) to the melt.
  • the stretching step includes a first stretching step of stretching an unstretched polyester substrate in either the transport direction or the width direction to form a uniaxially oriented polyester substrate, and a uniaxially oriented polyester substrate. in the other of the machine direction and the width direction to form a biaxially oriented polyester base material.
  • One of the first stretching step and the second stretching step is a longitudinal stretching step of stretching the polyester base material in the conveying direction (hereinafter also referred to as “longitudinal stretching”), and the other of the first stretching step and the second stretching step. is a lateral stretching step of stretching the polyester base material in the width direction (hereinafter also referred to as “lateral stretching”). During stretching, the polyester polymer is aligned in each direction.
  • the stretching step may be simultaneous biaxial stretching in which longitudinal stretching and lateral stretching are performed simultaneously, or sequential biaxial stretching in which longitudinal stretching and lateral stretching are performed in stages.
  • sequential biaxial stretching include longitudinal stretching ⁇ lateral stretching, longitudinal stretching ⁇ lateral stretching ⁇ longitudinal stretching, and longitudinal stretching ⁇ longitudinal stretching ⁇ lateral stretching, with longitudinal stretching ⁇ lateral stretching being preferred.
  • longitudinal stretching ⁇ transverse stretching will be described, but the production method is not limited to this mode.
  • the draw ratio in the longitudinal drawing step is appropriately set, but is preferably 2.0 to 5.0 times, more preferably 2.5 to 4.0 times, and even more preferably 2.8 to 4.0 times.
  • the stretching speed in the longitudinal stretching step is preferably 800 to 1500%/second, more preferably 1000 to 1400%/second, even more preferably 1200 to 1400%/second.
  • the "stretching speed" is a value obtained by dividing the length ⁇ d of the polyester substrate in the transport direction stretched per second in the longitudinal stretching step by the length d0 of the polyester substrate in the transport direction before stretching. , is the value expressed as a percentage.
  • the lateral stretching step it is preferable to preheat the uniaxially oriented polyester base material before lateral stretching.
  • the draw ratio (lateral draw ratio) in the width direction of the uniaxially oriented polyester base material in the transverse drawing step is not particularly limited, but is preferably larger than the draw ratio in the longitudinal drawing step.
  • the draw ratio in the transverse drawing step is preferably 3.0 to 6.0 times, more preferably 3.5 to 5.0 times, even more preferably 3.5 to 4.5 times.
  • the stretching speed in the lateral stretching step is preferably 8 to 45%/second, more preferably 10 to 30%/second, even more preferably 15 to 20%/second.
  • the particle-containing layer forming step is a step of forming a particle-containing layer by applying a particle-containing layer-forming composition containing organic particles and a non-polyester resin to one surface of a polyester base material.
  • the particle-containing layer forming step is performed, for example, between the extrusion molding step and the first stretching step, between the first stretching step and the second stretching step, or after the stretching step.
  • the particle-containing layer formed on one surface of the polyester substrate in the particle-containing layer forming step has the same meaning as the layer described in the item of the particle-containing layer.
  • a mode of applying the composition for forming a particle-containing layer will be described below.
  • the composition for forming the particle-containing layer can be prepared by mixing the organic particles contained in the particle-containing layer, the non-polyester resin, additives added as necessary, and the solvent.
  • solvents include water and alcohol solvents.
  • the particle-containing layer-forming composition may contain a single solvent, or may contain two or more solvents.
  • the content of the solvent is preferably 80 to 99.5% by mass, more preferably 90 to 99% by mass, based on the total mass of the composition for forming a particle-containing layer. That is, in the particle-containing layer-forming composition, the total content of components (solid content) other than the solvent is preferably 0.5 to 20% by mass with respect to the total mass of the particle-containing layer-forming composition. ⁇ 10% by mass is more preferred.
  • the organic particles, non-polyester resin, and optional additives contained in the particle-containing layer-forming composition are as described in the section on the particle-containing layer. be.
  • the content of each component relative to the total mass of the solid content of the composition for forming a particle-containing layer is preferably the content of each component relative to the total mass of the particle-containing layer. It is preferable to adjust the content of each component in the particle-containing layer-forming composition so as to be the same as the content.
  • the composition for forming a particle-containing layer may contain a cross-linking agent.
  • the cross-linking agent is not particularly limited, and known ones can be used.
  • cross-linking agents include melamine-based compounds, oxazoline-based compounds, epoxy-based compounds, isocyanate-based compounds, and carbodiimide-based compounds, with oxazoline-based compounds and carbodiimide-based compounds being preferred.
