Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
  • B29B17/04—Disintegrating plastics, e.g. by milling
  • B29B17/0404—Disintegrating plastics, e.g. by milling to powder
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/07—Flat, e.g. panels
  • B29C48/08—Flat, e.g. panels flexible, e.g. films
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/26—Polymeric 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
  • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
• • 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
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/70—Scrap or recycled material
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/141—Feedstock
  • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/20—Waste processing or separation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• the present invention relates to a laminated polyethylene terephthalate film, a release film, and a method for producing a laminated polyethylene terephthalate film.
• the present invention particularly relates to a laminated polyethylene terephthalate film useful as a base material (hereinafter sometimes referred to as a process film) used after providing a functional layer, and a method for producing the same.
• Films containing functional layers with various functions on the surface of base films such as synthetic resins are used in fields such as electronic components, optical components, labels, and mold release.
• used films, films that are out of specification, films that are damaged during the distribution process, etc. are usually discarded (hereinafter, such films may be referred to as films to be discarded).
• Patent Document 1 discloses a method for measuring the amount of impurities in a used film, a method for recycling the used film, and a method for forming the recycled raw material into a film.
• Patent Document 1 discloses that a silicone-containing release layer, barium titanate, and an adhesive formed on the surface of a base film are removed as a residue.
• Patent Document 1 discloses a recycling technology regarding films.
• the recycling yield varies depending on the amount of impurities contained in the film, and as the amount of impurities increases, the recycling yield tends to deteriorate.
• the technology of Patent Document 1 applies thermal recycling when the amount of film impurities is 0.2% by weight or more when the weight of the entire film is 100% by weight, and in this case, the recycling yield is 0. It is.
• release films are always required to have low surface roughness from the viewpoint of surface transfer to processed products, and the same applies to recycled films.
• Patent Document 1 although there is a description regarding the amount of impurities, there is no description regarding the film surface roughness, and there is a concern that the desired surface roughness may not be satisfied.
• an object of the present invention is to provide a laminated polyethylene terephthalate film, a method for manufacturing the same, and a release film that can suppress the transfer of surface shape to processed products.
• Some preferred embodiments of the present invention relate to films to be disposed of, particularly laminated polyethylene terephthalate films with low surface roughness obtained from raw materials recovered from laminated films, such as base films for mold release.
• the present invention compared to the impurity amounts of Si component, Ti component, and Ba component contained in the film of the prior art, contains these components under specific conditions, so that the recycling yield is excellent and the surface A laminated polyethylene terephthalate film with low roughness can be provided.
• the present inventors succeeded in controlling the surface roughness within a predetermined range in a recycled film containing impurities such as Si, Ti, and Ba components. They discovered that the problem could be solved and completed the present invention.
• a laminated polyethylene terephthalate film comprising a surface layer A and a surface layer B
• the laminated polyethylene terephthalate film contains one or more of Si, Ti, and Ba components,
• the total amount of Si element, Ti element, and Ba element is 0.1 ppm or more and 5000 ppm or less based on 100 parts by mass of the laminated polyethylene terephthalate film
• the surface layer A is a layer on which a functional layer is laminated, and the three-dimensional center plane average surface roughness (SRa) of the surface layer A is 1 nm or more and 7 nm or less, and the maximum peak height (SRp) of the surface layer A is 1 nm or more and 7 nm or less.
• the laminated polyethylene terephthalate film according to [1] which contains a resin obtained by materially recycling and/or chemically recycling the laminated film with a functional layer in an amount of 5% by mass or more and 50% by mass or less.
• [3] The laminated polyethylene terephthalate film according to [1] or [2], wherein the laminated polyethylene terephthalate film contains SiO 2 whose longest side has a length of 0.5 ⁇ m or more and 5.0 ⁇ m.
• the surface layer B is a layer that forms the surface of the laminated polyethylene terephthalate film opposite to the surface on which the functional layer is laminated,
• the surface layer B contains at least one type of particles selected from calcium carbonate particles or silica particles in a total amount of 3000 ppm or more and 15000 ppm or less, based on 100 parts by mass of the laminated polyethylene terephthalate film,
• the three-dimensional center plane average surface roughness (SRa) of the surface layer B is 20 nm or more and 40 nm or less,
• the laminated polyethylene terephthalate film according to any one of [1] to [3].
• IV intrinsic viscosity
• Step 1 A pulverization step comprising pulverizing the functional layer-equipped laminated film to form a pulverized product.
• Step 2 A chipping step including chipping the pulverized product obtained in Step 1 to form recycled chips.
• Step 3 A step of forming a recycled film, which includes forming the recycled chips obtained in Step 2 into a film and winding up the film.
• the present invention it is possible to provide a laminated polyethylene terephthalate film that suppresses transfer of surface shape to processed products. Furthermore, the present invention provides a method for improving the surface shape of processed products even when using recycled resin obtained through material recycling and/or chemical recycling from a film containing particles containing at least one of Si, Ti, and Ba. A laminated polyethylene terephthalate film that can suppress transfer can be provided.
• the laminated polyethylene terephthalate film according to the embodiment of the present invention contains one or more types of Si, Ti, and Ba components, and the polyethylene terephthalate film includes: Contains the Si, Ti, and Ba components in a total amount of 0.1 ppm or more and 5000 ppm or less with respect to 100 parts by mass of the film, Surface layer A is a layer on which functional layers are laminated, and is a laminated polyethylene terephthalate film having a three-dimensional center plane average surface roughness (SRa) of 1 nm or more and 7 nm or less, and a maximum peak height (SRp) of 200 nm or less.
• the total amount of Si, Ti, and Ba components means the total amount of Si element, Ti element, and Ba element. This total amount can be measured by the method described in Examples below.
• the laminated polyethylene terephthalate film according to the embodiment of the present invention can also be expressed as follows.
• a laminated polyethylene terephthalate film comprising a surface layer A and a surface layer B,
• the laminated polyethylene terephthalate film contains one or more of Si, Ti, and Ba components,
• the total amount of Si element, Ti element, and Ba element is 0.1 ppm or more and 5000 ppm or less based on 100 parts by mass of the laminated polyethylene terephthalate film
• the surface layer A is a layer on which a functional layer is laminated, and the three-dimensional center plane average surface roughness (SRa) of the surface layer A is 1 nm or more and 7 nm or less, and the maximum peak height (SRp) of the surface layer A is 1 nm or more and 7 nm or less. ) is 200 nm or less, Laminated polyethylene terephthalate film.
• Laminated polyethylene terephthalate film contains one or more of Si, Ti, and Ba components, so it is suitable for use with recycled resins (e.g., resins made from recycled silicone release films, release films used in the production of ceramic green sheets). It can be manufactured using recycled resin), thus contributing to reducing the environmental burden. This will be explained.
• a laminated polyethylene terephthalate film is produced using a silicone-based release film, that is, a resin obtained by recycling (e.g., material recycling, chemical recycling) a laminated film with a silicone-based release layer
• the laminated polyethylene terephthalate film has a silicone-containing release layer. May contain Si components derived from the mold layer.
• the laminated polyethylene terephthalate film when a laminated polyethylene terephthalate film is made using a resin that is made by recycling (for example, material recycling or chemical recycling) the release film used in the production of ceramic green sheets containing barium titanate, the laminated polyethylene terephthalate film does not release easily. It may contain Ti and Ba components derived from barium titanate remaining in the mold film. Of course, the laminated polyethylene terephthalate film may further contain a Si component derived from the release film used to produce the ceramic green sheet. In this way, when a laminated polyethylene terephthalate film is produced using recycled resin, the laminated polyethylene terephthalate film may contain one or more of Si, Ti, and Ba components.
• the laminated polyethylene terephthalate film of the present invention contains one or more of Si, Ti, and Ba components, it can be used in the production of such recycled resins (for example, resins made from recycled silicone release films, and ceramic green sheets). It can be manufactured using a resin made by recycling used release film. Therefore, the laminated polyethylene terephthalate film of the present invention can contribute to reducing environmental load. Although the laminated polyethylene terephthalate film of the present invention is preferably manufactured using recycled resin, it may be manufactured without using recycled resin. Moreover, since the upper limit of the total amount of Si element, Ti element, and Ba element is 5000 ppm, the recycled resin that can be used for manufacturing the laminated polyethylene terephthalate film may contain a certain amount of these components.
