WO2023145938A1 - Film de polyester stratifié - Google Patents

Film de polyester stratifié Download PDF

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Publication number
WO2023145938A1
WO2023145938A1 PCT/JP2023/002888 JP2023002888W WO2023145938A1 WO 2023145938 A1 WO2023145938 A1 WO 2023145938A1 JP 2023002888 W JP2023002888 W JP 2023002888W WO 2023145938 A1 WO2023145938 A1 WO 2023145938A1
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Prior art keywords
polyester film
film
resin layer
meth
less
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PCT/JP2023/002888
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English (en)
Japanese (ja)
Inventor
良亮 舟津
陽太 菅井
洋平 仲川
祐輝 今井
Original Assignee
三菱ケミカル株式会社
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Priority claimed from JP2022013620A external-priority patent/JP2023111665A/ja
Priority claimed from JP2022199567A external-priority patent/JP2024085182A/ja
Priority claimed from JP2023010000A external-priority patent/JP2024105973A/ja
Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to KR1020247025148A priority Critical patent/KR20240144159A/ko
Priority to CN202380018705.3A priority patent/CN118591462A/zh
Publication of WO2023145938A1 publication Critical patent/WO2023145938A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • 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

Definitions

  • the present invention relates to laminated polyester films.
  • Polyester films represented by polyethylene terephthalate film and polyethylene naphthalate film have excellent mechanical properties, dimensional stability, flatness, heat resistance, chemical resistance, optical properties, etc., and are excellent in cost performance. are used for various purposes.
  • polyester film is used in various applications such as release films for molding green sheets of laminated ceramic capacitors, base materials for releasing interlayer insulating resins, and base materials for dry film resists. It is suitable for use.
  • a sheet-forming polyester film having excellent surface smoothness is required to have no wrinkles and a good roll appearance when wound into a roll.
  • the surface smoothness is increased, the slipperiness is lowered, and the air escape during winding into a roll or unwinding from the roll is deteriorated, so that winding misalignment or blocking occurs, resulting in poor handling.
  • polyester films to become thinner and longer, and roll appearance quality at a higher level is required.
  • Patent Document 1 discloses a slippery composite polyester film in which a continuous coating layer having a fine mesh uneven structure is provided on at least one side of the polyester film for the purpose of improving handling properties.
  • JP 2015-33811 A Japanese Patent Application Laid-Open No. 2000-211082
  • the present invention has been made in view of the above-mentioned circumstances, and the problem to be solved is to provide a laminated polyester film that has excellent handleability when winding the film into a roll by forming a fine uneven structure. That is.
  • the present invention has the following aspects.
  • a laminated polyester film comprising a polyester film and a resin layer formed of a resin composition on at least one side of the polyester film, wherein the laminate satisfies all of the following requirements (1) to (4): polyester film.
  • the resin layer has an uneven structure.
  • the resin composition contains the following compounds (A) and (B). (A) one or more selected from the group consisting of a binder resin and a cross-linking agent; (B) particles; % by mass or more. (4) Kurtosis (Sku) of the surface of the resin layer is less than 3.0.
  • (B) The laminated polyester film according to [3] above, wherein the kurtosis (Sku) of the resin layer surface is less than 3.0.
  • [5] The laminated polyester film according to [3] or [4] above, wherein the content of the particles (B) is 5% by mass or more relative to the total non-volatile components in the resin composition.
  • a laminated polyester film is provided that is excellent in handleability when the film is wound into a roll, etc., due to the formation of a fine uneven structure.
  • the laminated polyester film of the present invention can form a fine uneven structure on the surface of the resin layer. There is an advantage that it exerts the property and wrinkles are less likely to occur.
  • the polyester film of the present invention can be made into a thin film, the polyester film can be made thin and long, and it can contribute to productivity improvement by reducing the frequency of switching product rolls during processing. can.
  • the laminated polyester film of the present invention (hereinafter also referred to as “this laminated polyester film”) comprises a polyester film (hereinafter also referred to as “this polyester film”) and a resin formed on at least one side of the polyester film from a resin composition. layer (hereinafter, also referred to as "this resin layer”).