  • Examples of commercially available products include Carbodilite V-02-L2 (manufactured by Nisshinbo Corp.) and Epocross K-2020E (manufactured by Nippon Shokubai Co., Ltd.).
  • cross-linking agents described in [0082] to [0084] of International Publication No. 2017/169844 can also be preferably used.
  • the descriptions in [0038] to [0040] of JP-A-2017-087421 can be referred to.
  • cross-linking agents described in [0074] to [0075] of WO 2018/034294 can also be preferably used.
  • the content of the cross-linking agent is preferably 0 to 50% by mass with respect to the total mass of the particle-containing layer.
  • the weight ratio of the cross-linking agent to the binder in the particle-containing layer-forming composition is preferably 2 to 50% by weight.
  • the method of applying the particle-containing layer-forming composition is not particularly limited, and a known method can be used.
  • coating methods include spray coating, slit coating, roll coating, blade coating, spin coating, bar coating and dip coating.
  • the particle-containing layer forming step is preferably performed between the first stretching step and the second stretching step.
  • the heating temperature for forming the particle-containing layer is preferably 180° C. or lower, more preferably 150° C. or lower, and even more preferably 120° C. or lower.
  • the lower limit is not particularly limited, and may be 60°C or higher.
  • the surface of the polyester base material is subjected to pretreatment such as anchor coating, corona treatment, and plasma treatment. may be applied.
  • the release layer forming step is a step of forming a release layer by applying a release layer forming composition to the surface of the polyester substrate opposite to the particle-containing layer.
  • the release layer forming step is performed between the extrusion molding step and the first stretching step, between the first stretching step and the second stretching step, or after the stretching step.
  • the release layer forming step is performed after the stretching step, it is preferably performed after the cooling step described below, and more preferably after the winding step and trimming step described below.
  • the release layer formed on one surface of the polyester substrate in the release layer forming step has the same meaning as the layer described in the item of the release layer.
  • the release layer-forming composition can be prepared by mixing the silicone compound, the above-mentioned other resins that are added as necessary, additives that are added as necessary, and a solvent.
  • solvents include water, alcohol solvents, ether solvents, ketone solvents, and aromatic hydrocarbon solvents.
  • the release layer-forming composition may contain a single solvent, or may contain two or more solvents.
  • the content of the solvent is preferably 80 to 99.5% by mass, more preferably 90 to 99% by mass, based on the total mass of the release layer-forming composition. That is, in the release layer-forming composition, the total content of components (solid content) other than the solvent is preferably 0.5 to 20% by mass, preferably 1 to 10%, based on the total mass of the release layer-forming composition. % by mass is more preferred.
  • the silicone compound, other resins, and optional additives contained in the release layer-forming composition are as described in the release layer section above.
  • the release layer-forming composition contains the above resin and solvent, and if necessary, may contain the above additives and/or the above catalyst used for curing the resin.
  • the release layer forming composition contains a cross-linking agent.
  • the cross-linking agent is not particularly limited, and known ones can be used.
  • the release layer-forming composition may also contain a polymerization initiator. Examples of the polymerization initiator include photopolymerization initiators, and known ones can be used.
  • the content of each component relative to the total mass of solids in the release layer-forming composition is the preferred content of each component relative to the total mass of the release layer. It is preferable to adjust the content of each component in the release layer-forming composition so as to be the same.
  • the method of applying the release layer-forming composition is not particularly limited, and a known method can be used.
  • a specific example of the coating method is as described in the particle-containing layer forming step.
  • the heating temperature for forming the release layer is preferably 180°C or lower, more preferably 150°C or lower, and even more preferably 120°C or lower.
  • the lower limit is not particularly limited, and may be 60°C or higher.
  • the surface of the polyester base material is subjected to pretreatment such as anchor coating, corona treatment, and plasma treatment.
  • the production method for the release film may include a heat setting step as a heat treatment for the polyester film obtained in the stretching step after the stretching step.
  • the polyester film obtained by the stretching step can be heated and heat-set.
  • the surface temperature (heat setting temperature) of the polyester film in the heat setting step is not particularly limited, but is preferably less than 240°C, more preferably 235°C or less, and even more preferably 230°C or less.
  • the lower limit is not particularly limited, it is preferably 190°C or higher, more preferably 200°C or higher, and even more preferably 210°C or higher.
  • the heating time in the heat setting step is preferably 5 to 50 seconds, more preferably 5 to 30 seconds, even more preferably 5 to 10 seconds.
  • the method for producing the release film may include a heat relaxation step after the heat setting step.
  • thermal relaxation step it is preferable to thermally relax the polyester film heat-set in the heat-setting step by heating at a temperature lower than that in the heat-setting step.
  • Thermal relaxation can relax the residual strain of the polyester film.