• the recycling yield (see Patent Document 1), specifically, the recycling yield of recycled resin that can be used for manufacturing a laminated polyethylene terephthalate film can be improved. Furthermore, since the three-dimensional center plane average surface roughness (SRa) of surface layer A is 7 nm or less and the maximum peak height (SRp) is 200 nm or less, processed products manufactured using laminated polyethylene terephthalate film (for example, ceramic green It is possible to avoid excessive unevenness from being formed on the surface of the resin sheet (such as a sheet).
• SRa center plane average surface roughness
• SRp maximum peak height
• a ceramic green sheet is manufactured using a release film including a laminated polyethylene terephthalate film and a release layer, it is possible to avoid forming excessive irregularities on the surface of the ceramic green sheet. In other words, it is possible to suppress the transfer of the surface shape to the ceramic green sheet.
• a laminated film with a functional layer hereinafter sometimes referred to as a "film with a functional layer").
• the functional layer is a release layer, it may be referred to as a "release film with a functional layer”.
• the "laminated film with functional layer” includes a base material (hereinafter sometimes referred to as "film base material”, “base film”, etc.) and a functional layer.
• material recycling and/or chemical recycling may be simply referred to as recycling.
• material recycling may be simply referred to as recycling.
• material recycling may be simply referred to as material recycling.
• material recycling may be simply referred to as recycling.
• material recycling may be described as material recycling.
• the laminated polyethylene terephthalate film is used for mold release (typically, as a base film for a mold release film)
• the laminated polyethylene terephthalate film is not limited to this configuration. That is, the laminated polyethylene terephthalate film may be used for other purposes.
• various aspects will be listed below, but these aspects can be combined as appropriate.
• the laminated polyethylene terephthalate film for mold release has a surface layer A and a surface layer B (sometimes simply referred to as a laminated film).
• the surface layer A is a layer on which the functional layer is laminated
• the surface layer B is a layer forming the surface opposite to the surface on which the release layer is laminated in the laminated polyethylene terephthalate film.
• the laminated polyethylene terephthalate film of the present invention includes a resin obtained by materially and/or chemically recycling a film with a functional layer.
• the functional layer-equipped film may be a release film, for example, a used release film (hereinafter sometimes referred to as a used functional layer-equipped film).
• a used film means, for example, a release film after forming and laminating a release material on a release layer, and further peeling the release material from the release layer.
• used release films include films that have not been used after production and have been stored for a long period of time, release films that have not been used for reasons such as not meeting the required characteristics, and edges that have been cut. It may contain a release film that does not serve the purpose.
• the functional layer-equipped laminated film is a release film used for molding a resin sheet containing an inorganic compound.
• the inorganic compound include metal particles, metal oxides, minerals, and the like, such as calcium carbonate, silica particles, aluminum particles, barium titanate particles, and the like.
• the resin contained in the resin sheet include polyvinyl acetal resin, poly(meth)acrylate resin, and the like.
• the laminated film with a functional layer is used in the production of resin sheets that require high smoothness, such as semiconductor components, ceramic green sheets, and optical films. By recycling the laminated film used for such uses, various physical properties such as haze and surface roughness in the present invention can be more effectively demonstrated.
• the laminated film with a functional layer (release film) used for such uses preferably contains particles in order to maintain smoothness and exhibit windability.
• the functional layer can contain resins such as silicone-based, cyclic olefin-based, acyclic olefin-based, fluorine-based, alkyd-based, acrylic-based, melamine-based, and epoxy-based resins, as described below.
• a laminated film with a functional layer that is subjected to material and/or chemical recycling is a film in which a functional layer is provided on at least one surface of a base film containing a thermoplastic resin.
• the base film is preferably a polyester film, and may be, for example, a laminated polyethylene terephthalate film for mold release having at least surface layer A and surface layer B according to the present invention. That is, the present invention is suitable for the efficient use of resources required in a recycling-oriented society, since the laminated polyethylene terephthalate film for mold release according to the present invention can be recycled multiple times.
• components other than the polyester component can also be reused without departing from the scope of the present invention.
• the material is not particularly limited as long as it falls within the scope of the present invention.
• a resin obtained by material and/or chemical recycling of a laminated film with a functional layer in which a functional layer is directly laminated on a base material can be used.
• the base material with fewer impurities can be recycled, so the haze and surface roughness according to the present invention can be more effectively reduced.
• the material of the polyester film contained in the base material polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polycyclohexanedimethanol-terephthalate, etc. can be used without particular limitation.
• the base film may be made of a single material, a mixed material such as a polymer alloy, or a structure in which multiple materials are laminated.
• the polyester resin contained in the polyester film is preferably an aromatic polyester obtained by polycondensation of a diol component and an aromatic dicarboxylic acid component, from the viewpoint of mechanical properties and reduction of surface defects.
• aromatic dicarboxylic acid components include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 6,6'-(ethylenedioxy)di-2-naphthoic acid, etc.
• Examples include 6,6'-(alkylenedioxy)di-2-naphthoic acid, and examples of diol components include ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, and 1,6-hexanediol. can be mentioned.
• diol components include ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, and 1,6-hexanediol.
• diol components include ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, and 1,6-hexanediol.
• diol components include ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, and 1,6-hexanediol. can be mentioned.
• the 6,6'-(ethylenedioxy)di-2-naphthoic acid component 6,6'-( Also preferred are those obtained by copolymerizing a trimethylenedioxy)di-2-naphthoic acid component and a 6,6'-(butylenedioxy)di-2-naphthoic acid component.
• the repeating unit of ethylene terephthalate is preferably 90 mol% or more, more preferably 95 mol% or more, and a small amount of other dicarboxylic acid component or diol component may be copolymerized, but from the viewpoint of cost.
• the polyester film is preferably a stretched polyester film for reasons such as high bidirectional elastic modulus.
• the laminated polyethylene terephthalate film of the present invention preferably contains particles.
• it can contain one or more types of inorganic particles or organic particles.
• the particles contained are not limited to specific inorganic particles or organic particles, and include, for example, titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay, calcium phosphate, mica, hectorite, and zirconia.
• examples include inorganic particles such as tungsten oxide, lithium fluoride, and calcium fluoride, and organic polymer particles such as styrene, acrylic, melamine, benzoguanamine, and silicone.
• a film containing a combination of two or more types may also be used.
• titanium oxide, calcium carbonate, and silica which are highly versatile, are included.
• the above-described particles can also be contained in a functional layer-equipped laminated film subjected to material and/or chemical recycling.
• the polyester resin composition that is the raw material for the laminated polyethylene terephthalate film can also contain the above particles.
• the polyester resin composition that is the raw material for the functional layer-equipped laminated film subjected to material and/or chemical recycling and the laminated polyethylene terephthalate film of the present invention may also contain the above particles under the following conditions.
• the raw material for the laminated polyethylene terephthalate film of the present invention may be a resin composition obtained by recycling the base material portion of the laminated film with a functional layer, for example, a polyester resin composition.
• the average particle diameter of the particles contained in the polyester resin composition according to the present invention is preferably 0.2 ⁇ m or more and 5.0 ⁇ m or less, more preferably 0.4 ⁇ m or more and 5.0 ⁇ m or less.
• the thickness is 0.2 ⁇ m or more, air can be released evenly when the film is rolled up into a roll for both film production and use, and the roll shape is good and the flatness is good, making it an ultra-thin ceramic green sheet.
• This is preferable because it is suitable for manufacturing (hereinafter referred to as having good handling properties).
• it is 5.0 ⁇ m or less, surface irregularities are small and there is no transfer to processed products (for example, semiconductor parts, ceramic green sheets, optical films), which is preferable.
• the content of the particles is preferably from 100 ppm to 10,000 ppm, more preferably from 300 ppm to 8,000 ppm, based on the laminated polyethylene terephthalate film.