  • the laminated structure of the present laminated polyester film may be a structure in which a resin layer is formed on one side of the polyester film and the surface of the polyester film is left as it is on the other side. It may be a configuration formed by forming a layer of Moreover, the structure formed by forming a resin layer on both surface sides of a polyester film may be sufficient. Furthermore, the resin layer may be formed directly on the polyester film, or another layer may be provided between the polyester film and the resin layer.
  • a first aspect is a laminated polyester film comprising a polyester film and a resin layer formed of a resin composition on at least one side of the polyester film, and satisfying all the requirements of the following (1) to (4). It is a laminated polyester film that (1) The resin layer has an uneven structure.
  • the resin composition contains the following compounds (A) and (B).
  • the content of the (B) particles is 20 as a proportion of the total non-volatile components in the resin composition. % by mass or more.
  • Kurtosis (Sku) of the surface of the resin layer is less than 3.0.
  • a second aspect is a laminated polyester film comprising a polyester film and a resin layer formed of a resin composition on at least one side of the polyester film, wherein the following (1), (2) and (5) ) is a laminated polyester film that satisfies all the requirements.
  • the resin layer has an uneven structure.
  • the resin composition contains the following compounds (A) and (B). (A) one or more selected from the group consisting of a binder resin and a cross-linking agent; (B) particles; The rate (Rmr(70)) should be 80% or less. Note that the above requirements (1) and (2) are common to the first aspect and the second aspect. Each component will be described in detail below.
  • the present polyester film serves as a base material for the present laminated polyester film.
  • the present polyester film may have a single layer structure or a multilayer structure.
  • the present polyester film may have a two-layer structure, a three-layer structure, or the like, or may have a multilayer structure of four or more layers, provided that the gist of the present invention is not deviated. It is not particularly limited.
  • the present polyester film has a multi-layer structure of two or more layers, it is particularly preferable to have two kinds of three layers or three kinds of three layers.
  • the present polyester film has a multilayer structure, it is also preferable to have a structure in which surface layers are provided on both sides of an intermediate layer.
  • Such a design method includes, for example, a method of designing the present polyester film as a single layer, a 2-kind 3-layer structure, and a 3-kind 3-layer structure so that both surfaces of the polyester film are designed to have excellent smoothness, and the present polyester film is a three-layered structure of three types, one surface of the present polyester film is in a state of excellent smoothness, and the other surface is designed to have different roughness.
  • the present polyester film may be a non-stretched film (sheet) or a stretched film.
  • stretched films uniaxially or biaxially stretched are preferred.
  • a biaxially stretched film is more preferable in terms of excellent balance of mechanical properties and flatness.
  • the polyester which is the raw material of the present polyester film, refers to a polymer compound having continuous ester bonds in the main chain, and may be a homopolyester or a copolymer polyester. Specifically, a polyester obtained by subjecting a dicarboxylic acid component and a diol component to a polycondensation reaction can be mentioned. Moreover, it is preferable to use a polyester containing more than 50 mol % of an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid when the dicarboxylic acid component is taken as 100 mol %.
  • dicarboxylic acid component examples include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyletherdicarboxylic acid and 4,4'-diphenylsulfonedicarboxylic acid, such as adipic acid, suberic acid, sebacic acid, dimer acid, dodecanedioic acid, cyclohexanedicarboxylic acid and their esters Mention may be made of aliphatic dicarboxylic acids such as derivatives.
  • diol component examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1 ,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-hexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2-bis(4-hydroxyethoxy phenyl)propane, isosorbate and spiroglycol, and the like.
  • polyester is a homopolyester, it is preferably obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic diol.
  • aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid
  • preferred aliphatic diols include ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol.
  • Representative homopolyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylate (PEN), etc., with polyethylene terephthalate being preferred.
  • the copolyester is preferably a polycondensation polymer of, for example, a dicarboxylic acid component and an aliphatic diol.
  • a dicarboxylic acid component preferably one or two of isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid and oxycarboxylic acid (e.g., p-oxybenzoic acid, etc.) species or more.
  • the aliphatic diol one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol and the like are preferably used.
  • the copolymer polyester preferably contains terephthalic acid as the dicarboxylic acid component and ethylene glycol as the aliphatic diol.
  • the above polyester is a copolymerized polyester, it is preferably a copolymer containing 30 mol % or less of the third component.