  • the surface temperature (thermal relaxation temperature) of the polyester film in the heat relaxation step is preferably 5°C or more lower than the heat setting temperature, more preferably 15°C or more lower, still more preferably 25°C or more lower, and 30°C or higher. Lower temperatures are particularly preferred.
  • the thermal relaxation temperature is preferably 235°C or lower, more preferably 225°C or lower, still more preferably 210°C or lower, and particularly preferably 200°C or lower.
  • the lower limit of the thermal relaxation temperature is preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher.
  • the method for producing the release film may include a cooling step of cooling the heat-relaxed polyester film.
  • the cooling rate of the polyester film in the cooling step is preferably more than 2000° C./min and less than 4000° C./min, more preferably 2000 to 3500° C./min, more than 2200° C./min and less than 3000° C./min.
  • 2300-2800° C./min is particularly preferred.
  • the cooling step preferably includes a step (expansion step) of expanding the thermally relaxed polyester film in the width direction.
  • the expansion rate of the polyester film in the width direction by the expansion step is preferably 0% or more, and more preferably 0.001% or more. Preferably, 0.01% or more is more preferable.
  • the upper limit of the expansion rate is not particularly limited, it is preferably 1.3% or less, more preferably 1.2% or less, and even more preferably 1.0% or less.
  • the production method may have a winding step of obtaining a roll-shaped polyester film by winding the polyester film obtained through the above steps.
  • the manufacturing method further comprises a trimming step of continuously cutting the polyester film along the transport direction and cutting off at least one end in the width direction of the polyester film before performing the winding step. good too.
  • the transport speed of the polyester film in each step other than the longitudinal stretching step of the present production method is not particularly limited, but in the lateral stretching step, heat setting step, heat relaxation step, and cooling step, in terms of productivity and quality, 50 to 200 m/min is preferred, and 80 to 150 m/min is more preferred.
  • a method for producing a release film described above a method of forming a particle-containing layer by applying a composition for forming a particle-containing layer in the step of forming a particle-containing layer has been described. is not limited to, and a known method can be used. For example, there is a method of forming an unstretched polyester substrate laminated with a particle-containing layer by coextrusion molding.
  • a method for producing a release film preferably includes a step of applying the particle-containing layer-forming composition to one surface of a polyester base material.
  • the stretching step of stretching an unstretched polyester base material and/or the particle-containing layer forming step of forming a particle-containing layer on one surface of the polyester base material may be performed at the same time or before or after the shows an embodiment in which the peeling layer forming step is performed, but the timing of performing the peeling layer forming step is not limited to the above embodiment.
  • the stretching step, and the particle-containing layer forming step to produce a laminated film having a polyester substrate and a particle-containing layer formed on one surface of the polyester substrate may be performed at the same time or before or after the shows an embodiment in which the peeling layer forming step is performed, but the timing of performing the peeling layer forming step is not limited to the above embodiment.
  • the stretching step, and the particle-containing layer forming step to produce a laminated film having a polyester substrate and a particle-containing layer formed on one surface of the polyester substrate.
  • a release layer forming composition is applied to the surface of the polyester substrate opposite to the particle-containing layer to form a release layer.
  • a release film can be made comprising, in that order, a layer, a polyester substrate and a release layer.
  • the release film is preferably used as a release film (carrier film) for producing a ceramic green sheet.
  • a ceramic green sheet manufactured using the above-described release film can be suitably used for manufacturing ceramic capacitors for which multi-layered internal electrodes are required in accordance with miniaturization and increase in capacity.
  • a method for producing a ceramic green sheet using the release film is not particularly limited, and a known method can be used.
  • a method for producing the ceramic green sheet includes, for example, a method in which a prepared ceramic slurry is applied to the release surface of the release film, and the solvent contained in the ceramic slurry is removed by drying. The method of applying the ceramic slurry is not particularly limited.
  • a known method such as applying a ceramic slurry obtained by dispersing ceramic powder and a binder in a solvent by a reverse roll method and removing the solvent by heating and drying. method can be applied.
  • the binder agent is not particularly limited, and examples thereof include polyvinyl butyral.
  • the solvent is not particularly limited, and examples thereof include ethanol and toluene.
  • the ceramic green sheets produced in this manner are used to produce ceramic capacitors.
  • a known method can be applied as a method of manufacturing a ceramic capacitor using a ceramic green sheet, and examples thereof include the following method.
  • internal electrodes are provided by coating or printing a conductive paste on the laminate of the release film and the ceramic green sheets produced by the above method.
  • the release film is removed from the laminate of ceramic green sheets, the ceramic green sheets with internal electrodes are successively laminated, and the resulting laminate is pressed to produce an intermediate laminate. After cutting the intermediate laminate into a desired shape, the cut intermediate laminate is fired.
