WO2024053483A1 - 離型フィルム - Google Patents

離型フィルム Download PDF

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Publication number
WO2024053483A1
WO2024053483A1 PCT/JP2023/031214 JP2023031214W WO2024053483A1 WO 2024053483 A1 WO2024053483 A1 WO 2024053483A1 JP 2023031214 W JP2023031214 W JP 2023031214W WO 2024053483 A1 WO2024053483 A1 WO 2024053483A1
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Prior art keywords
film
release layer
group
less
mol
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English (en)
French (fr)
Japanese (ja)
Inventor
真司 矢野
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Toyobo Co Ltd
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Toyobo Co Ltd
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Priority to CN202380063716.3A priority Critical patent/CN119855864A/zh
Priority to JP2024545596A priority patent/JPWO2024053483A1/ja
Priority to KR1020257002615A priority patent/KR20250029174A/ko
Publication of WO2024053483A1 publication Critical patent/WO2024053483A1/ja
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a release film having a base film and a release layer, and more particularly to a release film useful as a film for various processes.
  • release films based on polyester films have high heat resistance and mechanical properties, and are used as process films for forming adhesive sheets, cover films, resin sheets such as ceramic slurries and polymer electrolyte membranes. It is used. Further, as a release layer of a release film, many release layers formed from coating compositions containing silicone have been proposed because they have good heat resistance and peelability (for example, Patent Documents 1 to 4).
  • Patent Documents 1 and 2 disclose a release film in which a release layer is formed from a coating composition containing a polysiloxane having an unsaturated group, a polysiloxane having an Si-H group, a platinum group metal catalyst, etc., and an organic solvent. Proposed.
  • Patent Document 3 describes an aqueous coating composition containing an alkenyl group-containing silicone and a Si-H group-containing silicone.
  • a release film in which a release layer is formed using a material has been proposed.
  • a release film is disclosed in which a release layer is formed using an alkenyl group-containing silicone having a number average molecular weight of 25,000 and a Si--H group-containing silicone having a number average molecular weight of 4,500.
  • Patent Document 4 discloses that in order to achieve both easy releasability and good wettability, an aqueous silicone containing an alkenyl group-containing silicone having a Q unit represented by SiO 4/2 and a Si-H group-containing silicone is disclosed.
  • a release film in which a release layer is formed using a coating composition has been proposed.
  • a release film is disclosed in which a release layer is formed using an alkenyl group-containing silicone having a Q unit and a number average molecular weight of 25,000 and a Si-H group-containing silicone having a number average molecular weight of 4,500. There is.
  • Patent Document 6 discloses a technique that uses a polyester film as a base material, has a mold release coating layer on one surface, and nanoindensed resin on the mold release coating layer.
  • a film is proposed.
  • a nanoindentation test was performed using a microhardness evaluation device at a maximum indentation depth of 50 nm, and the film elastic modulus of the release coating layer was measured.
  • the sheet-like molded product such as a ceramic green sheet formed on the surface is half-cut using a cutting blade, and then released from the mold. It is often peeled off from the film and transported to the next process. At that time, even if the release film has sufficient peelability, the sheet-like molded product may not be able to be properly peeled off at the part where the peeling occurs (half-cut part), which leads to a decrease in yield. .
  • an object of the present invention is to provide a release film that is less likely to cause problems due to adhesion to half-cut portions when peeling off a sheet-like molded product after half-cutting.
  • the present inventors found that the above problems could be solved by forming a mold release layer whose erosion was within a specific range as determined by a micro-slurry jet erosion test. , we have completed the present invention. That is, the present invention includes the following contents.
  • release film according to any one of [1] to [4], wherein the release film is a release film for a multilayer ceramic capacitor or a release film for a resin sheet.
  • the present invention it is possible to provide a release film that is less likely to cause problems due to adhesion to half-cut portions when peeling off a sheet-like molded product after half-cutting.
  • a mold release layer with a certain level of erosion obtained in a micro-slurry jet erosion test has low toughness (brittleness) against microscopic physical effects, so it is difficult for the mold release layer to denature during half-cutting. It is thought that this makes it possible to effectively prevent the sheet-like molded product in close contact with the mold release layer from deforming and adhering to the half-cut portion. This can be understood from the fact that after the sheet-like molded product is peeled off, there is little remaining in the half-cut portion of the release film.
  • the mold release film of the present invention is a mold release film having a base film (hereinafter sometimes referred to as "base material”) and a mold release layer, and the mold release layer is Erosion when a slurry of polygonal alumina particles with an average particle diameter (D 50 ) of 0.3 ⁇ m dispersed in water is projected at a projection force that gives an erosion rate of 0.019 ⁇ m/g to polymethyl methacrylate resin. It is characterized in that the ratio is 0.003 ⁇ m/g or more.
  • MSE test Micro Slurry Jet Erosion (MSE) tester, manufactured by Palmeso Co., Ltd., device name: MSE-A, to collide particles with the measurement target.
  • MSE Micro Slurry Jet Erosion
  • the erosion depth can be measured using a measuring device, and the erosion rate can be calculated from the erosion depth relative to the amount of particles collided with.
  • particles are made of materials such as resins, metals, and ceramics, and have an average particle diameter of 10 ⁇ m or less, and particles of specific sizes such as polygonal alumina, spherical alumina, and spherical silica are used for quantitative comparison between measurement samples. Particles can be used.
  • the erosion rate of the release layer in the present invention in the MSE test is measured as follows. A slurry containing 1% by mass of polygonal alumina particles with an average particle diameter (D 50 ) of 0.3 ⁇ m was projected onto the surface of the mold release layer using a nozzle diameter of 0.3 mm ⁇ at a distance of 4 mm from the nozzle tip to the sample, and the mold release layer was cut. do. The cutting displacement with respect to the amount of slurry sprayed and the cutting depth per 1 g of slurry were expressed as erosion rate ( ⁇ m/g). In other words, a large erosion rate value indicates that the cut material is brittle and weak, and a small erosion rate value indicates that the cut material is flexible and strong.
  • the erosion rate of the release layer in the present invention in the MSE test is 0.003 ⁇ m/g or more, preferably 0.003 ⁇ m/g or more and 0.020 ⁇ m/g or less, and 0.004 ⁇ m/g or more and 0.010 ⁇ m/g or more. g or less is more preferable.
  • the mold release layer is considered to be flexible and strong, and when the ceramic green sheet laminated on the surface of the mold release layer is half-cut, if the mold release layer is flexible and strong, it is considered a ceramic green sheet. Since the ceramic green sheet cannot be cut cleanly and follows along with the mold release layer, there is a possibility that the ceramic green sheet may stretch or remain at the half-cut portion. If the ceramic green sheet stretches or remains in the half-cut portion, it is not preferable because it will not be able to be peeled off uniformly in the peeling process.
  • the erosion rate is 0.003 ⁇ m/g or more
  • the release layer is brittle when the ceramic green sheet is half-cut, so that the cut portion can be instantly and cleanly cut. Therefore, the ceramic green sheets do not elongate or remain, and can be peeled off uniformly in the peeling process, and can be peeled off stably in the peeling process. Further, it is preferable that the erosion rate is less than or equal to the upper limit of the above-mentioned preferable range, since detachment and cohesive failure of the release layer are less likely to occur.
  • a method of adjusting the erosion rate for example, a method of adjusting the density of crosslinking points of the resin contained in the mold release layer, specifically, a method of adjusting the density of crosslinking points of the resin contained in the release layer, specifically, using alkenyl group-containing silicone or Si-H group-containing silicone with a lower number average molecular weight.