  • the third component is a compound other than the compound that is the main component of the dicarboxylic acid component that constitutes the polyester (that is, the component that has the highest content) and the compound that is the main component of the diol component.
  • copolymerized polyethylene terephthalate are components other than terephthalic acid and ethylene glycol.
  • the copolyester may also contain a structural unit derived from a bifunctional compound other than the dicarboxylic acid component and the aliphatic diol.
  • Structural units derived from bifunctional compounds other than dicarboxylic acid components and aliphatic diols are preferably 20 mol % or less, more preferably 10 mol % or less, relative to the total mol of all structural units constituting the polyester.
  • Bifunctional compounds include various hydroxycarboxylic acids, aromatic diols, and the like.
  • the content of terephthalic acid in all dicarboxylic acid components constituting the present polyester film is preferably 50 mol % or more, more preferably 70 mol % or more, still more preferably 90 mol % or more.
  • the content of ethylene glycol in all diol components constituting the present polyester film is preferably 50 mol % or more, more preferably 70 mol % or more, still more preferably 90 mol % or more.
  • the upper limit of the content of terephthalic acid and ethylene glycol is 100 mol %.
  • the polyester may be a recycled polyester or a biomass-derived polyester.
  • the polycondensation catalyst for polycondensing the above polyester is not particularly limited, and conventionally known compounds can be used, for example, titanium compounds, germanium compounds, antimony compounds, manganese compounds, aluminum compounds, magnesium compounds and calcium compounds. compounds and the like. Among these, at least one of a titanium compound and an antimony compound is preferred, and it is particularly preferred to use a polyester obtained using a titanium compound. Therefore, the present polyester film preferably contains at least one of a titanium compound and an antimony compound, and more preferably contains a titanium compound.
  • the polyester constituting at least one surface layer uses a titanium compound.
  • the content of titanium element derived from the titanium compound in the surface layer is preferably 3 ppm or more and 40 ppm or less, more preferably 4 ppm or more and 35 ppm or less, based on mass.
  • the antimony element content in the surface layer is preferably 0 ppm or more and 100 ppm or less. Within this range, it is possible to reduce the amount of foreign substances originating from the catalyst without lowering the production efficiency. From the viewpoint of productivity and cost, it is also preferable not to use a titanium compound in the polyester constituting the layers other than the surface layer.
  • a polyester film having excellent smoothness can be obtained. If the laminated polyester film is provided with the present resin layer on such a basis, the laminated polyester film can be suitably used for sheet molding and the like.
  • the intrinsic viscosity (IV) of the polyester constituting the present polyester film is preferably 0.50 dL/g or more, more preferably 0.55 dL/g or more, still more preferably 0.60 dL/g or more. Within this range, there is an advantage that the particles are highly dispersed due to an increase in shear stress during kneading. Moreover, the intrinsic viscosity (IV) of the polyester is, for example, 1.00 dL/g or less. In addition, "the intrinsic viscosity (IV) of the polyester constituting the present polyester film” means the intrinsic viscosity (IV) of these mixed polyesters when using two or more polyesters having different intrinsic viscosities (IV). It shall be.
  • the intrinsic viscosity (IV) of the polyester forming the surface layer is preferably within the above range.
  • Particles can also be incorporated into the present polyester film.
  • the polyester film is imparted with slipperiness and prevents the occurrence of scratches in each step, thereby improving handleability.
  • the type of particles to be contained in the present polyester film is not particularly limited as long as it is particles capable of imparting lubricity. Specific examples include silica, calcium carbonate, magnesium carbonate, barium carbonate, and calcium sulfate.
  • crosslinked polymers such as crosslinked silicone resin particles, crosslinked acrylic resin particles, crosslinked styrene-acrylic resin particles, and crosslinked polyester particles, calcium oxalate and organic particles such as ion exchange resins.
  • organic particles, silica, aluminum oxide and the like are preferred.
  • aluminum oxide is preferably contained from the viewpoint of hardening the layer to prevent damage to the film surface and maintaining smoothness.
  • precipitated particles obtained by precipitating and finely dispersing a part of a metal compound such as a catalyst during the polyester production process can also be used.
  • the shape of the particles to be used is also not particularly limited, and any of spherical, massive, rod-like, flattened and the like may be used. Moreover, there are no particular restrictions on its hardness, specific gravity, color, and the like. Two or more types of these series of particles may be used in combination, if necessary.