  • a ceramic capacitor is obtained by forming external electrodes electrically connected to the internal electrodes on the two end surfaces of the fired intermediate laminate using a conductive paste such as silver.
  • the release film of the present invention includes a protective film for dry film resist, a film for sheet molding such as a decorative layer and a resin sheet, a release film for process manufacturing such as a semiconductor manufacturing process, and a release film for a polarizing plate manufacturing process. , and can also be used as a separator for adhesive films for labels, medical and office supplies.
  • Example 1 Polyethylene terephthalate pellets were produced using a titanium compound described in Japanese Patent No. 5575671 (citric acid chelate titanium complex, VERTEC AC-420, manufactured by Johnson Matthey) as a polymerization catalyst. Specifically, 1 ton (1000 kg) of terephthalic acid, 390 kg of ethylene glycol, and 9 ppm by mass of Ti atoms with respect to polyethylene terephthalate, which produces a titanium compound, were mixed. The resulting mixture was continuously supplied to the reactor to carry out an esterification reaction.
  • a titanium compound described in Japanese Patent No. 5575671 citric acid chelate titanium complex, VERTEC AC-420, manufactured by Johnson Matthey
  • magnesium acetate tetrahydrate in an amount such that the Mg atom is 81 mass ppm relative to the polyethylene terephthalate produced, and trimethyl phosphate in an amount such that the P atom is 73 mass ppm relative to the polyethylene terephthalate produced. was added to the mixture to carry out a polycondensation reaction to produce polyethylene terephthalate pellets.
  • the obtained pellets were dried to a moisture content of 50 ppm or less, put into a hopper of a single-screw kneading extruder with a diameter of 30 mm, melted at 280° C. and extruded.
  • the melt was passed through a filter (pore size of 3 ⁇ m) and then extruded from a die onto a cooling drum at 25° C. to obtain an unstretched polyester substrate made of polyethylene terephthalate.
  • the extruded melt (melt) was brought into close contact with the cooling drum by an electrostatic application method.
  • the melting point (Tm) of polyethylene terephthalate constituting the unstretched polyester base material was 258°C, and the glass transition temperature (Tg) was 80°C.
  • the unstretched film was subjected to a longitudinal stretching step by the following method.
  • a uniaxially oriented film was produced by passing the preheated unstretched film between two pairs of rolls having different circumferential speeds and stretching it in the machine direction (conveying direction) under the following conditions.
  • composition A1 particle-containing layer-forming composition
  • composition L1 composition for forming a release layer
  • the coating amounts of the composition A1 and the composition L1 were adjusted so that the thickness of the particle-containing layer formed after the lateral stretching was 40 nm and the thickness of the release layer was 100 nm.
  • composition A1 Composition A1 was prepared by mixing each component shown below. The prepared composition A1 was subjected to filtration treatment using a filter with a pore size of 6 ⁇ m (F20, manufactured by Mahle Filter Systems Co., Ltd.), and membrane degassing (2x6 radial flow superphobic, manufactured by Polypore Co., Ltd.). , the obtained composition A1 was applied to the surface of the uniaxially oriented film.
  • ⁇ Urethane resin 1 (Hydran (registered trademark) AP-40N, manufactured by DIC Corporation, an aqueous dispersion with a solid concentration of 25% by mass): 157 parts by mass ⁇ Anionic hydrocarbon surfactant (Rapisol (registered Trademark) A-90, di-2-ethylhexyl sodium sulfosuccinate, manufactured by NOF Corporation, solid content concentration 1% by mass diluted with water): 56 parts by mass Organic particles O1 (crosslinked PMMA particles, Eposter (registered trademark) MX050W , Nippon Shokubai Co., Ltd., average particle diameter 70 nm, solid content concentration 10% by mass aqueous dispersion): 8 parts by mass, water: 779 parts by mass
  • composition L1 Composition L1 was prepared by mixing each component shown below. Filtration treatment and membrane degassing in the same manner as composition A1 were performed on the prepared composition L1 to obtain composition L1.
  • ⁇ Silicone emulsion DEHESIVE EM480, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.
  • 20 parts by mass ⁇ Silicone emulsion
  • CROSSLINKER V72 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.
  • ⁇ Silane coupling agent KBM403, Shin-Etsu Chemical Co., Ltd. ( Co., Ltd.): 0.1 parts by mass, water: 77 parts by mass
  • Thermal relaxation process was subjected to a heat relaxation step for relaxing the tension of the film by heating under the following conditions. Also, in the heat relaxation step, the film width was reduced compared to that at the end of the heat setting step by narrowing the distance (tenter width) between the gripping members of the tenter that grips both ends of the film.