• handling property is good and it is preferable.
• it is 10,000 ppm or less, there is no transfer to processed products, which is preferable.
• the laminated polyethylene terephthalate film of the present invention can be obtained even when the polyester resin composition, which is the raw material for the laminated film with a functional layer subjected to material and/or chemical recycling, does not contain particles. be able to.
• particles having the conditions described herein may be added, for example, in the process of recycling the functional layer-equipped film.
• the laminated polyethylene terephthalate film for mold release may be a biaxially stretched laminated polyethylene terephthalate film.
• the intrinsic viscosity (IV) of the laminated polyethylene terephthalate film for mold release is preferably 0.500 dl/g or more and 0.700 dl/g or less, for example, 0.500 dl/g or more and 0.700 dl/g or less. It is 510 dl/g or more and 0.650 dl/g or less, and more preferably 0.510 dl/g or more and 0.620 dl/g or less.
• it is 0.510 dl/g or more and 0.580 dl/g or less.
• the intrinsic viscosity is 0.500 dl/g or more, it is preferable because breakage is less likely to occur during the stretching process. Moreover, biaxial stretching can be performed without impairing film formability.
• it is 0.700 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.
• the filter filtration pressure can be suppressed, so there is no problem with operability. It is preferable that the raw material is sufficiently vacuum dried.
• the laminated polyethylene terephthalate film according to the present invention desirably exhibits the above-mentioned limiting viscosity even in an embodiment in which the film is obtained by forming a recycled chip into a film.
• the laminated polyethylene terephthalate film of the present invention which includes a resin obtained by materially and/or chemically recycling a film with a functional layer containing one or more types of inorganic particles or organic particles, has an intrinsic viscosity (IV) of 0.
• IV intrinsic viscosity
• the present invention should not be interpreted as being limited to a specific theory, it is believed that by including particles in the recycled resin, problems such as prolonged cooling time and quality deterioration during film formation can be suppressed; It is presumed that it is possible to suppress temperature irregularities during the time. It is also presumed that it contributes to improving the smoothness of the surface shape of the obtained film. Therefore, the surface roughness SRa according to the present invention can be guided to a predetermined range, and, for example, a laminated polyethylene terephthalate film with excellent handling properties and low surface roughness can be obtained.
• the laminated polyethylene terephthalate film according to the present invention preferably has a thickness of 12 to 100 ⁇ m, more preferably 12 to 85 ⁇ m, and even more preferably 15 ⁇ m to 80 ⁇ m. If the thickness of the film is 12 ⁇ m or more, there is no risk of deformation due to heat during film production or when used as a process film, which is preferable. On the other hand, if the thickness of the film is 100 ⁇ m or less, the amount of film to be discarded after use will not be excessively large, which is preferable in terms of reducing environmental impact.Furthermore, the amount of material per area of the release film used is small. Therefore, it is preferable from an economic point of view. In one embodiment, the thickness ratio of the surface layer A is 30% or more and 50% or less of the total layer. That is, the thickness of the surface layer A is preferably 30% or more and 50% or less of the 100% thickness of the laminated polyethylene terephthalate film.
• the laminated polyethylene terephthalate film in the present invention contains one or more types of Si, Ti, and Ba components, and the polyethylene terephthalate film contains a total of 0.1 ppm or more and 5000 ppm or less of Si, Ti, and Ba components based on 100 parts by mass of the film. do.
• the laminated polyethylene terephthalate film for mold release has a surface layer A and a surface layer B, and may further have a core layer C.
• the core layer C is arranged between the surface layer A and the surface layer B, and the core layer C may have a plurality of laminated structures.
• the surface layer A, the surface layer B, and the core layer C may contain one or more types of Si, Ti, and Ba components, and all the layers may contain one or more types of Si, Ti, and Ba components.
• the layer structure in the thickness direction may be an A/B laminated structure, an A/C/B laminated structure, or the like.
• the laminated polyethylene terephthalate film in the present invention includes a surface layer A that does not substantially contain particles with a particle size of 1.0 ⁇ m or more, and a surface layer B that contains particles. It is preferable that the 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 laminated polyethylene terephthalate film for mold release of the present invention is preferably a laminated film having a surface layer A substantially free of inorganic particles on at least one side. Thereby, it is possible to more effectively suppress the transfer of the particle shape in the base material to the resin sheet and the occurrence of defects.
• the surface layer A that does not substantially contain particles with a particle size of less than 1.0 ⁇ m also substantially does not contain particles with a particle size of 1.0 ⁇ m or more.
• substantially no particles means, for example, in the case of inorganic particles less than 1.0 ⁇ m, the amount of inorganic elements determined by fluorescent X-ray analysis is 50 ppm or less, preferably 10 ppm. Hereinafter, it most preferably means a content that is below the detection limit. Even if particles are not actively added to the film, contaminants derived from foreign substances or dirt attached to the raw resin or the line or equipment in the film manufacturing process are peeled off and mixed into the film. This is because there is. Moreover, "substantially not containing particles with a particle size of 1.0 ⁇ m or more” means that particles with a particle size of 1.0 ⁇ m or more are not included. In one embodiment, the surface layer A preferably does not contain particles such as lubricant and does not use recycled raw materials. Surface roughness can be reduced more effectively.
• a coating layer containing a binder forming the surface layer B may be applied during film formation.
• the surface layer B preferably contains at least one type of particles selected from calcium carbonate particles and silica particles, from the viewpoint of the slipperiness of the film and the ease with which air can escape.
• the content of particles contained in the entire layer is preferably 500 to 20,000 ppm.
• the surface layer B may contain particles in an amount of 500 to 15,000 ppm, for example, in an amount of 3,000 ppm to 15,000 ppm.
• surface layer B contains 500 to 10,000 ppm of silica particles and/or calcium carbonate particles.
• the surface layer B contains silica particles and/or calcium carbonate particles within the above range, 500 to 10,000 ppm of silica particles and/or calcium carbonate particles are included in all layers of the laminated polyethylene terephthalate film of the present invention.
• the surface layer A, the surface layer B, and the core layer C provided as necessary. means the total amount of particles contained in the whole.
• the surface layer A is a layer on which functional layers are laminated, and has a three-dimensional central plane average surface roughness (SRa) of 1 nm or more and 7 nm or less. Moreover, it is preferable that the maximum peak height (SRp) is 200 nm or less. By having such three-dimensional central plane average surface roughness and maximum peak height, it is possible to suppress surface unevenness, and it is possible to suppress transfer of unevenness to a processed product, that is, a molded product.
• the average surface roughness (SRa) of the surface layer A is 1.5 nm or more and 6.5 nm or less, for example, 2.0 nm or more and 6.0 nm or less.
• a functional layer laminated on the surface layer A can also have high smoothness.
• the three-dimensional center surface average surface roughness (SRa) and maximum peak height (SRp) of the surface layer A can be controlled within the scope of the present invention.
• the total amount of Si, Ti, and Ba components contained in the surface layer A is such that when inorganic elements are quantified by fluorescent X-ray analysis, the content is 50 ppm or less, preferably 10 ppm or less, and most preferably less than the detection limit. means quantity.
• the total amount of Si, Ti, and Ba components is it is assumed that the amount is 50 ppm or less. This is because, for example, contaminant components originating from foreign substances or dirt adhering to the raw resin or the line or equipment in the film manufacturing process may be peeled off and mixed into the film.
• the three-dimensional central plane average surface roughness (SRa) of the surface layer B may be 20 nm or more and 40 nm or less.
• the surface layer B may also exhibit a maximum peak height (SRp) within the above range.
• At least one of the surface roughness (SRa) or the maximum peak height (SRp) of the surface layer A and the surface layer B exhibits different numerical ranges.
• the particle content in the laminated polyethylene terephthalate film is 500 ppm or more and the SRa of at least the surface layer A is 1 nm or more, air must be released uniformly when the film is rolled up in both production and use. , the winding appearance is good, and the flatness is also good. Therefore, it is suitable for producing ultra-thin ceramic green sheets.