  • the average particle size of the particles used is usually 5 ⁇ m or less, preferably 0.01 to 3 ⁇ m, more preferably 0.02 to 1 ⁇ m, still more preferably 0.03 to 0.5 ⁇ m.
  • the surface roughness of the film is 5 ⁇ m or less, the surface roughness of the film does not become too rough, and problems do not occur when the resin layer and various surface functional layers other than the resin layer are formed in a post-process.
  • the average particle size is in the range, the haze can be kept low, and it is easy to ensure the transparency of the laminated polyester film as a whole.
  • the average particle size of the particles can be obtained by observing 10 or more particles with a scanning electron microscope (SEM) to measure the diameter of the particles, and calculating the average value. At that time, in the case of non-spherical particles, the average value of the longest diameter and the shortest diameter can be measured as the diameter of each particle.
  • SEM scanning electron microscope
  • the present polyester film contains particles
  • particles may be contained in at least one of the surface layers.
  • the content of the particles depends on the average particle diameter, it is usually 5000 ppm or less, preferably 3000 ppm or less, more preferably 1000 ppm or less, based on the mass of the layer containing the particles.
  • the lower limit of the particle content is not particularly limited, and is, for example, 50 ppm or more, preferably 100 ppm or more.
  • the resin layer to be described later may be provided on a layer containing particles of the polyester film, or may be provided on a layer substantially free of particles.
  • the surface of the polyester film opposite to the surface on which the resin layer is provided may be a layer containing substantially no particles or a layer containing particles.
  • the resin layer having the concave-convex structure described later can improve the windability and the like. Further, by forming a layer containing particles on one or both of the surface on which the resin layer is provided and the surface on the opposite side, windability is further improved.
  • the surface layer on the smooth side may contain particles or may contain substantially no particles, If a very smooth film is desired, it is preferably substantially free of particles.
  • the term "substantially does not contain” means that it does not contain intentionally, and specifically, the content of particles (particle concentration) is less than 50 ppm, more preferably 40 ppm or less, more preferably 40 ppm or less based on mass. means 30 ppm or less.
  • the handling property when winding the film into a roll can be improved.
  • the method of adding particles to the present polyester film is not particularly limited, and conventionally known methods can be employed.
  • it can be added at any stage in the production of the polyester constituting each layer, but it is preferably added after the esterification or transesterification reaction is completed.
  • the film may be produced using a polyester having a low content of the oligomer component as a raw material.
  • a method for producing a polyester having a low content of oligomer components various known methods can be used.
  • the polyester film may have a structure of three or more layers, and the surface layer of the polyester film may be a layer using a polyester raw material with a low content of the oligomer component, thereby suppressing the precipitation amount of the oligomer component.
  • the polyester may also be obtained by subjecting the polyester to esterification or transesterification, followed by melt polycondensation under reduced pressure at a higher reaction temperature.
  • the thickness of the polyester film is not particularly limited as long as it can be formed as a film. More preferably 19 ⁇ m or more, particularly preferably 25 ⁇ m or more, and preferably 200 ⁇ m or less, more preferably 125 ⁇ m or less, still more preferably 80 ⁇ m or less, particularly preferably 50 ⁇ m or less.
  • the invention is not limited to the following production examples.
  • the dried pellets of the polyester raw material described above are extruded as a molten sheet from a die using a melt extruder such as an extruder, and cooled and solidified with a cooling roll such as a rotating cooling drum.
  • a method of obtaining an unstretched sheet is preferred.
  • the resulting unstretched sheet is then biaxially stretched.
  • the unstretched sheet is stretched in one direction by a roll or tenter type stretching machine.
  • the stretching temperature is usually 70 to 120° C., preferably 80 to 110° C.
  • the stretching ratio is usually 2.5 to 7.0 times, preferably 3.0 to 6.0 times.
  • the film is stretched in a direction perpendicular to the stretching direction of the first stage. .0 times.
  • heat treatment is carried out at a temperature of usually 180 to 270° C. under tension or under relaxation of 30% or less to obtain a biaxially stretched film.
  • This heat treatment is also called a heat setting process.
  • the heat treatment may be performed in two or more steps with different temperatures.
  • cooling may be performed in a cooling zone after the heat treatment.