  • the erosion rate can be increased by using silicone or by using silicone containing Si--H groups with a high molar ratio of Si--H groups.
  • by adjusting the density of the branched structure of the resin contained in the release layer specifically, by using an alkenyl group-containing silicone having a Q unit represented by SiO 4/2 , it is possible to can increase the John's rate.
  • the erosion rate can be increased by using a resin with a high crosslinking density in addition to the mold release component, or by using a substance with a large number of reactive points, such as a low molecular weight crosslinking agent or a coupling agent. It is possible.
  • the release layer may contain a release agent component such as a silicone compound, a long-chain alkyl group-containing compound, a fluorine-containing compound, or an acrylic compound, and may also contain a binder component, a crosslinking agent, a modifying resin, and a solvent. , a catalyst, a surfactant, a crosslinking reaction inhibitor, a coupling agent, and the like.
  • a reactively curable composition containing a silicone compound is reacted and solidified from the viewpoint of good heat resistance and peelability, and easy control of surface free energy and erosion rate.
  • the release layer is preferably made of: Further, from the viewpoint of environmental consideration and safety, a release layer formed by reacting and solidifying an aqueous coating composition is more preferable.
  • the aqueous coating composition includes an alkenyl group-containing silicone having a number average molecular weight of 1,000 or more and less than 10,000, which has two or more alkenyl groups in the molecule and may have a Q unit represented by SiO 4/2 ; , those containing Si--H group-containing silicone having two or more Si--H groups in the molecule and having a number average molecular weight of 1,000 to 5,000 are preferred.
  • an alkenyl group-containing silicone having a number average molecular weight of 1,000 or more and less than 10,000, which has two or more alkenyl groups in the molecule and may have a Q unit represented by SiO 4/2 ; , those containing Si--H group-containing silicone having two or more Si--H groups in the molecule and having a number average molecular weight of 1,000 to 5,000 are preferred.
  • the alkenyl group-containing silicone includes an alkenyl group-containing silicone having two or more alkenyl groups in the molecule and a Q unit represented by SiO 4/2 , and/or an alkenyl group-containing silicone having two or more alkenyl groups in the molecule. Alkenyl group-containing silicones having a group and no Q unit represented by SiO 4/2 can be used.
  • the alkenyl group-containing silicone having a Q unit may be any compound having two or more alkenyl groups and a Q unit represented by SiO 4/2 in the molecule and having a siloxane bond in the main chain.
  • polyorganosiloxanes having alkenyl groups at the terminals and/or side chains are preferred.
  • a copolymer containing a dialkylsiloxane unit or an alkylphenylsiloxane unit is preferable because the amount of alkenyl groups in one molecule can be easily adjusted while exhibiting releasability.
  • the terminal silicon atom preferably has an alkenyl group, but may have a trialkylsilane structure such as trimethylsilane.
  • the alkenyl group-containing silicone that does not have a Q unit may be any compound as long as it has two or more alkenyl groups in the molecule and a siloxane bond in the main chain, but Polyorganosiloxanes having alkenyl groups are preferred. Further, a copolymer containing a dialkylsiloxane unit or an alkylphenylsiloxane unit is preferable because the amount of alkenyl groups in one molecule can be easily adjusted while exhibiting releasability.
  • the terminal silicon atom preferably has an alkenyl group, but may have a trialkylsilane structure such as trimethylsilane.
  • the alkenyl group may be introduced at one end, both ends, or a side chain, but it is preferably introduced at least at either end, and at both ends of the main chain. More preferably, it is introduced at the end.
  • the alkenyl group has two or more in the molecule, preferably 2 or more and 20 or less, and more preferably 2 or more and 10 or less.
  • the content of Q units expressed as SiO 4/2 is 0.5 mol% when all silicon atoms including terminals in the molecule are 100 mol%. It is preferably 30 mol% or less, more preferably 0.5 mol% or more and 20 mol% or less.
  • the content of Q units is 0.5 mol % or more, it becomes easy to form a dense mold release layer with high cohesive force, and it becomes easy to achieve both releasability and wettability of the mold release layer.
  • the content of Q units is 30 mol % or less, it becomes easy to suppress the formation of an excessively dense structure and the coating film from becoming brittle.
  • alkenyl group-containing silicones examples include organopolysiloxanes represented by the following general formula (I).
  • R 1 is an alkenyl group having 2 to 8 carbon atoms, or a monovalent hydrocarbon having 1 to 16 carbon atoms containing an alkyl group or an aryl group, which may be the same or different.
  • One or more of R 1 bonded to the silicon atom represented by [SiO] b1 is an alkenyl group having 2 to 8 carbon atoms
  • R 2 is an alkyl group or It is a monovalent hydrocarbon group containing an aryl group and having 1 to 16 carbon atoms
  • Y 1 may be the same or different and is represented by the general formula (Ia).
  • R 1 is the same as R 1 in general formula (I), and may be the same or different.
  • a1 is 50 mol% or more and 98 mol% or less
  • b1 is 0 mol% or more and 10 mol% or less
  • c1 is 0 mol% or more and 30 mol% or less
  • d1 is 0 mol% or more and 50 mol% or less.
  • two or more of R 1 are alkenyl groups having 2 or more and 8 or less carbon atoms.
  • the alkenyl group-containing silicone is, for example, a silicone represented by the following general formula (I').
  • Examples include organopolysiloxanes.
  • [SiO] R 2 bonded to the silicon atom represented by a1 may be a monovalent hydrocarbon group including an alkyl group or an aryl group, but may be a monovalent hydrocarbon group having 1 to 16 carbon atoms selected from an alkyl group or an aryl group. It is preferably a monovalent hydrocarbon group, more preferably a methyl group or a phenyl group, and even more preferably a methyl group.
  • R 1 bonded to the silicon atom represented by b1 is an alkenyl group having 2 or more and 8 or less carbon atoms, or a monovalent hydrocarbon group containing an alkyl group or an aryl group, and one or more of them has 2 or more carbon atoms. Any alkenyl group having 8 or less carbon atoms may be used, but it is preferably an alkenyl group having 2 or more carbon atoms and 8 or less carbon atoms, or a monovalent hydrocarbon group having 1 or more carbon atoms and 16 or less carbon atoms selected from an alkyl group or an aryl group.
  • R 1 is a hydrocarbon group other than an alkenyl group, a methyl group or a phenyl group is more preferable, and a methyl group is even more preferable.
  • R 1 bonded to the silicon atom represented by d1 may be an alkenyl group having 2 to 8 carbon atoms, or a monovalent hydrocarbon group containing an alkyl group or an aryl group, but may be a monovalent hydrocarbon group containing 2 to 8 carbon atoms. It is preferably a monovalent hydrocarbon group having 1 to 16 carbon atoms selected from the following alkenyl groups, alkyl groups, and aryl groups; More preferably, it is a monovalent hydrocarbon group.
  • R 1 is a hydrocarbon group other than an alkenyl group, a methyl group or a phenyl group is more preferable, and a methyl group is even more preferable.
  • R 1 at both ends of the main chain is also the same as R 1 bonded to the silicon atom shown in [SiO] b1 , but the preferred structure is an alkenyl group having 2 to 8 carbon atoms, and the alkenyl group at the end is Si It is particularly preferred because when it reacts with the -H group, steric structural hindrance becomes relatively small and peelability is easily improved.