• a resin layer substantially free of inorganic particles for example, a polyester resin layer, may be provided on the functional layer side of the surface layer A, and substantially free of particles having a particle size of 1.0 ⁇ m or more.
• a resin layer for example a polyester resin layer, may be provided on the functional layer side of the surface layer A.
• the surface layer A has a maximum peak height (SRp) of 200 nm or less.
• SRp maximum peak height
• the surface layer A has a maximum peak height (SRp) of 20 nm or more and 200 nm or less, and may be 25 nm or more and 180 nm or less.
• SRp maximum peak height
• the core layer C is a layer in which the surface layer A is laminated on one side and the surface layer B is laminated on the opposite side.
• the surface shape of the core layer C contains one or more of Si, Ti, and Ba components, and can exhibit the content specified in the present invention. Further, the surface shape may be controlled by adding particles as appropriate.
• the core layer C according to the present invention can include material and/or chemically recycled resin.
• the present invention is a laminated polyethylene terephthalate film that uses a raw material obtained by materially recycling a film with a functional layer and contains at least one of Si, Ti, and Ba components, and contains each component in a total amount of 0.1 ppm or more.
• the three-dimensional center plane average surface roughness (SRa) of the polyester film surface is 1 nm or more and 7 nm or less, for example, SRa is 1.5 nm or more and 6.5 nm or less, and the maximum peak height (SRp) is 200 nm or less. It is preferable that there be.
• the laminated polyethylene terephthalate film contains one or more types of Si, Ti, and Ba components, and the polyethylene terephthalate film contains the Si, Ti, and Ba components in a total of 0.1 ppm or more and 5000 ppm or less based on 100 parts by mass of the film. .
• the total amount of Si, Ti, and Ba components is 0.3 ppm or more and 3000 ppm or less, for example, the total amount of Si, Ti, and Ba components is 0.3 ppm or more and 1000 ppm or less.
• the laminated polyethylene terephthalate film has good handling properties, and It is possible to suppress unevenness on the surface of the film, and to prevent the unevenness from being transferred to a processed product, that is, a molded product.
• a processed product that is, a molded product.
• conventional recycled films there has been a tendency to actively remove Si, Ti, and Ba components.
• the handling properties of the laminated polyethylene terephthalate film can be maintained well, and furthermore, the unevenness on the film surface can be suppressed, and the unevenness transfer to the molded product can be prevented.
• the film of the present invention can exhibit mechanical properties such as tensile strength and elastic modulus that are comparable to or higher than those of a film formed from a virgin material that does not contain recycled resin.
• the present invention can improve various physical properties of the resulting polyester and exhibit high recyclability.
• the core layer C and/or the surface layer B when having a core layer C, contains one or more types of Si, Ti, and Ba components, and the core layer C and/or the surface layer B contains Si, Ti, and Ba.
• the total amount of the components (that is, the total amount of Si element, Ti element, and Ba element) is 0.1 ppm or more and 5000 ppm or less.
• the surface layer A since the surface layer A does not substantially contain Si, Ti, and Ba components, the surface layer A not only has high surface smoothness but also has the ability to function as a functional layer. can exhibit high adhesion.
• the content of the Si component in the entire laminated polyethylene terephthalate film is 0.3 ppm or more and 2000 ppm or less, for example, 0.3 ppm or more and 1500 ppm or less, and may be 0.3 ppm or more and 1000 ppm or less. In another embodiment, the content of the Si component may be 0.3 ppm or more and 500 ppm or less.
• the core layer C can contain a Si component. Further, the core layer C can contain a resin obtained by materially recycling a release film with a functional layer in an amount of 5% by mass or more and 50% by mass or less, and can contain a Si component within the above range.
• a resin obtained by materially recycling a release film with a functional layer is contained in an amount of 5% by mass or more and 50% by mass or less, and the content of the Si component in the entire laminated polyethylene terephthalate film is 0.3ppm or more and 2000ppm or less.
• the film can exhibit good mechanical properties, such as tensile strength, elasticity, surface hardness, and tear strength, even though it contains recycled resin.
• material recycling a release film with a functional layer it was necessary to almost completely remove the silicone component present on the surface of the base material.
• the Si component in the entire laminated polyethylene terephthalate film is 0.3 ppm or more and 2000 ppm or less.
• the interpretation should not be limited to a specific theory, it is presumed that the Si component contributes to the formation of the crystal structure of the polyester film.
• the content of the Ti component in the entire laminated polyethylene terephthalate film is 0.3 ppm or more and 2000 ppm or less, for example, 0.3 ppm or more and 1500 ppm or less, and may be 0.3 ppm or more and 1000 ppm or less.
• the surface roughness (SRa) and maximum peak height (SRp) of the polyester film are significantly lower than when the Ti component is less than 0.3 ppm. It can be largely controlled in the range of nanometer to several tens of nanometers.
• the surface roughness (SRa) and maximum peak height (SRp) of the polyester film can be controlled more precisely according to the required characteristics of the release layer laminated on the laminated polyethylene terephthalate film, so for example, ceramic green Improves sheet processability. Moreover, the mold releasability of the ceramic green sheet can also be improved.
• the content of the Ba component is 0.3 ppm or more and 2000 ppm or less, for example, 0.3 ppm or more and 1500 ppm or less, and may be 0.3 ppm or more and 1000 ppm or less.
• the Ba component also increases the surface roughness (SRa) and maximum peak height (SRp) of a polyester film by several nanometers to several tens of nanometers compared to when the Ti component is less than 0.3 ppm. It can be largely controlled within the order range.
• SRa surface roughness
• SRp maximum peak height
• the total amount of Si, Ti, and Ba components that is, the total amount of Si element, Ti element, and Ba element
• the composition of the present invention Residues of green sheet components, release layer components, and base materials can be recycled and used within a range that does not deviate from the following. Therefore, in the present invention, for example, the material recycling process of resin, which is material recycling of a release film with a functional layer, can be simplified and shortened compared to the conventional method, resulting in more efficient recycling with reduced waste. can be promoted.
• the laminated polyethylene terephthalate film of the present invention contains material-recycled resin (also referred to as material recycled raw material) in an amount of 5% by mass or more and 50% by mass or less based on 100% by mass of the laminated polyethylene terephthalate film.
• material recycling raw material is contained in an amount of 8% by mass or more and 47% by mass or less, for example, 10% by mass or more and 45% by mass or less.
• the resin may be a material obtained by recycling a release film with a functional layer that is used or scheduled to be discarded.
• the laminated polyethylene terephthalate film has a multilayer structure
• the recycled material contained in the surface layer A has a total of 5% by mass or more and 50% by mass or less in the two layers. It can be blended as appropriate so that.
• the recycled material contained in the core layer C can be appropriately blended so that the total in each layer forming the layer C is 5% by mass or more and 50% by mass or less. .
• silica particles and/or calcium carbonate particles as the particles contained in the laminated polyethylene terephthalate film from the viewpoint of transparency and cost.
• inert inorganic particles and/or heat-resistant organic particles can be used.
• Other usable inorganic particles include alumina-silica composite oxide particles, hydroxyapatite particles, etc. It will be done.
• 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 particles that may be included have a longest side length of 0.5 ⁇ m or more and 5.0 ⁇ m or less, and for example, the average particle size of the particles is 0.2 ⁇ m to 4 ⁇ m. .0 ⁇ m is preferable, and 0.4 ⁇ m to 3.6 ⁇ m is more preferable.
• the content of particles is preferably 100 to 10,000 ppm, more preferably 300 to 8,000 ppm, based on the laminated polyethylene terephthalate film.
• the average particle diameter of the particles can be measured by observing the particles in the cross section of the processed film with a scanning electron microscope, observing 100 particles, and using the average value as the average particle diameter. .
• the shape of the particles is not particularly limited as long as the object of the present invention is met, and spherical particles and irregularly shaped non-spherical particles can be used.
• the particle diameter of irregularly shaped particles can be calculated as a circular equivalent diameter.
• the equivalent circle diameter is a value obtained by dividing the area of the observed particle by pi ( ⁇ ), calculating the square root, and doubling the square root.