  • the cooling temperature is preferably higher than the glass transition temperature (Tg) of the polyester forming the film, and more specifically, preferably in the range of 100 to 160°C.
  • Tg glass transition temperature
  • This cooling may be performed in two or more steps with different temperatures.
  • a method of stretching in one direction in two or more stages can also be employed. In that case, it is preferable to carry out so that the stretching ratios in the two directions finally fall within the above ranges.
  • a simultaneous biaxial stretching method can also be employed for the production of the present polyester film.
  • the unstretched sheet is usually 70 to 120 ° C., preferably 80 to 110 ° C. while the temperature is controlled at the same time in the machine direction (longitudinal direction) and the width direction (horizontal direction).
  • the draw ratio is preferably 4 to 50 times, more preferably 7 to 35 times, and still more preferably 10 to 25 times in terms of area ratio.
  • heat treatment is performed at a temperature of usually 170 to 250° C. under tension or under relaxation of 30% or less to obtain a stretched and oriented film.
  • Conventionally known stretching methods such as a screw method, a pantograph method and a linear drive method can be used for the simultaneous biaxial stretching apparatus employing the above-described stretching method.
  • This laminated polyester film is provided with a resin layer formed from a resin composition on at least one side of the polyester film.
  • the resin layer may be a cured resin layer.
  • the present resin layer is formed from a resin composition (hereinafter also referred to as "the present composition") and has an uneven structure.
  • the concave-convex structure of the present resin layer has a fine shape.
  • the shape of the concave-convex structure includes a concave-convex shape and/or a mesh shape.
  • the irregular shape is formed by fine protrusions formed by particles described later, thereby forming an uneven structure on the surface.
  • the above-mentioned mesh shape intentionally makes the stretchability of the present composition inferior, and forms an uneven structure on the surface due to cracks in the coating film caused by making the film inferior in stretchability.
  • the mesh shape and the uneven shape may be mixed on the surface of the resin layer.
  • the structure can be confirmed by means of various surface analysis techniques, such as an atomic force microscope (scanning probe microscope).
  • the present composition contains the following compounds (A) and (B) in both the first aspect and the second aspect.
  • (A) one or more selected from the group consisting of a binder resin and a cross-linking agent (B) particles
  • the content of the (B) particles is the total non-volatile components in the present composition As a proportion of the whole, it is 20% by mass or more.
  • the total content of compounds (A) and (B) contained in the present composition is preferably 80% by mass or more as non-volatile components. More preferably 85% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more. If the said total content is the range which requires, it will become easy to obtain the fine uneven structure for which it desires.
  • the upper limit of the total content is not particularly limited as long as it is 100% by mass or less.
  • composition contains one or more selected from (A) a binder resin and a cross-linking agent.
  • binder resin ((binder resin))
  • the binder resin selected as the above (A) is determined by gel permeation chromatography (GPC) measurement according to the "Polymer compound safety evaluation flow scheme” (November 1985, sponsored by the Chemical Substances Council). It is defined as a polymer compound having an average molecular weight (Mn) of 1,000 or more and having film-forming properties.
  • GPC gel permeation chromatography
  • Mn average molecular weight
  • binder resin what is illustrated as a crosslinking agent mentioned later is excluded.
  • Such (A) binder resin is not particularly limited, and includes polyester resin, (meth)acrylic resin, polyurethane resin, polyvinyl resin (polyvinyl alcohol, vinyl chloride vinyl acetate copolymer, etc.), polyalkylene glycol, polyalkylene Conventionally known binder resins such as imine, methylcellulose, hydroxycellulose, and starches can be used. Among them, from the viewpoint of film-forming properties and adhesion to a polyester film, it is preferable to include one or more selected from the group consisting of polyester resins, (meth)acrylic resins and polyurethane resins. In this composition, (A) binder resin may be used individually by 1 type, and may use 2 or more types together.
  • the present composition can form a film (resin layer) in which (B) particles are held and fixed.
  • polyester resin examples include those composed of polyvalent carboxylic acids and polyvalent hydroxy compounds as shown below as main constituents. That is, polyvalent carboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4′-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6- Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid , succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride
  • Polyvalent hydroxy compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neo Pentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylol Propionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate, and the like can be used. One or more of these compounds may be appropriately selected, and a polyester resin may be synthesized by a conventional polycondensation reaction.