  • R 1 bonded to the terminal silicon atom in general formula (Ia) is also the same as R 1 bonded to the silicon atom represented by [SiO] b1 , but the preferred structure is an alkenyl group having 2 or more and 8 or less carbon atoms. is preferable because it improves the cohesive force of the release layer and improves the release characteristics of process materials such as those using organic solvents.
  • Examples of the alkenyl group having 2 or more and 8 or less carbon atoms represented by R 1 include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and among these, a vinyl group is particularly preferred.
  • a1 is 50 mol% or more and 98 mol% or less, but 70 mol% or more and 98 mol% or less is preferred.
  • b1 is 0 mol% or more and 10 mol% or less, but preferably 0 mol% or more and 5 mol% or less.
  • c1 is 0.5 mol% or more and 30 mol% or less, preferably 0.5 mol% or more and 20 mol% or less.
  • d1 is 0 mol% or more and 50 mol% or less, It is preferably 0 mol% or more and 30 mol% or less.
  • [SiO] a1 is The range of the constituent units is preferably 90 mol% or more and 100 mol% or less, and more preferably 95 mol% or more and 100 mol% or less.
  • the number average molecular weight of the alkenyl group-containing silicone is preferably 1,000 or more and less than 10,000, more preferably 3,000 or more and less than 10,000. If the number average molecular weight is smaller than 1000 or more, the hydrocarbon groups will be localized on the coating surface, making it easier to obtain sufficient removability. On the other hand, when the number average molecular weight is less than 10,000, the emulsifying property of the aqueous coating composition tends to be good and the uniform coating properties also tend to be good.
  • the Si-H group-containing silicone may be a compound that has two or more Si-H groups (that is, two or more hydrogen atoms directly bonded to a Si atom) in the molecule and has a siloxane bond in the main chain.
  • any compound may be used, polyorganosiloxane having a Si--H group in the side chain is preferred.
  • a copolymer containing a dialkylsiloxane unit or an alkylphenylsiloxane unit is preferable because it is easy to adjust the amount of Si--H groups in one molecule while exhibiting releasability.
  • the terminal silicon atom may have a Si--H group, but preferably has a trialkylsilane structure such as trimethylsilane.
  • Si--H group-containing silicone is organohydrogenpolysiloxane represented by the following general formula (II).
  • R 3 is a monovalent hydrocarbon group having 1 to 16 carbon atoms and containing an alkyl group or an aryl group, which may be the same or different, and a2+b2 is 100 mol%. (In this case, a2 is 30 mol% or more and 90 mol% or less, and b2 is 10 mol% or more and 70 mol% or less.)
  • SiO A hydrogen atom (hydrogen group) is bonded to the silicon atom represented by a2 , and R3 may be a monovalent hydrocarbon group including an alkyl group or an aryl group; It is preferable that it is a monovalent hydrocarbon group having 1 or more and 16 or less carbon atoms selected from the following.
  • [SiO] b2 and R3 bonded to the terminal Si atom may be any monovalent hydrocarbon group containing an alkyl group or an aryl group, but are selected from alkyl groups and aryl groups having 1 to 16 carbon atoms. The following monovalent hydrocarbon groups are preferred.
  • the alkyl group is preferably a methyl group, ethyl group, propyl group, butyl group, etc.
  • the aryl group is preferably a phenyl group, tolyl group, etc.
  • the range of the structural unit of [SiO] a2 is preferably from 30 mol% to 90 mol%, and from 40 mol% to 80 mol%. The following are more preferred.
  • the a2 structural unit is 30 mol% or more, there will be a sufficient amount of crosslinking reaction points, the cohesive force of the mold release layer will increase, and the scratch resistance and solvent resistance of the mold release layer will also be good. preferable.
  • Si-H groups are less likely to remain in the release layer, and the surface activity of the release layer is less likely to increase and releasability is maintained well. Therefore, it is preferable.
  • the number average molecular weight of the Si--H group-containing silicone in the present invention is preferably 1,000 or more and 5,000 or less, more preferably 3,000 or more and 5,000 or less.
  • the number average molecular weight is 1000 or more, sufficient releasability can be easily obtained.
  • the number average molecular weight is 5,000 or less, the emulsification properties of the aqueous coating composition tend to be good, and the coating uniformity tends to be good as well.
  • the crosslinking reaction is more likely to proceed efficiently, the amount of residual Si--H groups in the release layer is reduced, and releasability is improved.
  • aqueous coating composition preferably 1 part by mass or more and 50 parts by mass or less of the Si--H group-containing silicone is contained, more preferably 2 parts by mass or more and 40 parts by mass or less, per 100 parts by mass of the alkenyl group-containing silicone. , more preferably 3 parts by mass or more and 30 parts by mass or less.
  • content of the Si--H group-containing silicone is 1 part by mass or more, there will be a sufficient amount of crosslinking reaction points, making it easier to form a dense crosslinked structure and improving the release layer properties, which is preferable.
  • the content of the Si-H group-containing silicone is 50 parts by mass or less, the Si-H groups in the release layer are less likely to remain, and the surface activity of the release layer is less likely to increase, resulting in good releasability. Therefore, it is preferable.
  • Polyvinyl alcohol resin When using a modifying resin, it is preferable to use a polyvinyl alcohol resin as the modifying resin for adjusting surface free energy and the like.
  • the polyvinyl alcohol resin polyvinyl alcohol or a copolymer thereof is used.
  • polyvinyl alcohol copolymers include vinyl alcohol-vinyl acetate copolymers, vinyl alcohol-vinyl butyral copolymers, ethylene-vinyl alcohol copolymers, and polyvinyl alcohol polymers having silyl groups in the molecule. Among these, vinyl alcohol-vinyl acetate copolymer and ethylene-vinyl alcohol copolymer are preferred.
  • the repeating unit derived from vinyl alcohol is preferably 70 mol% or more and 100 mol% or less, more preferably 85 mol% or more and 99 mol% or less.
  • the degree of polymerization of the polyvinyl alcohol resin in the present invention can be indicated by the viscosity of a 4% by mass aqueous solution at 20°C, and the viscosity is preferably 5 mPa ⁇ s or more and 50 mPa ⁇ s or less.
  • the viscosity is within the above numerical range, the aqueous coating composition has high miscibility and a more uniform release layer can be easily obtained. That is, it is preferable that the viscosity is 5 mPa ⁇ s or more, since it becomes difficult to flow within the coating film after the mold release layer is formed and the mold release properties are hard to deteriorate. It is preferable that the viscosity is 50 mPa ⁇ s or less because the viscosity of the entire aqueous coating composition is difficult to increase and uniform coating is facilitated.
  • polyvinyl alcohol resin can be mixed with silicone before emulsification, and can also be used as an emulsifier.
  • polyvinyl alcohol is obtained by polymerizing vinyl acetate to form polyvinyl acetate and then saponifying it, and the amount of saponification is expressed as the degree of saponification.
  • the degree of saponification of the polyvinyl alcohol resin is preferably 85 mol% or more and 99 mol% or less.
  • the degree of saponification is within the above-mentioned numerical range, the miscibility in the aqueous coating composition is high and a more uniform release layer can be easily obtained.
  • the degree of saponification is 85 mol% or more, adhesion to the base material is improved and miscibility with silicone is also improved.
  • the degree of saponification is 99% or less, the hydrophilicity of the release layer will not become too high, the cohesive force of the release layer coating will be easily maintained, and cases of deterioration of the adhesion of the release layer will be less likely to occur. .