  • a cooling step was performed on the thermally relaxed film under the following conditions. Further, in the cooling step, an expansion step was performed to expand the width of the film compared to that at the end of the thermal relaxation step by expanding the width of the tenter.
  • the following cooling rates were measured when the film surface temperature was measured when the film was transported into the cooling unit and when the film was transported out of the cooling unit, with the cooling time ta being the residence time from when the film was transported into the cooling unit of the stretching machine until it was transported out. It was obtained by dividing the temperature difference ⁇ T (°C) from the film surface temperature by the cooling time ta.
  • the film cooled in the cooling step was continuously cut along the conveying direction at positions 20 cm from both ends in the width direction of the film to trim both ends of the film. Then, the film was wound up with a tension of 40 kg/m after extrusion processing (knurling) was performed on a region from both ends of the film to 10 mm in the width direction.
  • a release film was produced by the above method. The obtained release film had a thickness of 31 ⁇ m, a width of 1.5 m, and a winding length of 7000 m.
  • Examples 2-9 and 12-13 As shown in Table 1, the release films of Examples 2 to 9 and 12 to 13 were prepared in the same manner as in Example 1, except that the types of particles and resin in the particle-containing layer and the thickness of each layer were changed. made.
  • Composition A6 of Example 6 was obtained by replacing organic particles O1 in Example 4 with 6.7 masses of organic particles O2 (Eposter (registered trademark) MX100W, average particle diameter 150 nm, solid content concentration 10% by mass aqueous dispersion). part and organic particles O4 (Eposter (registered trademark) MX300W, average particle diameter 450 nm, solid content concentration 10% by mass aqueous dispersion) 1.3 parts by mass in the same manner as composition A4 of Example 4. prepared.
  • Composition A7 of Example 7 was obtained by replacing the organic particles O1 in Example 4 with 2.7 masses of organic particles O3 (Eposter (registered trademark) MX200W, average particle diameter 350 nm, solid content concentration 10% by mass aqueous dispersion).
  • organic particles O3 Eposter (registered trademark) MX200W, average particle diameter 350 nm, solid content concentration 10% by mass aqueous dispersion.
  • composition A4 of Example 4 Part and inorganic particles I1 (Snowtex (registered trademark) MP-2040, manufactured by Nissan Chemical Co., Ltd., colloidal silica, average particle diameter 200 nm, adjusted to a solid content concentration of 10% by mass aqueous dispersion) Replaced with 5.3 parts by mass It was prepared in the same manner as composition A4 of Example 4, except that Composition A8 of Example 8 was obtained by replacing the organic particles O1 in Example 4 with 6.7 masses of organic particles O2 (Eposter (registered trademark) MX100W, average particle diameter 150 nm, solid content concentration 10% by mass aqueous dispersion).
  • composition A12 of Example 12 the organic particles O1 in Example 4 were replaced with 7.0 parts by mass of organic particles O2 (Eposter (registered trademark) MX100W, average particle diameter 150 nm, solid content concentration 10% by mass aqueous dispersion).
  • organic particles O2 Organic particles O2
  • Inorganic particles I1 Snowtex (registered trademark) MP-2040, manufactured by Nissan Chemical Co., Ltd., colloidal silica, average particle diameter 200 nm, adjusted to a solid content concentration of 10% by mass aqueous dispersion
  • Replaced with 1.0 parts by mass Except that, it was prepared in the same manner as composition A4 of Example 4.
  • Composition A13 of Example 13 was obtained by replacing the organic particles O1 in Example 4 with 6.0 parts by mass of organic particles O3 (Eposter (registered trademark) MX200W, average particle diameter 350 nm, solid content concentration 10% by mass aqueous dispersion). , Inorganic particles I2 (Snowtex (registered trademark) ZL, manufactured by Nissan Chemical Co., Ltd., colloidal silica, particle diameter 70 to 100 nm, adjusted to a solid content concentration of 10% by mass aqueous dispersion) 2.0 parts by mass Except that, it was prepared in the same manner as composition A4 of Example 4.
  • organic particles O3 Organic particles O3
  • Inorganic particles I2 Snowtex (registered trademark) ZL, manufactured by Nissan Chemical Co., Ltd., colloidal silica, particle diameter 70 to 100 nm, adjusted to a solid content concentration of 10% by mass aqueous dispersion
  • Example 10 A biaxially oriented film was prepared according to the method described in Example 1, except that no release layer was formed. The obtained film was unwound, and the following composition L2 was applied to the surface of the polyester substrate opposite to the particle-containing layer so that the thickness after curing was 500 nm. After the formed coating film was dried at 90° C., it was thermally cured by heating at 120° C. for 1 minute to form a release layer, thereby producing a release film.