• the laminated polyethylene terephthalate film may contain two or more types of different particles. Further, particles of the same type but having different average particle diameters may be contained. Methods for adding particles include side-feeding during material recycling, creating a masterbatch by melting and kneading raw materials and particles obtained through material recycling, and mixing two or more types of recycled materials. However, it is not limited to these methods. Functionality may be imparted by a coating layer.
• the method for providing this coat layer is not particularly limited, but it is preferably provided by a so-called in-line coating method in which coating is performed during the formation of a polyester film.
• the laminated polyethylene terephthalate film includes SiO 2 having a longest side length of 0.5 ⁇ m or more and 5.0 ⁇ m.
• at least one of the core layer C and the surface layer B contains SiO 2 .
• the functional layer of the functional layered film to be recycled (i.e., the functional layered film used as a raw material for recycled resin) is not particularly limited, and may include silicone-based, cyclic olefin-based, acyclic olefin-based, fluorine-based, and alkyd-based. , acrylic, melamine, and epoxy resins.
• the functional layer contains silicone-based, acrylic-based, or melamine-based resin.
• the functional layer contains these resins, it is possible to improve the adhesion between the surface layer A and the surface layer B in the laminated polyethylene terephthalate film for mold release, and in one embodiment, the core layer C, the surface layer A, and the surface layer B It is possible to obtain a laminated polyethylene terephthalate film for mold release that can improve adhesion to the mold and has high smoothness.
• the functional layer include an antistatic layer, a release layer, and an adhesive layer.
• the functional layer is used as a release layer, there may be residues of the object to be released (ie, the processed product) on the surface of the release layer.
• the object to be released may be an adhesive, an optical film, a ceramic green sheet, etc., and some of these may exist as the deposit according to the present invention.
• the release layer of the present invention is required to have high adhesion to the object to be released.
• release layers for adhesives, release layers for optical films, and release layers for ceramic green sheets can be used in the manufacturing process of objects to be released and devices using them. It is necessary to show high adhesion between processes.
• the mold release layer in the present invention is a mold release layer exposed to high temperature (e.g., 60° C.
• the removal process which involves removing deposits from films with functional layers (e.g. release layers subjected to these conditions), increases the purity of the recycled substrate and improves, e.g. the required optical properties, mechanical It can bring about the strength of the objective.
• the silicone-based compound is a compound having a silicone structure in its molecule, and includes curable silicone, silicone graft resin, modified silicone resin such as alkyl-modified resin, and the like.
• the reactive cured silicone resin addition reaction type, condensation reaction type, ultraviolet ray or electron beam curing type, etc. can be used.
• addition reaction type silicone resins include those that are cured by reacting polydimethylsiloxane into which a vinyl group has been introduced into the terminal or side chain with hydrogen siloxane using a platinum catalyst. At this time, it is more preferable to use a resin that can be cured within 30 seconds at 120° C., as this allows processing at low temperatures. Examples include low-temperature addition-curing types manufactured by Dow Corning Toray Co., Ltd.
• thermal UV curing Types LTC851, BY24-510, BY24-561, BY24-562, etc.
• Solvent addition type KS-774, KS-882, X62-2825, etc.
• Solvent addition + UV curing type X62-5040, X62-5065, X62-5072T, KS5508, etc.
• dual cure type X62-2835, X62-2834, X62-1980, etc.
• condensation reaction silicone resins include those that create a three-dimensional crosslinked structure by condensing polydimethylsiloxane having an OH group at the end and polydimethylsiloxane having an H group at the end using an organotin catalyst.
• condensation reaction silicone resins include those that create a three-dimensional crosslinked structure by condensing polydimethylsiloxane having an OH group at the end and polydimethylsiloxane having an H group at the end using an organotin catalyst.
• UV-curable silicone resins include those that use the same radical reaction as normal silicone rubber crosslinking as the most basic type, those that are photocured by introducing unsaturated groups, and those that are cured by photocuring by introducing unsaturated groups, and those that are made by decomposing onium salts with UV rays.
• Examples include those that generate a strong acid and use this to cleave the epoxy groups to effect crosslinking, and those that effect crosslinking by addition reaction of thiol to vinylsiloxane.
• an electron beam can also be used instead of the ultraviolet rays. Electron beams have more energy than ultraviolet rays, and it is possible to carry out a crosslinking reaction using radicals without using an initiator as in the case of ultraviolet curing.
• resins used include UV-curing silicones manufactured by Shin-Etsu Chemical (X62-7028A/B, X62-7052, X62-7205, X62-7622, X62-7629, X62-7660, etc.), Momentive Performance UV curing silicone manufactured by Materials (TPR6502, TPR6501, TPR6500, UV9300, UV9315, XS56-A2982, UV9430, etc.), UV curing silicone manufactured by Arakawa Chemical Co., Ltd. (Silicolease UVPOLY200, POLY215, POLY201, KF-UV265A) M etc.) can be mentioned.
• acrylate-modified or glycidoxy-modified polydimethylsiloxane can also be used.
• modified polydimethylsiloxanes can also be mixed with polyfunctional acrylate resins, epoxy resins, etc. and used in the presence of an initiator.
• the cyclic olefin resin contains a cyclic olefin as a polymerization component.
• Cyclic olefins are polymerizable cyclic olefins having an ethylenic double bond in the ring, and can be classified into monocyclic olefins, bicyclic olefins, polycyclic olefins having three or more rings, and the like.
• Examples of monocyclic olefins include cyclic C4-12 cycloolefins such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene.
• Examples of the bicyclic olefin include alkyl groups such as 2-norbornene; 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, and 5-butyl-2-norbornene.
• Norbornenes having an alkenyl group such as (C1-4 alkyl group); norbornenes having an alkenyl group such as 5-ethylidene-2-norbornene; 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, etc.
• norbornenes having an alkoxycarbonyl group norbornenes having a cyano group such as 5-cyano-2-norbornene; having an aryl group such as 5-phenyl-2-norbornene and 5-phenyl-5-methyl-2-norbornene
• polycyclic olefins include dicyclopentadiene; 2,3-dihydrodicyclopentadiene, methanooctahydrofluorene, dimetanooctahydronaphthalene, dimanocyclopentadienonaphthalene, methanooctahydrocyclopentadienonaphthalene, etc.
• the acyclic olefin resin contains an acyclic olefin as a polymerization component.
• acyclic olefins include ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, Examples include alkenes such as 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-icosene. Rubber can also be used as a surface treatment resin.
• Examples include copolymers of butadiene, isoprene, and the like. Regardless of whether it is a cyclic olefin or an acyclic olefin, the olefin resin may be used alone or two or more types may be copolymerized. The cyclic olefin resin and the acyclic olefin resin may be partially modified with hydroxyl groups or acid modified, and crosslinked with these functional groups using a crosslinking agent.
• the crosslinking agent may be appropriately selected according to the modifying group, and examples thereof include aromatic diisocyanates such as tolylene diisocyanate, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and polymethylene polyphenylisocyanate.
• aromatic diisocyanates such as tolylene diisocyanate, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and polymethylene polyphenylisocyanate.
• isocyanate-based crosslinking such as lower aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, and hydrogenated products of the above aromatic diisocyanates.
• lower aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate
• alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate
• hydrogenated products of the above aromatic diisocyanates include melamine crosslinking agents such as methyl etherified melamine resin and butyl etherified melamine resin, epoxy crosslinking agents, and the like.
• the fluorine-based compound is not particularly limited as long as it is a compound having at least either a perfluoroalkyl group or a perfluoroalkyl ether group.
• a portion of the fluorine-based compound may be modified with an acid, a hydroxyl group, an acrylate group, or the like.
• a crosslinking agent may be added to crosslink at the modified site.
• a compound having at least one of a perfluoroalkyl group and a perfluoroalkyl ether group may be added to the UV-curable resin and polymerized.
• a small amount of a compound having a perfluoroalkyl group that does not have a reactive functional group may be added to the binder resin.