  • polyvinyl alcohol resin commercially available products can be used as they are. Specific examples of such commercial products include Poval manufactured by Kuraray Co., Ltd. and Gohsenol manufactured by Mitsubishi Chemical Corporation.
  • a polyvinyl alcohol resin in the mold release layer When using a polyvinyl alcohol resin in the mold release layer, it is preferably contained in a range of 1% by mass or more and 20% by mass or less based on the mold release layer. A more preferred range is 1% by mass or more and 15% by mass or less, and an even more preferred range is 1% by mass or more and 10% by mass or less. When the content of the polyvinyl alcohol resin is within the above-mentioned numerical range, the two properties of miscibility with silicone and adhesion between the base material and the release layer can be achieved more favorably.
  • the content of the polyvinyl alcohol resin in the release layer is 1% by mass or more, the stability of the silicone emulsion in the coating liquid tends to be good, and when the content is 20% by mass or less, the release layer tends to be good. Mold characteristics are less likely to deteriorate.
  • Platinum-based catalyst The crosslinking reaction between the alkenyl group-containing silicone and the Si--H group-containing silicone is an addition reaction, and in one embodiment, it is preferable to use a platinum-based catalyst to accelerate the reaction.
  • platinum-based catalysts can be used, such as platinum chloride and chloroplatinic acid.
  • the platinum-based catalyst may be a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum(0) complex (Karstedt catalyst) in consideration of its dispersibility in silicone, and emulsifies the silicone. By simultaneously dispersing them, uniform dispersibility can be ensured.
  • the content of the platinum-based catalyst is preferably such that the mass of the platinum element is in the range of 10 ppm or more and 400 ppm or less based on the combined mass of the alkenyl group-containing silicone and the Si—H group-containing silicone. By setting it within such a range, it is possible to sufficiently cure the silicone, suppress the generation of silicone aggregates, and obtain a release film with excellent surface properties. When the mass ratio of the platinum element is below the upper limit, the addition reaction between the alkenyl group and the Si--H group becomes appropriate, and the generation of silicone aggregates tends to be suppressed. From this viewpoint, the content of the platinum-based catalyst is more preferably 300 ppm or less, still more preferably 200 ppm or less.
  • the mass ratio of the platinum element is at least the lower limit, the addition reaction will proceed sufficiently, making it difficult to cause insufficient curing of silicone.
  • the content of the platinum catalyst is more preferably 15 ppm or more, and still more preferably 20 ppm or more.
  • the aqueous coating composition When using an aqueous coating composition, the aqueous coating composition usually contains an aqueous solvent in addition to the alkenyl group-containing silicone and the Si-H group-containing silicone, and the aqueous solvent preferably contains water. used.
  • an aqueous dispersion of a silicone containing alkenyl groups and an aqueous dispersion of a silicone containing Si-H groups are used for preparing an aqueous coating composition.
  • the aqueous dispersion of each silicone preferably an aqueous emulsion is used.
  • the release layer is formed from such an aqueous emulsion, and the release layer is formed by applying an aqueous coating composition containing an aqueous emulsion (hereinafter sometimes referred to as "aqueous coating solution"). It is formed.
  • aqueous coating solution an aqueous coating composition containing an aqueous emulsion
  • a release layer can be formed during the film forming process without using explosion-proof equipment and recovery equipment that are required for organic solvents. It is also possible to contain some organic solvent, if necessary.
  • aqueous coating composition for example, surfactants, coupling agents, crosslinking reaction inhibitors, antistatic agents, ultraviolet absorbers, pigments, colorants, organic Or other additives such as inorganic particles, lubricants, antiblocking agents, etc. can be mixed into the aqueous coating composition.
  • surfactant In one embodiment, it is preferable to add a surfactant to the aqueous coating composition in order to promote wetting to the base film when providing the release layer.
  • surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, etc., and it is also possible to use one or more of these.
  • a nonionic surfactant In order to prevent the aqueous emulsions of silicone from coagulating with each other and not to affect the curing reaction of silicone, it is preferable to use a nonionic surfactant as the emulsifier.
  • the nonionic surfactant preferably has an HLB value in the range of 6 or more and 18 or less, such as higher alcohols, alkylene oxide adducts of higher fatty acids, esters of alkylene oxide adducts of higher fatty acids and alcohols, and alkanolamides. At least one selected from alkylene oxide adducts such as alkylene oxide adducts of , alkylene oxide adducts of sorbitan esters, and alkylene oxide adducts of higher fatty acid glycerides.
  • the HLB value is a value calculated using the Griffin calculation formula.
  • alkylene oxide examples include ethylene oxide, propylene oxide, and butylene oxide, and one or more of these may be used.
  • the HLB value is preferably in the range of 8 or more and 18 or less, and more preferably in the range of 10 or more and 15 or less, although it does not matter whether the addition format is block or random.
  • nonionic surfactants polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, and the like are preferably mentioned. If necessary, two or more types of nonionic surfactants may be mixed.
  • a nonionic surfactant whose HLB value falls outside of this range is used as an emulsifier for a silicone aqueous dispersion, the emulsifying dispersion power and stability of the aqueous dispersion may decrease.
  • the surfactant is preferably used in a range of from 0.1% by mass to 20% by mass, more preferably from 0.2% by mass to 15% by mass, and even more preferably from 0.2% by mass to 15% by mass based on the total solid content. is in the range of 0.5% by mass or more and 10% by mass or less. If it is above the lower limit of this range, the emulsification state will be good, and if it is below the upper limit of this range, it will be difficult to cause heavy exfoliation.
  • a reaction inhibitor is preferably contained in order to suppress the activity of the platinum-based catalyst at room temperature in the form of an aqueous coating liquid.
  • a reaction inhibitor is preferably a reaction inhibitor having an alkynyl group.
  • the reaction inhibitor having an alkynyl group is not particularly limited as long as it has an alkynyl group, but specific examples include 1-ethynyl-1-cyclohexanol, 4-ethyl-1-octyn-3-ol, 3- Methyl-1-dodecyn-3-ol, 3,7,11-trimethyl-1-dodecyn-3-ol, 1,1-diphenyl-2-propyn-3-ol, 3-ethyl-6-ethyl-1- Examples include nonyn-3-ol, 3-methyl-1-pentadecyn-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, and 3-phenyl-1-butyn-3-ol.
  • the present invention is an aqueous coating solution
  • a reaction inhibitor having an alkynyl group and a hydroxyl group as exemplified in view of the balance between affinity and solubility in water, ability to coordinate with platinum, and boiling point.
  • the platinum-based catalyst may be mixed with a general organopolysiloxane to be added to an aqueous coating solution and used as an aqueous emulsion.
  • the content of the crosslinking reaction inhibitor is preferably 5 ppm or more and 1000 ppm or less, more preferably 10 ppm or more and 700 ppm or less, and even more preferably 20 ppm or more and 500 ppm or less, based on the mass of the aqueous coating composition used to form the release layer. .
  • the content of the crosslinking reaction inhibitor is at least the lower limit, the pot life becomes long, the addition curing reaction of silicone is difficult to proceed at room temperature, and silicone aggregates tend to be difficult to generate.
  • the content of the crosslinking reaction inhibitor is below the upper limit, it will be difficult for silicone to transfer to the other material after the other material is peeled off, and the amount of reaction inhibitor that evaporates during heat treatment will be reduced, thereby preventing contamination inside the oven. Hard to occur.
  • a coupling agent can be added to the aqueous coating composition in order to improve the adhesion between the silicone component and the base film.