  • composition L2 Acrylic resin 2 (a copolymer obtained by polymerizing methyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, and methacrylic acid at a mass ratio of 47:26:20:7, solid content 40% by mass toluene solution):1.
  • 75 parts by mass Polyester-modified silicone resin (BYK-370, manufactured by BYK-Chemie Japan Co., Ltd., solid content concentration 25% by mass): 0.05 parts by mass Thermally polymerizable compound (hexamethoxymelamine, Tokyo Chemical Industry Co., Ltd.
  • composition L3 was used instead of composition L2 in the release layer forming step.
  • Composition L3 ⁇ Amino alkyd resin (Tesfine 305, Showa Denko Materials Co., Ltd., solid content 50% by mass): 2.0 parts by mass ⁇ Polyester-modified silicone resin (BYK-370, manufactured by BYK-Chemie Japan Co., Ltd., solid content concentration 25 mass) %): 0.01 parts by mass Acid catalyst (p-toluenesulfonic acid, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., solid content 100% by mass): 0.02 parts by mass Methyl ethyl ketone: 58 parts by mass Toluene: 40 part by mass
  • Comparative Example 1 11 parts by mass of inorganic particles I1 (Snowtex (registered trademark) MP-2040, manufactured by Nissan Chemical Industries, Ltd., colloidal silica, average particle diameter 200 nm, solid content concentration 40% by mass aqueous dispersion) instead of organic particles O1 and that "Surflon (registered trademark) S-211" (manufactured by AGC Seimi Chemical Co., Ltd., fluorine-based surfactant) was used instead of "Rapisol A-90" as a surfactant.
  • Composition CA1 was prepared according to the method for preparing composition A2 in Example 2. Except for using the composition CA1 instead of the composition A1 in the particle-containing layer forming step, changing the thickness of the particle-containing layer, and changing the thickness of the release layer in the release layer forming step. prepared a release film according to the method described in Example 10.
  • Comparative Example 2 Using 8 parts by mass of organic particles O2 (crosslinked PMMA particles, Eposter (registered trademark) MX100W, manufactured by Nippon Shokubai Co., Ltd., average particle diameter 150 nm, solid content concentration 40% by mass aqueous dispersion) instead of inorganic particles I1, and , instead of urethane resin 2, the copolymer polyester resin contained in the polyester water dispersion (Aw-1) prepared according to the method described in International Publication No. 2017/199774 was changed to Comparative Example 1.
  • Composition CA2 was prepared according to the method for preparing composition CA1.
  • a release film was produced according to the method described in Comparative Example 1, except that the composition CA2 was used instead of the composition CA1 in the particle-containing layer forming step.
  • composition L4 was used instead of composition L2 in the release layer forming step.
  • composition L4 ⁇ Amino alkyd resin (Tesfine 305, Showa Denko Materials Co., Ltd., solid content 50% by mass): 2.0 parts by mass ⁇ Acid catalyst (p-toluenesulfonic acid, Fuji Film Wako Pure Chemical Co., Ltd., solid content 100 % by mass): 0.02 parts by mass Methyl ethyl ketone: 58 parts by mass Toluene: 40 parts by mass
  • Barium titanate powder (BaTiO 3 ; manufactured by Sakai Chemical Industry Co., Ltd., product name “BT-03”) 100 parts by mass, polyvinyl butyral resin as a binder (manufactured by Sekisui Chemical Co., Ltd., product name “S-Lec (registered trademark) B ⁇ K BM-2”) 8 parts by mass, 4 parts by mass of dioctyl phthalate as a plasticizer (manufactured by Kanto Chemical Co., Ltd., dioctyl phthalate, deer 1st class), and a mixed solution of toluene and ethanol (mass ratio 6: 4) 135 parts by mass were mixed.
  • a ceramic slurry was prepared by dispersing the mixture in the presence of zirconia beads using a ball mill and removing the beads from the resulting dispersion.
  • the release films obtained in each example and each comparative example were stored in an environment of normal temperature and normal humidity (25° C., 50% RH) for 1 week.
  • the ceramic slurry was coated on the release surface of the release film after storage with a die coater over a width of 250 mm and a length of 10 m so that the film thickness after drying was 1 ⁇ m.
  • the resulting coating film was dried at 100° C. for 2 minutes in a dryer, and then wound into a roll.
  • a fluorescent lamp is illuminated from the release film side, and a 1 m2 area on the surface of all the molded ceramic green sheets is visually inspected to detect minute irregularities such as pinholes. was inspected for the presence of Based on the number of confirmed defects, defects on the surface of the ceramic green sheet were evaluated according to the following evaluation criteria.