• Mold release agents such as polyolefin mold release agents, long-chain alkyl group-containing resin mold release agents, fluorine mold release agents, and silicone mold release agents are used as the main resin in the mold release layer of the mold release film. Alternatively, it may be used as an additive to the binder resin.
• binder resin There are no particular limitations on the binder resin, and examples include UV-curable resins obtained by curing functional groups such as acrylic groups, vinyl groups, and epoxy groups with UV irradiation, ester-based resins, urethane-based resins, olefin-based resins, and acrylic resins. It is also possible to use thermoplastic resins such as epoxy resins, thermosetting resins such as epoxy resins, and melamine resins.
• a functional layer-equipped film to be recycled (that is, a functional layer-equipped film used as a raw material for recycled resin) has a functional layer provided on at least one surface of a base material (that is, a film base material). That is, the film with a functional layer includes a base material and a functional layer provided on at least one surface of the base material. After using a film with a functional layer, deposits may remain on the surface of the film, for example, on the surface of the functional layer. Furthermore, regarding films with functional layers, used films, films that do not meet specifications, films that are damaged during the distribution process, etc. are usually discarded.
• the step of removing deposits from the film to be discarded ie, the functional layer-equipped film to be discarded
• the step of removing the deposits may be omitted.
• the present invention may include removing deposits not only from the surface of the functional layer but also from the surface of the base material opposite to the functional layer.
• the method may include a step of removing deposits adhering to the base material.
• the present invention provides a method for manufacturing a laminated polyethylene terephthalate film for mold release.
• the manufacturing method includes the following (Step 1), (Step 2), and (Step 3).
• (Step 1) A pulverization step comprising pulverizing the functional layer-equipped laminated film to form a pulverized product.
• (Step 2) A chipping step including chipping the pulverized product obtained in Step 1 to form recycled chips.
• Step 3) A step of forming a recycled film, which includes forming the recycled chips obtained in Step 2 into a film and winding up the film.
• a laminated polyethylene terephthalate film for mold release can be obtained without impairing the physical properties of the recycled film even if the step of removing deposits on the surface of the film having a functional layer is not included. be able to.
• Step 1 A pulverization step comprising pulverizing the functional layer-equipped laminated film to form a pulverized product.
• the pulverization process can be performed without removing deposits on the surface of the film having the functional layer. For example, deposits such as adhesives, ceramic green sheets, impurities, etc. may be present on the surface of the functional layer. Furthermore, some of these deposits may be removed before the pulverization step. By removing some of the deposits, it becomes easier to control the content of Si, Ti, and Ba components.
• the content of Si, Ti, and Ba components in the core layer C and the surface layer B can be controlled by the steps 2 and 3 described later, so that the content of Si, Ti, and Ba components present on the surface of the functional layer can be controlled as in the conventional recycling technology.
• the functional layer and the base material in which such deposits are present can be directly subjected to the pulverization process. Therefore, compared to conventional recycling techniques, the steps and time required to manufacture resin pellets and form them into a film can be significantly reduced. Furthermore, the amount of waste can be reduced.
• the present invention includes, as Step 1, a pulverization step that includes pulverizing the functional layer-equipped laminated film to form a pulverized product.
• a pulverization step that includes pulverizing the functional layer-equipped laminated film to form a pulverized product.
• it includes pulverizing a substrate containing at least deposits to form a pulverized product.
• the functional layer from which deposits have been removed may be further ground, and then mixed with the ground material of the base material.
• at least a pulverized product obtained by pulverizing a base material may be mixed with a pulverized functional layer product obtained by pulverizing a functional layer from which deposits have been removed, and a pulverized product of the base material.
• a pulverized product may be obtained by laminating the functional layer from which deposits have been removed and the base material, or by separating the functional layer from which deposits have been removed and the base material and then pulverizing each using the same pulverizer.
• the powder may be ground in a separate process using a different grinder.
• the film with a functional layer can be pulverized using a pulverizer such as a single-screw pulverizer, a twin-screw pulverizer, a tri-screw pulverizer, a cutter mill, or the like.
• a rotor with a plurality of rotating blades attached at regular intervals on the periphery is housed in a housing with a plurality of fixed blades attached, and the tip of each rotating blade rotates as the rotor rotates. Grind the solid material by cutting it with the tip of the fixed blade.
• pulverized materials those that pass through a predetermined mesh screen are obtained as pulverized products. Any known method can be used as long as it can be pulverized to a predetermined size.
• the pulverized product obtained by pulverization in the pulverization step is, for example, in the form of flakes, powder, lumps, or strips, and preferably includes flakes.
• the flake-like pulverized product refers to one that is flaky or flat.
• the size of the screen holes used in the crushing step is preferably 1 mm or more and 10 mm or less, more preferably 3 mm or more and 8 mm or less. If the screen hole size is less than 1 mm, the pulverized product will become powdery and difficult to handle, so it is preferably 1 mm or more.
• the bulk density becomes too low, making it difficult to control the discharge amount in the extrusion process described below, so it is preferably 10 mm or less.
• the width of the film with a functional layer is narrow, for example, 20 mm or less, a method of cutting in the machine direction may be used.
• Step 2 A chipping step including chipping the pulverized product obtained in Step 1 to form recycled chips.
• the granulating device for chipping include a single screw extruder, a twin screw extruder, and a multi-screw extruder.
• a twin-screw extruder or a multi-screw extruder is used, which can control kneading strength and suppress resin deterioration.
• the granulation shape may be any shape such as columnar, pillow-like, spherical, or ellipsoidal shape.
• the method may include a step of filtering the granulated product through a filter.
• a filter By filtering the granules, it is possible to remove coarse foreign substances that may cause roughness of the surface of the resulting film.
• the step of filtering the granules may be repeated multiple times.
• the laminated polyethylene terephthalate film in the present invention contains one or more types of Si, Ti, and Ba components, and the polyethylene terephthalate film has a total of 0.1 ppm or more of the Si, Ti, and Ba components with respect to 100 parts by mass of the film. Since it contains 5000 ppm or less, it does not completely remove Si, Ti, and Ba components.
• Step 3 A step of forming a recycled film, which includes forming the recycled chips obtained in Step 2 into a film and winding up the film.
• the recycled chip obtained in step 2 can form a surface layer B and a core layer C.
• the surface layer A can have extremely high surface smoothness.
• the resin obtained by material recycling of a used film with a functional layer is a resin from which the functional layer and/or the object (for example, a mold material to be released) attached to the functional layer have been removed.
• the base film before recycling that is, the film from which the functional layer has been removed, may contain particles in an amount of 0.01 parts by mass or more and 1.0 parts by mass or less, based on 100 parts by mass of the film base material before recycling. , for example, 0.03 parts by mass or more and 1.0 parts by mass or less, for example, 0.21 parts by mass or more and 1.0 parts by mass or less, of particles.
• the recycled film that is, the laminated polyethylene terephthalate film of the present invention, also has good rigidity and moisture resistance. , can have anti-blocking properties.
• the interpretation should not be limited to a specific theory, in the present invention, by having a predetermined amount of particles in the base film, it not only provides the required handling properties and surface shape, but also provides additional properties such as rigidity. It can provide a good balance of functions. For this reason, for example, in the past, a step was required to remove particles that were treated as impurities, but the present invention eliminates the step of actively removing particles as long as the haze and surface shape according to the present invention are achieved. can.
• the film from which the functional layer has been removed is 0.01 parts by mass or more and 1.0 parts by mass or less, for example, 0.21 parts by mass or more, 1.0 parts by mass, based on 100 parts by mass of the film base material before recycling.
• the functional layer residue, the residue adhering to the functional layer, for example, a mold release material may be included in an amount equal to or less than parts by mass.
• the method for removing the residual deposits is not particularly limited, and includes, for example, attaching an adhesive roll and removing it during peeling, removing it by suction with a vacuum, scraping it off with a blade, and removing it with high-pressure water or high-pressure air.
• method to remove by blowing sand or dry ice, method to soak a film in the cleaning layer and remove it by adsorbing it with microbubbles, etc.