  • the coupling agent include a compound represented by the general formula YRSiX 3 , such as a silane coupling agent.
  • Y is an organic functional group such as a vinyl group, an epoxy group, an amino group, a mercapto group, etc., and it is particularly preferable that Y is an epoxy group or a vinyl group.
  • R is an alkylene group such as methylene, ethylene, or propylene group, or a single bond.
  • X is a hydrolyzable group such as a methoxy group, an ethoxy group, an acetoxy group, or an alkyl group, and at least one of the three X's is a hydrolyzable group, preferably three X's are a hydrolyzable group. .
  • the hydrolyzable group a methoxy group is preferred.
  • Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and vinyltris(2-methoxyethoxysilane). ) silane, vinylmethyldimethoxysilane, etc.
  • coupling agents include organometallic compounds containing metals such as zirconium, titanium, aluminum, etc.
  • the organometallic compounds are preferably classified into alkoxides, chelates, and acylates. Specific examples include zirconium tetraacetylacetonate, zirconium acetate, titanium acetylacetonate, triethanolamine titanate, titanium lactate, etc., but are not limited to these.
  • coupling agents such as a silane coupling agent where Y is an epoxy group and a silane coupling agent where Y is a vinyl group.
  • the addition of a coupling agent improves the durable adhesion between silicone, which is the main component of the release layer, and a polyester film or the like.
  • silicone which is the main component of the release layer
  • a polyester film or the like For example, when casting a resin sheet using a solution casting method using an organic solvent, the organic solvent component may penetrate into the release layer and the release layer may be eroded, but the addition of a coupling agent can prevent this erosion. Can be suppressed.
  • the mold release layer is exposed to high temperatures and there is a possibility of thermal deterioration, but by adding a coupling agent, thermal deterioration can be suppressed and the mold release layer can be maintained.
  • the content of the coupling agent is 0.1 parts by mass or more and 20 parts by mass based on the total of 100 parts by mass of the alkenyl group-containing silicone and the Si-H group-containing silicone contained in the release layer. Part or less is preferable, and more preferably 1 part or more and 10 parts or less by weight.
  • the aqueous emulsion can be prepared by emulsifying a predetermined alkenyl group-containing silicone or Si-H group-containing silicone, an aqueous solvent, and a surfactant.
  • these components can be emulsified using a known method.
  • pre-prepared predetermined silicone, a surfactant, and other components as necessary are mixed using a stirring device such as a homogenizer, ajihomo mixer, or an ultra planetary mixer. Examples include a method of mechanically emulsifying in an aqueous medium using
  • the particle size of the aqueous dispersion can be adjusted by adjusting the size of the stirring blade, stirring speed, and stirring time.
  • the average particle diameter of the dispersed particles of each silicone aqueous dispersion is preferably 200 nm or less, more preferably 100 nm or more and 200 nm or less.
  • the base film in the present invention is not particularly limited, but examples include sheets or films made of polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polycarbonate, polyethylene and polypropylene, polystyrene triacetylcellulose, acrylic, polyimide, etc. be able to.
  • a film made of polyester is preferred from the viewpoint of excellent mechanical properties and heat resistance, and a good balance between these properties and price.
  • the case of a polyester film will be explained as an example, but even when using other resin films, the copolymerization components, blend components, additives, film manufacturing method, laminated structure, etc. are the same as described below.
  • polyester film The polyester constituting the polyester film used as the base film is not particularly limited, and a film formed from a polyester commonly used as a base material for a release film can be used.
  • a film formed from a polyester commonly used as a base material for a release film can be used.
  • it is a crystalline linear saturated polyester consisting of an aromatic dibasic acid component and a diol component, such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, or a combination of these resins. More preferred are copolymers containing the constituent components as main components.
  • polyester films formed from polyethylene terephthalate are particularly suitable.
  • the repeating units of ethylene terephthalate are preferably 90 mol% or more, more preferably 95 mol% or more, and a small amount of other dicarboxylic acid components and diol components may be copolymerized.
  • a small amount of other dicarboxylic acid components and diol components may be copolymerized.
  • known additives such as antioxidants, light stabilizers, ultraviolet absorbers, crystallizing agents, etc. may be added within a range that does not impede the effects of the release film of the present invention.
  • the polyester film is preferably a biaxially oriented polyester film for reasons such as high elastic modulus in both directions.
  • the intrinsic viscosity of the polyester film is preferably 0.50 dl/g or more and 0.70 dl/g or less, more preferably 0.52 dl/g or more and 0.62 dl/g or less.
  • the intrinsic viscosity is 0.50 dl/g or more, it is preferable because many breaks do not occur during the stretching process.
  • it is 0.70 dl/g or less it is preferable because the cutting properties are good when cutting into a predetermined product width and dimensional defects do not occur. Further, it is preferable that the raw material pellets be sufficiently vacuum dried.
  • polyester film when it is simply described as a "polyester film", it means a polyester film having (laminated) a surface layer A and a surface layer B.
  • the method for producing the polyester film in the present invention is not particularly limited, and conventionally commonly used methods can be used.
  • it can be obtained by melting the polyester in an extruder, extruding it into a film, cooling it in a rotating cooling drum to obtain an unstretched film, and then biaxially stretching the unstretched film.
  • a biaxially stretched film can be obtained by sequentially biaxially stretching a uniaxially stretched film in the longitudinal or transverse direction in the transverse or longitudinal direction, or by simultaneously biaxially stretching an unstretched film in the longitudinal and transverse directions. I can do it.
  • the stretching temperature during stretching of the polyester film is preferably at least the secondary transition point (Tg) of the polyester. It is preferable to stretch the film by a factor of 1 to 8 times, particularly 2 times to 6 times, in both the longitudinal and transverse directions.
  • the thickness of the polyester film is preferably 12 ⁇ m or more and 50 ⁇ m or less, more preferably 15 ⁇ m or more and 38 ⁇ m or less, and even more preferably 19 ⁇ m or more and 33 ⁇ m or less. If the thickness of the film is 12 ⁇ m or more, there is no risk of deformation due to heat during film production, processing, and molding, which is preferable. On the other hand, if the thickness of the film is 50 ⁇ m or less, the amount of film to be discarded after use will not be excessively large, which is preferable in terms of reducing environmental burden.
  • the polyester film base material may be a single layer or a multilayer of two or more layers.
  • the base film may be a polyester film having a surface layer A that does not substantially contain particles having a particle size of 1.0 ⁇ m or more and a surface layer B that contains particles.
  • surface layer A does not substantially contain inorganic particles having a particle size of 1.0 ⁇ m or more.
  • particles having a particle size of less than 1.0 ⁇ m and 1 nm or more may be present in the surface layer A. Since the surface layer A does not substantially contain particles having a particle size of 1.0 ⁇ m or more, for example, inorganic particles, it is possible to reduce problems caused by transfer of the shape of particles in the base material to the resin sheet.
  • the surface layer A does not contain particles with a particle size of less than 1.0 ⁇ m, so that problems caused by transfer of the particle shape in the base material to the resin sheet can be more effectively suppressed.
  • the polyester film base material is preferably a laminated film having a surface layer A substantially free of inorganic particles on at least one side.
  • the surface layer A that does not substantially contain particles with a particle size of less than 1.0 ⁇ m also substantially does not contain particles with a particle size of 1.0 ⁇ m or more.