  • the release film the same method as described in Defect Evaluation 1 of Ceramic Green Sheet was used, except that a release film wound under high-speed transport conditions according to the method described in the method for evaluating winding properties at high-speed transport was used.
  • a ceramic green sheet was provided on the release surface of the release film.
  • the obtained release film with ceramic green sheets was unwound and laminated on a glass substrate with electrodes so that the ceramic green sheets formed on the release film were in contact with the glass substrate.
  • the resulting laminate was thermocompression bonded (100° C., 0.5 MPa) using a heating roller.
  • the release film was peeled off from the laminate, and the glass substrate to which the ceramic green sheet was pressure-bonded was fired at 400°C for 20 minutes. By firing for 30 minutes, a glass substrate having a ceramic layer formed on its surface was obtained. An observation area (100 mm ⁇ 100 mm) on the surface of the resulting ceramic layer was observed for the presence or absence of uneven defects using an optical microscope. Based on the confirmed number of defects in the observation area, defects in the fired ceramic layer were evaluated according to the following criteria. If there are few defects in the ceramic layer after firing as confirmed by the above evaluation method, even in a multilayer ceramic capacitor manufactured using ceramic green sheets formed on the release surface of the same release film, the characteristics as a capacitor are affected. Since it is possible to suppress the formation of minute irregularities that may occur, it is considered that the performance of suppressing the defect rate of the multilayer ceramic capacitor is superior.
  • the adhesive tape side of the sample is fixed to the surface of the glass plate, and using a Tensilon universal tester manufactured by A&D Co., Ltd., under the conditions of a peeling angle of 180 ° and a peeling speed of 100 mm / min, the release film from the ceramic green sheet. was peeled off and the force required to peel off was measured.
  • Peelability was evaluated according to the following criteria. (Evaluation criteria) A: When peeling from the ceramic green sheet, it can be peeled off with a force of 45 mN or less. B: When peeling from the ceramic green sheet, a force of more than 45 mN and 100 mN or less is required. C: A force of more than 100 mN is required when peeling from the ceramic green sheet.
  • composition and characteristics of the particle-containing layer and the release layer, and the evaluation results of the evaluation test described above are shown in Table 1 below for the release films produced in each example and each comparative example.
  • Binder ⁇ Urethane resin 1: Hydran (registered trademark) AP-40N, manufactured by DIC Corporation ⁇ Urethane resin 2: ADEKA BONDITTER (registered trademark) HUX-524, manufactured by ADEKA Corporation.
  • Olefin resin Zaixen (registered trademark) NC, manufactured by Sumitomo Seika Co., Ltd.
  • Acrylic resin 1 a copolymer obtained by polymerizing methyl methacrylate, styrene, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate and acrylic acid at a mass ratio of 59:8:26:5:2.
  • -Polyester resin Polymerization of dimethyl terephthalate, dimethyl isophthalate, dimethyl-5-sodium sulfoisophthalate, ethylene glycol and neopentyl glycol at a mass ratio of 194.2:184.5:14.8:185.1:185.1 A copolymer formed by
  • the "thickness” column indicates the thickness of the particle-containing layer and the release layer, respectively.
  • the method for measuring the thickness of each layer is as described above. After taking out the cross section of the release film with a microtome, etching treatment is performed with Ar ions, Pt is deposited, and SEM (S-4800, manufactured by Hitachi High Tech). was observed and measured.
  • the "Sp” column indicates the maximum protrusion height Sp of the particle-containing layer and the peeling layer
  • the "Sa” column indicates the surface average roughness Sa of the peeling layer.
  • the definitions of the “maximum protrusion height Sp” and the “surface average roughness Sa” of each layer are as described above, and the measurement method is also as described above.
  • the "Surface E” column shows the surface free energies of the conveying surface and the peeling surface.
  • the definition and measurement method of the surface free energy of each layer are as described above. It was obtained from the results of dripping drops of methylene and ethylene glycol.
  • ratio of organic particle protrusions indicates the ratio (number ratio) of protrusions formed by organic particles among the protrusions present on the conveying surface.
  • the method for measuring the proportion of protrusions formed by organic particles is as described above, and "P” indicates that the proportion of protrusions formed by organic particles is 50% or more among the protrusions present on the conveying surface. and "N” when the percentage of protrusions formed by organic particles is less than 50%.
  • the column "Sp Forming Particles" indicates whether or not the protrusions having the maximum protrusion height Sp among the protrusions present on the conveying surface are protrusions formed of organic particles.