• method to remove it by floating it with micro vibrations such as ultrasonic waves, method to remove it by using ultrasonic wave etc. Examples include a method of dissolving and removing deposits using CO 2 . These methods may be combined. These methods are not particularly limited, but in terms of efficiency, methods that allow roll-to-roll processing are preferred.
• the functional layer may be removed together with the deposits, or the functional layer may not be removed and may remain on the film.
• the step of removing deposits from a film having a functional layer includes removing adhesives, ceramic green sheets, impurities, etc. remaining on the surface of the functional layer.
• it may be a step of removing the functional layer from the base material.
• the step of removing deposits is a step of removing a functional layer, such as a release layer or a slippery layer, from the base material.
• the laminated polyethylene terephthalate film of the present invention includes a resin obtained by separating the base material from a used or unused functional layer-equipped film and recycling the base material.
• a resin obtained by separating the base material from a used or unused functional layer-equipped film for example, with respect to a release film used in the production of ceramic green sheets, it is desirable to remove the residue of the object to be released (green sheet) and the release layer, and to recycle the base material portion.
• the laminated polyethylene terephthalate film contains one or more types of Si, Ti, and Ba components, and the polyethylene terephthalate film has a total content of 0.1 ppm or more and 5000 ppm of Si, Ti, and Ba components based on 100 parts by mass of the film. As long as this condition is satisfied, the recycling process may be carried out with the residue of the material to be released (green sheet) and the release layer remaining.
• the method for biaxially stretching the polyester film in the present invention is not particularly limited, and any conventionally commonly used method 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.
• a filter may be used between melting the recycled chips and extruding them.
• a known filter may be appropriately employed depending on the target level of surface defects.
• a filter with a smaller 95% filtration accuracy the particle size of the glass beads that remain on the filter without allowing 95% or more of the glass beads to pass through
• the 95% filtration accuracy of the filter used is preferably 30 ⁇ m or less, and more preferably 20 ⁇ m or less.
• the lower limit of the 95% filtration accuracy of the filter is preferably, but not limited to, 5 ⁇ m or more, and more preferably 10 ⁇ m or more. Note that if the foreign matter accumulated in this way leaks out, the subsequent products will be defective.
• Such a filter for molten resin may be inserted during the production of recycled chips, after the resin is brought into a molten state and before it is extruded.
• the filtration accuracy of the filter at this time can be appropriately selected depending on the level of defects in the target resin, and removes those necessary for the physical properties of the film, such as particles to maintain slipperiness. It is preferable to select a filter size that can remove aggregates of the functional layer that are unnecessary for film properties.
• the film forming method in the present invention is not limited, but specifically, material recycled polyester pellets are sufficiently vacuum dried, then fed to an extruder, melted and extruded at about 255 to 280 ° C. into a sheet shape, cooled and solidified, An unstretched PET sheet is formed.
• the obtained unstretched sheet is stretched 3.0 to 6.0 times in the longitudinal direction using rolls heated to 75 to 140°C to obtain a uniaxially oriented PET film.
• the ends of the film are held with clips and introduced into a hot air zone heated to 75 to 140°C, and after drying, the film is stretched 3.0 to 6.0 times in the width direction. Subsequently, it can be guided to a heat treatment zone at 180 to 260°C and heat treated for 1 to 60 seconds. During this heat treatment step, a relaxation treatment of 0 to 10% may be performed in the width direction or length direction, if necessary.
• the laminated polyethylene terephthalate film of the present invention can be used as a base material in a release film for molding a resin sheet.
• a resin sheet it is not particularly limited and may be applied to the production of adhesives and optical films.
• it is a release film for molding a resin sheet containing an inorganic compound.
• the inorganic compound include metal particles, metal oxides, minerals, and the like, such as calcium carbonate, silica particles, aluminum particles, barium titanate particles, and the like.
• the resin include polyvinyl acetal resin and poly(meth)acrylic acid ester resin.
• the laminated polyethylene terephthalate film of the present invention is suitable for laminating a release layer with high smoothness, and even in an embodiment in which the resin sheet contains these inorganic compounds, there are problems that may be caused by the inorganic compounds, such as problems with the resin sheet. Problems such as breakage and difficulty in peeling the resin sheet from the release layer can be suppressed.
• the resin component forming the resin sheet can be appropriately selected depending on the application.
• the resin sheet containing an inorganic compound is a ceramic green sheet.
• the ceramic green sheet can include barium titanate as an inorganic compound.
• the resin sheet has a thickness of 0.2 ⁇ m or more and 1.0 ⁇ m or less.
• the release film of the present invention includes a laminated polyethylene terephthalate film and a release layer.
• the release layer is provided on the surface layer A of the laminated polyethylene terephthalate film. That is, the release film includes a laminated polyethylene terephthalate film and a release layer laminated on the surface layer A of the laminated polyethylene terephthalate film.
• the description of the release layer of the release film is omitted because it overlaps with the description of the release layer of the above-mentioned film with a functional layer (that is, the film with a functional layer to be recycled). Therefore, the above explanation of the release layer of the film with a functional layer can also be treated as an explanation of the release layer of the release film according to the present invention.
• the same operation was performed continuously 150 times at intervals of 2 ⁇ m in the width direction of the biaxially stretched polyethylene terephthalate film, that is, over 0.3 mm in the width direction of the biaxially stretched polyethylene terephthalate film, and the data was imported into the analysis device.
• the center surface average roughness (SRa) and center line peak height (SRp) were determined using an analyzer.
• Average particle size The roughening agent was observed with a scanning electron microscope (manufactured by Hitachi, Model S-51O), the magnification was changed as appropriate depending on the particle size, and the photograph was enlarged and copied. Next, the outer periphery of at least 200 randomly selected particles was traced, and the equivalent circle diameter of the particles was measured from the traced images using an image analysis device, and the average of these was taken as the average particle diameter.
• MLCC ceramic green sheet
• the composition of the coating liquid used to produce the release film is as follows.
• the solid content of the coating liquid was 1.0% by mass, the surface tension was 27 mN/m, and the viscosity was 5 mPa ⁇ s. Note that this coating liquid was used after being passed through a filter that can remove 99% or more of foreign matter of 0.5 ⁇ m or more.
• Crosslinking agent hexameth
• the mixture was diluted with toluene, and 0.5 mol% of azobisisobutyronitrile was added and copolymerized under a nitrogen stream.
• a resin solution A that is, a long-chain alkyl group-containing acrylic polyol solution
• the weight average molecular weight of the polymer obtained at this time was 30,000.
• Defective rate (%) (Number of ceramic green sheets determined to be defective/100 sheets) x 100 The defect rate of each example is shown in Table 3 according to the following classifications. ⁇ Defective rate is 3% or less ⁇ Defective rate is over 3% and 5% or less ⁇ Defective rate is over 5%
• PET3 A used PET film having a silicone release layer on one side and containing 600 ppm of calcium carbonate with a particle size of 1.0 ⁇ m was prepared.
• This PET film is a PET film used for manufacturing ceramic green sheets.
• the silicone release layer was removed from this PET film by sandblasting (it may go without saying that when the silicone release layer is removed, the impurities attached to the silicone release layer are also removed). I would like to clarify this point just in case.)
• the film from which the silicone release layer had been removed was placed in a uniaxial pulverizer and pulverized through a 4 mm hole screen at a speed of 100 kg/hour to obtain a pulverized film.
• the obtained pulverized product was put into a twin-screw extruder to obtain recycled PET3.
• the intrinsic viscosity of recycled PET3 was 0.57 dl/g, and the Si concentration was 5 ppm. Table 1 shows the evaluation results and various conditions.
• PET film having a silicone release layer on one side and containing 600 ppm of calcium carbonate with a particle size of 1.0 ⁇ m was used.
• This PET film is a PET film used for manufacturing ceramic green sheets.
• This film was placed in a uniaxial pulverizer and pulverized through a 4 mm hole screen at a speed of 100 kg/hour to obtain a pulverized film.
• the obtained pulverized product was put into a twin-screw extruder to obtain recycled PET4.
• the intrinsic viscosity of recycled PET4 was 0.56 dl/g, the Si concentration was 200 ppm, the Ti concentration was 50 ppm, and the Ba concentration was 150 ppm. Table 1 shows the evaluation results and various conditions.