  • substantially no particles means, for example, in the case of inorganic particles of less than 1.0 ⁇ m, the amount of inorganic elements determined by fluorescent X-ray analysis is 50 ppm or less, preferably 10 ppm. Hereinafter, it most preferably means a content that is below the detection limit. Even if particles are not actively added to the film, contaminants derived from foreign substances or dirt attached to the raw resin or the line or equipment in the film manufacturing process are peeled off and mixed into the film. This is because there is. Further, “substantially not containing particles with a particle size of 1.0 ⁇ m or more” means that particles with a particle size of 1.0 ⁇ m or more are not included.
  • the layer on the side to which the release layer is applied is layer A
  • the layer on the opposite side is layer B
  • the other core layer is layer C
  • the layer structure in the thickness direction is release layer/A/ B, or a laminated structure such as release layer/A/C/B.
  • the C layer may have a plurality of layers.
  • the surface layer B may not contain inorganic particles. In that case, it is preferable to provide a coating layer containing at least inorganic particles and a binder on the surface layer B in order to provide slipperiness for winding up the film into a roll.
  • the surface layer B forming the opposite surface to the surface to which the release layer is applied preferably contains inorganic particles from the viewpoint of the slipperiness of the film and the ease with which air can escape.
  • inorganic particles from the viewpoint of the slipperiness of the film and the ease with which air can escape.
  • silica particles and/or calcium carbonate particles it is preferable to use silica particles and/or calcium carbonate particles.
  • the total amount of inorganic particles contained in the surface layer B is preferably 1000 ppm or more and 15000 ppm or less.
  • the area surface average roughness (Sa) of the film of the surface layer B is preferably in the range of 1 nm or more and 40 nm or less. More preferably, the range is 5 nm or more and 35 nm or less.
  • the total amount of silica particles and/or calcium carbonate particles is 1000 ppm or more and Sa is 1 nm or more, air can be released uniformly when the film is rolled up, resulting in a good rolled shape and good flatness. , it is suitable for producing ultra-thin ceramic green sheets.
  • the lubricant is less likely to aggregate and coarse protrusions are not formed, resulting in stable quality when producing ultra-thin ceramic green sheets. It is preferable.
  • inert inorganic particles and/or heat-resistant organic particles can also be used as particles contained in layer B, but from the viewpoint of transparency and cost, silica particles and/or More preferably, calcium carbonate particles are used.
  • other inorganic particles that can be used include alumina-silica composite oxide particles, hydroxyapatite particles, and the like.
  • the heat-resistant organic particles include crosslinked polyacrylic particles, crosslinked polystyrene particles, and benzoguanamine particles.
  • porous colloidal silica is preferable, and when using calcium carbonate particles, light calcium carbonate whose surface is treated with a polyacrylic acid-based polymer compound is preferable from the viewpoint of preventing the lubricant from falling off. .
  • the average particle diameter of the inorganic particles added to the surface layer B is preferably 0.1 ⁇ m or more and 2.0 ⁇ m or less, particularly preferably 0.5 ⁇ m or more and 1.0 ⁇ m or less. It is preferable that the average particle diameter of the inorganic particles is 0.1 ⁇ m or more because the release film has good slip properties. Further, if the average particle diameter is 2.0 ⁇ m or less, there is no risk of adversely affecting the smoothness of the surface of the mold release layer, so there is no risk of pinholes occurring in the ceramic green sheet, which is preferable.
  • the surface layer A which is the layer on which the release layer is provided, in order to prevent inorganic particles such as lubricants from being mixed in.
  • the thickness ratio of the surface layer A which is the layer on which the release layer is provided, is preferably 20% or more and 50% or less of the total layer thickness of the base film. If it is 20% or more, it is difficult to be influenced by particles contained in the surface layer B etc. from inside the film, and it is easy for the area surface average roughness Sa to satisfy the above range, which is preferable.
  • the thickness is 50% or less of the total thickness of the base film, the ratio of recycled raw materials used in the surface layer B can be increased, and the environmental burden is small, which is preferable.
  • a film may be applied to the surface of surface layer A and/or surface layer B before or after uniaxial stretching during the film forming process.
  • a coating layer may be provided on the surface, and a surface treatment or the like may be performed.
  • the release layer formation surface to which the aqueous coating composition is applied can be subjected to surface treatment or provided with an easy-to-adhesion layer in order to improve adhesion to the release layer.
  • Surface treatments include plasma treatment, corona discharge treatment, ultraviolet treatment, flame treatment, and electron beam/radiation treatment.
  • the adhesive layer contains the same resin as the base film, and further contains antistatic agents and pigments. , a surfactant, a lubricant, an anti-blocking agent, and the like. If an adhesion improver such as a coupling agent is added to the aqueous coating composition, the release layer should have sufficient adhesion to the base film even without providing an easy-adhesion layer. Can be done.
  • the release layer is formed by applying an aqueous coating composition containing an aqueous emulsion of alkenyl group-containing silicone and an aqueous emulsion of Si—H group-containing silicone. At that time, a release layer is formed on at least one surface of the base film.
  • the release layer is formed by applying the aqueous coating liquid onto the base film and then heating and drying it to cause the components of the aqueous coating liquid to react and solidify.
  • the release layer is preferably formed in a film forming process.
  • the thickness of the release layer after drying is preferably 5 nm or more and 100 nm or less.
  • the thickness of the release layer is at least the lower limit, it is easy to obtain sufficient peelability, and when it is below the upper limit, the peel strength tends to be difficult to increase, and the release layer components of the aqueous coating solution are not concentrated. It also eliminates the need to increase the amount of coating, making it easier to apply. Therefore, the thickness of the release layer is more preferably 5 nm or more and 70 nm or less, and even more preferably 5 nm or more and 50 nm or less.
  • the solid content concentration is preferably 20% by mass or less, more preferably 1% by mass or more and 10% by mass based on the release layer components in the water-based coating liquid. % or less.
  • the solid concentration of the release layer component in the aqueous coating liquid is at least the lower limit, film forming properties tend to improve.
  • the solid content concentration is below the upper limit, the stability of the aqueous coating liquid and the appearance of the release layer tend to be good.
  • Water is preferably used as the aqueous solvent to adjust the solid content concentration.
  • the aqueous coating liquid applied to the base film to form the release layer can be applied at any stage, but it is preferably applied during the polyester film manufacturing process, and furthermore, the oriented crystallization is completed. Preferably it is applied to the previous polyester film. Thereafter, after stretching in at least one direction, heat treatment can be performed to complete crystal orientation.
  • polyester film before crystal orientation is completed refers to an unstretched film or an unstretched film in the longitudinal direction (hereinafter sometimes referred to as continuous film forming direction, longitudinal direction, MD direction) or transverse direction (hereinafter referred to as continuous film forming direction, longitudinal direction, MD direction). , a direction perpendicular to the machine direction, a width direction, or a TD direction), and a film oriented by low-magnification stretching in two directions, the machine direction and the width direction (sometimes referred to as the TD direction). This includes a biaxially stretched film (before finally being re-stretched in the longitudinal or transverse direction to complete oriented crystallization).
  • in-line coating in which an aqueous coating liquid is applied to an unstretched film or a uniaxially stretched film oriented in one direction, and the film is directly subjected to longitudinal stretching and/or transverse stretching and heat setting.
  • the release layer may be dried by a stretching process or a heat setting process after coating, and a drying process may be added if necessary.
  • the curing can be performed by a stretching process or a heat setting process, but a curing process may be added as necessary.
  • the film surface is subjected to physical treatment such as corona surface treatment, flame treatment, plasma treatment, etc. as a preliminary treatment to improve coating properties, or the above-mentioned emulsifier is added to the composition. It is preferable to use them together as a wetting agent or to additionally add a surfactant as a wetting agent.