  • the analysis as to whether or not the particles forming the maximum protrusion height Sp among the protrusions on the conveying surface are organic particles was performed as follows. Mark the transfer surface of the release film with a felt pen, and use an optical interferometer (Vertscan R3300G Lite, manufactured by Hitachi High-Tech Co., Ltd.) in the vicinity of the mark to measure the maximum protrusion height Sp under the following measurement conditions. bottom.
  • the projections present in the observation area (measurement field) of 100 ⁇ m ⁇ 100 ⁇ m select the projections that match the maximum projection height Sp, analyze the element distribution with an EDS analyzer, and match the maximum projection height It was determined whether the particles forming the protrusions were organic particles or inorganic particles.
  • the method for determining organic particles and inorganic particles is as described above. In 10 different observation areas on the conveying surface of the sample, it was specified whether the particles forming the protrusions exhibiting the maximum protrusion height Sp were organic particles or inorganic particles. A case where the number ratio of the organic particles to the particles forming the protrusions exhibiting the maximum protrusion height Sp was 50% or more was rated as "O", and the others were rated as "I”. When the determination result by the above method is "O", the release film is evaluated as having a conveying surface on which protrusions having the maximum protrusion height Sp are formed by organic particles.
  • the particle-containing layer does not contain a non-polyester resin. It was confirmed that, compared with Comparative Example 2, the occurrence of defects in the produced ceramic green sheets can be suppressed.
  • the release film when the maximum protrusion height Sp on the surface of the particle-containing layer opposite to the polyester substrate is 25 nm or more, it was confirmed that the release film has excellent winding properties during high-speed transportation. It was confirmed that when the height Sp is 1000 nm or less, the ceramic green sheet has excellent defect suppression performance (comparison with Examples 1 to 13).
  • the ceramic layer can be transported at a high speed. It was confirmed that the surface defect suppression performance was superior (comparison with Examples 5 to 7). If the surface of the particle-containing layer opposite to the polyester substrate has projections, and among these projections, the projections having the maximum projection height Sp are the projections formed by the organic particles, the high-speed transport is not possible. It was confirmed that the performance of suppressing defects on the surface of the ceramic layer is excellent (comparison with Examples 5-6 and 12-13).
  • Release film 2 Release layer 4: Polyester substrate 6: Particle-containing layer 21: Surface (release surface) 61: Surface (conveyance surface)

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Abstract

La présente invention aborde le problème consistant à fournir : un film de protection qui a d'excellentes propriétés de protection d'une feuille verte de céramique et une excellente suppression de taux de défauts d'un condensateur céramique même lorsqu'il est transporté à grande vitesse ; un procédé de fabrication du film de protection ; et un condensateur céramique.　Le présent film de protection comprend une couche de protection, un matériau de base de polyester et une couche contenant des particules, dans cet ordre. La couche contenant des particules contient des particules et une résine non polyester, les particules comprennent des particules organiques et la couche de protection comprend un composé de silicone.
PCT/JP2022/029725 2021-08-26 2022-08-03 Film de protection, procédé de fabrication d'un film de protection et condensateur céramique WO2023026800A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6402866B1 (en) * 1999-09-30 2002-06-11 International Business Machines Corporation Powdered metallic sheet method for deposition of substrate conductors
WO2018159247A1 (fr) * 2017-03-01 2018-09-07 東洋紡株式会社 Film de démoulage pour fabrication de feuille crue de céramique, et procédé de fabrication de celui-ci
WO2019088184A1 (fr) * 2017-11-02 2019-05-09 東洋紡株式会社 Film de démoulage pour fabrication de feuille de céramique crue
JP2019072850A (ja) * 2017-10-12 2019-05-16 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP2020185763A (ja) * 2019-05-17 2020-11-19 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP2021024175A (ja) * 2019-08-02 2021-02-22 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102342605B1 (ko) 2018-09-03 2021-12-23 도요보 가부시키가이샤 세라믹 그린시트 제조용 이형 필름

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6402866B1 (en) * 1999-09-30 2002-06-11 International Business Machines Corporation Powdered metallic sheet method for deposition of substrate conductors
WO2018159247A1 (fr) * 2017-03-01 2018-09-07 東洋紡株式会社 Film de démoulage pour fabrication de feuille crue de céramique, et procédé de fabrication de celui-ci
JP2019072850A (ja) * 2017-10-12 2019-05-16 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
WO2019088184A1 (fr) * 2017-11-02 2019-05-09 東洋紡株式会社 Film de démoulage pour fabrication de feuille de céramique crue
JP2020185763A (ja) * 2019-05-17 2020-11-19 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP2021024175A (ja) * 2019-08-02 2021-02-22 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム

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