• PET1 polyethylene terephthalate pellets
• a continuous esterification reactor consisting of a three-stage complete mixing tank having a stirrer, a partial condenser, a raw material inlet, and a product outlet was used.
• the amount of antimony trioxide was set at 2 mol to mol, and the amount of antimony trioxide was set so that Sb atoms were 160 ppm with respect to the produced PET, and the slurry was continuously supplied to the first esterification reactor of the esterification reactor and heated at normal pressure.
• the reaction was carried out at 255° C. with an average residence time of 4 hours.
• the reaction product in the first esterification reactor is continuously taken out of the system and supplied to the second esterification reactor, and the reaction product is distilled from the first esterification reactor into the second esterification reactor.
• an EG solution containing magnesium acetate in an amount such that Mg atoms are 65 ppm with respect to the generated PET, and 20 ppm of P atoms with respect to the generated PET is supplied.
• An EG solution containing an amount of TMPA was added, and the reaction was carried out at 260° C. at normal pressure with an average residence time of 1.5 hours.
• the reaction product in the second esterification reactor is continuously taken out of the system and supplied to the third esterification reactor, and further contains TMPA in an amount such that P atoms are 20 ppm with respect to the produced PET.
• the EG solution was added and reacted at 260° C. with an average residence time of 0.5 hours at normal pressure.
• the esterification reaction product produced in the third esterification reactor is continuously supplied to a three-stage continuous polycondensation reactor for polycondensation, and a stainless steel sintered filter medium (nominal filtration accuracy of 5 ⁇ m PET (I) (also referred to herein as "PET1”), which is a polyethylene terephthalate pellet having an intrinsic viscosity of 0.62 dl/g, was obtained. Table 1 shows the evaluation results and various conditions.
• the filters are made by melting at 285°C, melting at 290°C using a separate melt extruder extruder, and sintering stainless steel fibers with a 95% cut diameter of 15 ⁇ m, and a filter with a 95% cut diameter of 15 ⁇ m.
• Two stages of filtration are performed using a filter made of sintered stainless steel particles, which are combined in a feed block, and are mixed with 75% PET1 and 25% MB1 to form a B layer (anti-release side layer) and PET1.
• a layer (release surface side layer), 60% PET1 and 40% recycled PET1 are laminated to form C layer, extruded (casting) into a sheet at a speed of 45 m/min, and electrostatic The material was electrostatically adhered and cooled on a casting drum at 30° C. by the adhesion method to obtain an unstretched polyethylene terephthalate sheet having an intrinsic viscosity of 0.56 dl/g.
• the electrostatic adhesion conditions at this time were that the electrode material was tungsten, the cylinder shape (wire) was 0.2 mm in diameter and 0.5 m in length, the current was controlled at a constant rate of 5 mA, the tension of the electrode was 5 kg, and the renewal rate of the electrode was was set at 5 m/hour.
• this unstretched polyethylene terephthalate sheet was heated with an infrared heater, and then stretched 3.5 times in the longitudinal direction at a roll temperature of 80° C. using a speed difference between the rolls. Thereafter, it was introduced into a tenter and stretched 4.2 times in the transverse direction at 140°C. Then, heat treatment was performed at 210° C. in a heat fixing zone. Thereafter, a 2.3% relaxation treatment was performed at 170° C. in the transverse direction to obtain a mill roll (width: 5.0 m) of a biaxially stretched polyethylene terephthalate film having a thickness of 31 ⁇ m.
• This mill roll was transferred to a slitter, treated with a static eliminator (manufactured by Kasuga Denki Co., Ltd., high-density static eliminator processing system) and a web cleaner (manufactured by Shinkosha Co., Ltd., ultrasonic cleaner system), and then cut to a width of 1400 mm with an inner diameter of 6 inches.
• the film was wound up using a contact roll having a rubber hardness of 60 degrees, at a contact pressure of 200 kg/m and a tension of 15 MPa, to obtain a biaxially stretched polyethylene terephthalate film roll.
• a biaxially oriented polyethylene terephthalate film was cut out from a biaxially oriented polyethylene terephthalate film roll, and various evaluations were performed. The evaluation results are shown in Tables 2 and 3.
• Example 2 A biaxially stretched polyethylene terephthalate film roll shown in Table 2 was obtained by changing the raw material composition of the C layer from Example 1. A biaxially oriented polyethylene terephthalate film was cut out from a biaxially oriented polyethylene terephthalate film roll, and various evaluations were performed. The evaluation results are shown in Tables 2 and 3.
• Example 4 A biaxially stretched polyethylene terephthalate film roll shown in Table 2 was obtained in which the raw material for the C layer was changed from recycled PET 1 to recycled PET 2 from Example 1. A biaxially oriented polyethylene terephthalate film was cut out from a biaxially oriented polyethylene terephthalate film roll, and various evaluations were performed. The evaluation results are shown in Tables 2 and 3.
• Example 5 A biaxially oriented polyethylene terephthalate film roll shown in Table 2 was obtained in which the raw material for the C layer was changed from PET1 to recycled PET4 in Example 1. A biaxially oriented polyethylene terephthalate film was cut out from a biaxially oriented polyethylene terephthalate film roll, and various evaluations were performed. The evaluation results are shown in Tables 2 and 3.
• Example 6 A biaxially stretched polyethylene terephthalate film roll shown in Table 2 was obtained by changing the layer ratio (that is, thickness ratio) from Example 1 as shown in Table 2. A biaxially oriented polyethylene terephthalate film was cut out from a biaxially oriented polyethylene terephthalate film roll, and various evaluations were performed. The evaluation results are shown in Tables 2 and 3.
• Example 7 A biaxially stretched polyethylene terephthalate film roll shown in Table 2 was obtained by changing the layer structure from Example 1 to two layers, A/B, and changing the raw material for the B layer from PET1 to recycled PET3. A biaxially oriented polyethylene terephthalate film was cut out from a biaxially oriented polyethylene terephthalate film roll, and various evaluations were performed. The evaluation results are shown in Tables 2 and 3.
• Example 1 A biaxially stretched polyethylene terephthalate film roll shown in Table 2 was obtained by changing the raw materials from Example 1 as shown in Table 2. A biaxially oriented polyethylene terephthalate film was cut out from a biaxially oriented polyethylene terephthalate film roll, and various evaluations were performed. The evaluation results are shown in Tables 2 and 3.
• Comparative Example 1 the three-dimensional center plane average surface roughness (SRa) and maximum peak height (SRp) of the surface layer A were outside the range of the present invention, and the moldability of the MLCC was insufficient. Comparative Example 2 did not contain Si, Ti, and Ba components and was outside the scope of the present invention. In addition, recycled PET 1 to 4 are not used, which does not contribute to reducing environmental load. In Comparative Examples 3 and 4, the three-dimensional center surface average surface roughness (SRa) and maximum peak height (SRp) exceeded the range of the present invention, and the moldability of the MLCC was insufficient.
• MB indicates polyethylene terephthalate calcium carbonate masterbatch, ie, MB1.
• the present invention has industrial applicability because it can provide a laminated polyethylene terephthalate film, a release film, and a method for producing a laminated polyethylene terephthalate film.

Landscapes

• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Environmental & Geological Engineering (AREA)
• Laminated Bodies (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=89382924

Family Applications (1)

Country Status (5)

Cited By (6)

Citations (8)

Family Cites Families (1)

• 2023
  • 2023-06-22 JP JP2024530757A patent/JPWO2024004832A1/ja active Pending
  • 2023-06-22 WO PCT/JP2023/023213 patent/WO2024004832A1/ja not_active Ceased
  • 2023-06-22 KR KR1020247037859A patent/KR20250031148A/ko active Pending
  • 2023-06-22 CN CN202380049970.8A patent/CN119451817A/zh active Pending
  • 2023-06-27 TW TW112123747A patent/TW202408805A/zh unknown

Patent Citations (8)

Also Published As

Similar Documents

Legal Events