  • any known coating method can be used as the coating method.
  • a roll coating method, a gravure coating method, a roll brushing method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, etc. can be used alone or in combination.
  • the surface free energy of the release layer in the test method described below is preferably in the range of 10 mN/m or more and 40 mN/m or less, more preferably 12 mN/m or more and 38 mN/m or less, and even more preferably 14 mN/m.
  • the range is 36 mN/m or more, particularly preferably 15 mN/m or more and 35 mN/m.
  • the release film of the present invention can be used as a process film used in manufacturing multilayer ceramic capacitors, casting resin sheets, and the like.
  • the wettability is good, so pinholes in the processed layer are reduced, and, for example, when used as a release film for green sheet production. , it is possible to reduce the defective rate of thin-walled multilayer ceramic capacitors.
  • the static contact angles of ethylene glycol and methylene iodide were measured in the same manner, and the following simultaneous equations regarding the surface tension components of the release layer were established using the surface tension components of each liquid below (water, ethylene).
  • the measurement solutions of glycol and methylene iodide are designated as 1, 2, and 3, respectively, where ⁇ LD is the dispersion force component of the liquid, ⁇ LP is the polar force component of the liquid, ⁇ LH is the hydrogen bond component of the liquid, and ⁇ L is each surface tension component of the liquid.
  • ⁇ SD represents the dispersion force component of the mold release layer, ⁇ SP represents the polar force component of the mold release layer, ⁇ SH represents the hydrogen bond component of the mold release layer, and ⁇ represents the contact angle).
  • the nozzle diameter for projecting (spraying) the particles was set to 0.3 mm ⁇ , and the particles were made to collide with the surface of the mold release layer to cut the mold release layer.
  • the injection intensity at this time was determined by cutting a polymethyl methacrylate resin (Kuraray Co., Ltd., Paraglas P, sheet thickness 2 mm) under similar experimental conditions, and measuring the cut displacement with respect to the amount of slurry injection (i.e., 1 g of slurry was sprayed).
  • the standard projection force was calculated from the cutting depth (cutting depth when cutting), and the standard projection force was determined based on that value.
  • the standard projection force was defined as the projection force when the polymethyl methacrylate resin was shaved by 0.019 ⁇ m/g.
  • the erosion depth of the release layer was measured using the standard projection force.
  • the projection force is adjusted by the projection air pressure, so when the projection force is determined, the projection air pressure and the amount of projection air are also determined.
  • the erosion depth was measured using a stylus surface profile measuring device (manufactured by Kosaka Laboratory Co., Ltd., model PU-EU1, stylus tip R: 0.5 ⁇ m, load: 50 ⁇ N, measurement magnification: 50,000, measurement length: 4 mm). , measurement speed: 0.1 mm/s). More specifically, first, inclination correction was performed using reference areas A and B at both ends that were not worn within the measurement length. Next, the level difference from the regression line serving as a reference to the wear scar center C (average value of 50 ⁇ m width) was measured. Next, the difference between the level difference data at 0g projection (untreated surface) and the level difference data at each projection amount was taken to obtain the erosion depth. From the acquired data on the amount of projection versus the depth of erosion, the erosion rate ( ⁇ m/g) was determined from the change in the depth of erosion when the amount of slurry projection was between 0 g and 25 g.
  • BaTiO 3 manufactured by Kyoritsu Materials
  • This slurry was uniformly coated onto the release layer of the release film to a thickness of 2 ⁇ m after drying, and then dried to form a ceramic green sheet.
  • a rotary die cutter R.D.C (FB)-A4, manufactured by Tsukatani Shimono Seisakusho Co., Ltd.
  • the release film on which the ceramic sheet was formed was cut into a 16 mm x 32 mm square from the ceramic green sheet surface side, and the surface of the release layer. A half cut was made to a depth of approximately 3 ⁇ m.
  • the blade of the rotary die cutter is double-edged at 50°, blade depth is 0.3 mm, and blade height is 0.6 mm.
  • FIGS. 1 to 3 show photographs corresponding to each example of half-cut property evaluation of " ⁇ " to "x". ⁇ : No ceramic green sheet remains in the cut portion. ⁇ : An extremely small amount of ceramic green sheet remains in the cut portion. ⁇ : A large amount of ceramic green sheets remained in the cut portion.
  • Recyclability evaluation was determined by magnifying the size and number of foreign particles contained in the film 20 times using a universal projector and counting the number of foreign particles with a maximum diameter of 50 ⁇ m or more. The measurement area was 0.05 m2 .
  • ⁇ Number of foreign objects: 10 pieces/less than 0.05 m 2 , no problem in use.
  • ⁇ Number of foreign objects: 10 pieces/0.05 m 2 or more to 30 pieces/0.05 m 2 or more, slightly affecting flatness, but not a problem in use.
  • ⁇ Number of foreign objects: 30 pieces/0.05 m 2 or more to less than 100 pieces/0.05 m 2 , can be used for limited purposes.
  • ⁇ Number of foreign objects: 100 pieces/0.05 m 2 or more, the deformation of the cast surface is so noticeable that it cannot be used.
  • Thickness of release layer After cutting the release film into triangular pieces, a 2 nm thick Pt (platinum) layer was formed on the surface of the release layer by coating.
  • the obtained sample was fixed in a multiaxial embedding capsule, embedded using epoxy resin, and sliced in a direction perpendicular to the surface direction of the film using a microtome ULTRACUT-S to obtain a 50 nm thick sample.
  • An ultrathin sample was obtained.
  • the obtained ultra-thin sample was mounted on a grid and steam-stained with 2% osmic acid at 60° C. for 2 hours.
  • the cross section of the film was observed using a transmission electron microscope LEM-2000 at an accelerating voltage of 100 kV, and the thickness of the release layer was measured. Measurements were performed at arbitrary 10 points, and the average value was taken as the thickness of the release layer (unit: nm).
  • the coated film was dried at 105°C, stretched 4.7 times in the transverse direction at 150°C, and further heat-set at 235°C for about 10 seconds to react and solidify the aqueous coating solution.
  • a release film (thickness: 25 ⁇ m) having a mold layer was obtained and evaluated. The evaluation results are shown in Table 2.
  • the part of the release film that did not become a product due to defects or the part of the release film that did not become a product due to defects etc. was crushed until the major axis of the film piece was approximately 5 mm or less for each example and comparative example. 40% by mass of the raw material that was recycled by melting was used.
  • ⁇ Manufacture example 1> (Sample 1A) Using an emulsifying device (manufactured by NP Lab Co., Ltd., device name "Ultra Planetary Mixer”) that can stir the entire inside of the container, a1 of formula (1) is 100 mol%, b1 is 0 mol%, A raw material consisting of 95% by mass of silicone oil with a number average molecular weight of 9000 and 5% by mass of polyoxyethylene tridecyl ether (manufactured by ADEKA Co., Ltd., trade name "ADEKATOL TN-100”) as a surfactant was prepared in an aqueous medium.
  • ADEKATOL TN-100 polyoxyethylene tridecyl ether
  • emulsion particle size was adjusted to an average particle size of 210 nm by adjusting the stirring speed and stirring time during emulsification.
  • Example 2A Using an emulsifying device (manufactured by NP Lab Co., Ltd., device name "Ultra Planetary Mixer”) that can stir the entire inside of the container, a2 of formula (2) is 50 mol%, b2 is 50 mol%, A raw material consisting of 94% by mass of silicone oil with a number average molecular weight of 4000 and 6% by mass of polyoxyethylene tridecyl ether (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Leocol TD-90”) as a surfactant. It was mechanically emulsified in an aqueous medium to obtain an aqueous dispersion of Sample 2 with a solid content of 40% by mass. Furthermore, the emulsion particle size was adjusted to an average particle size of 170 nm by adjusting the stirring speed and stirring time during emulsification.
  • a2 of formula (2) is 50 mol%
  • b2 is 50 mol%
  • Water-based coating liquids were prepared so that the solid mass of silicone in Sample 1A and Sample 2A was as shown in Table 2, and the other components were as shown below. 5% by mass of the following coupling agent based on the total mass of silicone, 50 ppm of the following platinum-based catalyst based on the total solid mass of Sample 1A and Sample 2A, and 100 ppm of the following crosslinking agent based on the mass of the coating solution. A reaction inhibitor was mixed and the solid content concentration of the coating solution was diluted with water to obtain the target release layer thickness to prepare a coating solution.
  • Example 2 ⁇ Coupling agent: 3-glycidoxypropyltriethoxysilane (manufactured by JNC Co., Ltd., trade name "Sila Ace S510”) ⁇ Platinum-based catalyst: Platinum-based catalyst emulsion (manufactured by Wacker, product name "CATALYST EM440”) ⁇ Crosslinking reaction inhibitor: 1-ethynylcyclohexanol (manufactured by Alfa Lancaster) [Example 2] In Example 1, a release film was produced under exactly the same conditions as in Example 1, except that a water-based coating solution was prepared using Sample 1B produced in Production Example 2 instead of Sample 1A, and the above-mentioned evaluation was carried out. I did it. The results are shown in Table 2.
  • a1 of formula (1) is 100 mol%
  • b1 is 0 mol%
  • a raw material consisting of 95% by mass of silicone oil with a number average molecular weight of 5,000 and 5% by mass of polyoxyethylene tridecyl ether (manufactured by ADEKA Co., Ltd., trade name "ADEKATOL TN-100”) as a surfactant was prepared in an aqueous medium.
  • emulsion particle size was adjusted to an average particle size of 190 nm by adjusting the stirring speed and stirring time during emulsification.
  • Example 3 In Example 1, a release film was produced under exactly the same conditions as in Example 1, except that a water-based coating solution was prepared using Sample 1C produced in Production Example 3 instead of Sample 1A, and the above-mentioned evaluation was carried out. I did it. The results are shown in Table 2.
  • Example 1C Using an emulsifying device (manufactured by NP Lab Co., Ltd., device name "Ultra Planetary Mixer”) that can stir the entire inside of the container, a1 of formula (1) is 96 mol%, b1 is 4 mol%, A raw material consisting of 95% by mass of silicone oil with a number average molecular weight of 7,000 and 5% by mass of polyoxyethylene tridecyl ether (manufactured by ADEKA Co., Ltd., trade name "ADEKATOL TN-100”) as a surfactant was prepared in an aqueous medium.
  • ADEKATOL TN-100 polyoxyethylene tridecyl ether
  • emulsion particle size was adjusted to an average particle size of 200 nm by adjusting the stirring speed and stirring time during emulsification.
  • Example 4 In Example 1, a release film was produced under exactly the same conditions as in Example 1, except that a water-based coating solution was prepared using Sample 1D produced in Production Example 4 instead of Sample 1A, and the above-mentioned evaluation was carried out. I did this. The results are shown in Table 2.
  • Example 1D Using an emulsifying device (manufactured by NP Lab Co., Ltd., device name "Ultra Planetary Mixer”) that can stir the entire inside of the container, formula (A) is 2 mol%, formula (B) is 4 mol%, formula (B) is 4 mol%, (C) is 90 mol%, formula (D) is 2 mol%, formula (E) is 2 mol%, 95% by mass of silicone oil having a number average molecular weight of 8000, and polyoxy as a surfactant.
  • emulsifying device manufactured by NP Lab Co., Ltd., device name "Ultra Planetary Mixer”
  • a raw material consisting of 5% by mass of ethylene tridecyl ether (manufactured by ADEKA Co., Ltd., trade name "ADEKATOL TN-100") was mechanically emulsified in an aqueous medium to obtain an aqueous emulsion of sample 1D with a solid content of 45% by mass. Obtained. Furthermore, the emulsion particle size was adjusted to an average particle size of 200 nm by adjusting the stirring speed and stirring time during emulsification.
  • Example 5 In Example 4, when preparing the aqueous coating solution, a release film was produced under exactly the same conditions as in Example 4, except that the contents of Sample 1D and Sample 2A were changed as shown in Table 2. , the above-mentioned evaluation was performed. The results are shown in Table 2.
  • ⁇ Manufacture example 5> (Sample 1E) Using an emulsifying device (manufactured by NP Lab Co., Ltd., device name "Ultra Planetary Mixer”) that can stir the entire inside of the container, a1 of formula (1) is 97 mol%, b1 is 3 mol%, A raw material consisting of 96% by mass of silicone oil with a number average molecular weight of 30,000 and 4% by mass of polyoxyethylene tridecyl ether (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Leocol TD-90”) as a surfactant.
  • a1 of formula (1) is 97 mol%
  • b1 is 3 mol%
  • a raw material consisting of 96% by mass of silicone oil with a number average molecular weight of 30,000 and 4% by mass of polyoxyethylene tridecyl ether (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Leocol
  • sample 1E was mechanically emulsified in an aqueous medium to obtain an aqueous emulsion of sample 1E with a solid content of 50% by mass. Furthermore, the emulsion particle size was adjusted to an average particle size of 200 nm by adjusting the stirring speed and stirring time during emulsification.
  • a3 of formula (2) is 50 mol%
  • b3 is 50 mol%
  • a water-based coating liquid was prepared under the same conditions as in Production Example 1, except that the solid mass of silicone in Sample 1E and Sample 2B was prepared in the amount shown in Table 2.
  • the erosion rate was 0.003 ⁇ m/g or more, so the half-cut property evaluation was good, and when the sheet-like molded product was peeled off after half-cut. , problems caused by adhesion to the half-cut portion are less likely to occur.
  • the erosion rate was smaller than 0.003 ⁇ m/g, and the half-cut property evaluation was decreased despite the low surface free energy. , when peeling off the sheet-like molded product after half-cutting, problems are likely to occur due to adhesion to the half-cut portions.
  • the release film of the present invention is less likely to cause problems due to adhesion to the half-cut portion when peeling off the sheet-like molded product after half-cutting, so it is easy to use as a material for various processes and is recyclable, making it suitable for industrial use.
  • the value is extremely high.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
PCT/JP2023/031214 2022-09-06 2023-08-29 離型フィルム Ceased WO2024053483A1 (ja)

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JP2014083697A (ja) * 2012-10-19 2014-05-12 Teijin Dupont Films Japan Ltd シリコーン離型ポリエステルフィルム
WO2017200056A1 (ja) * 2016-05-20 2017-11-23 三菱ケミカル株式会社 離型フィルム
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JP6512378B1 (ja) 2017-09-29 2019-05-15 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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JP2013208810A (ja) * 2012-03-30 2013-10-10 Teijin Dupont Films Japan Ltd シリコーン離型ポリエステルフィルム
JP2014083697A (ja) * 2012-10-19 2014-05-12 Teijin Dupont Films Japan Ltd シリコーン離型ポリエステルフィルム
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