  • a product obtained by copolymerizing sulfoisophthalic acids such as 5-sodium sulfoisophthalic acid to introduce a sulfonic acid group into the polyester skeleton and neutralizing to make it hydrophilic is preferable.
  • the amount to be copolymerized is generally 1 to 13 mol %, preferably 3 to 10 mol %, more preferably 5 to 9 mol %, based on the total polycarboxylic acid.
  • a (meth)acrylic resin is a polymer composed of polymerizable monomers including acrylic and methacrylic monomers. These may be homopolymers, copolymers, or copolymers with polymerizable monomers other than acrylic and methacrylic monomers.
  • a (meth)acrylic polymer is a polymer having structural units derived from (meth)acrylic acid or (meth)acrylic acid alkyl esters.
  • the (meth)acrylic polymer may be at least one polymer selected from (meth)acrylic acid and (meth)acrylic acid alkyl ester, or at least one selected from these and monomers other than these , such as styrene or styrene derivatives, monomers containing hydroxyl groups, and the like. Copolymers of these polymers with other polymers (eg, polyester, polyurethane, etc.) are also included. Examples include block copolymers and graft copolymers. That is, the (meth)acrylic resin may be a (meth)acryl-modified polyester resin or a (meth)acryl-modified polyurethane resin.
  • a polymer obtained by polymerizing a polymerizable monomer in a polyester solution or a polyester dispersion is also included.
  • polymers obtained by polymerizing polymerizable monomers in polyurethane solutions and polyurethane dispersions are also included.
  • other polymer solutions or polymers obtained by polymerizing polymerizable monomers in dispersions are also included, and these are also referred to herein as (meth)acrylic-modified polyester resins and , (meth)acrylic-modified polyurethane resin.
  • the polyester and polyurethane used in the (meth)acrylic resin can be appropriately selected and used from those exemplified as the polyester and polyurethane used in the binder resin described later.
  • the (meth)acrylic resin may contain a hydroxy group and an amino group in order to further improve adhesion to the polyester film.
  • the polymerizable monomer is not particularly limited, but particularly representative compounds include various carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid. , and salts thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxy fumarate, monobutyl hydroxy itaconate, etc.
  • carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid. , and salts thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxy fumarate, monobutyl hydroxy itaconate, etc.
  • hydroxyl group-containing Monomers various alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate; (meth)acrylamide , diacetone acrylamide, or (meth)acrylonitrile; hydroxyl group-containing nitrogen-containing monomers such as N-methylol (meth)acrylamide; styrene, ⁇ -methylstyrene, divinylbenzene, vinyltoluene, etc.
  • styrene derivatives various vinyl esters such as vinyl propionate; various silicon-containing polymerizable monomers such as ⁇ -methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; various vinyl halides such as vinylidene chloride; and various conjugated dienes such as butadiene.
  • the polymerizable monomers contain alkyl (meth)acrylic acid esters.
  • the present composition containing a (meth)acrylic resin is preferably diluted with a solvent to form a coating liquid as described later, and the solvent preferably contains water as the main solvent (50% by mass or more). That is, the polymerizable monomer preferably has a hydrophilic group such as a hydroxyl group or a carboxyl group from the viewpoint of facilitating dissolution or dispersion when the coating liquid is an aqueous system.
  • the acrylic resin is also preferably a polymer obtained by polymerizing an alkyl (meth)acrylate and a polymerizable monomer containing a hydrophilic group-containing monomer such as a hydroxyl group-containing monomer and a carboxyl group-containing monomer.
  • the acrylic resin may also be an emulsion polymer obtained by polymerizing a polymerizable monomer in the presence of a surfactant, for example.
  • polyurethane resin is a polymer compound having a urethane bond in its molecule, and is preferably water-dispersible or water-soluble. In the present invention, it may be used alone or in combination of two or more.
  • hydrophilic groups such as hydroxyl groups, carboxyl groups, sulfonic acid groups, sulfonyl groups, phosphoric acid groups, ether groups, and the like into polyurethane resins.
  • hydrophilic groups a carboxyl group or a sulfonic acid group is particularly preferable from the viewpoint of adhesion between the resin layer and the polyester film.
  • introduction of carboxyl groups is preferably carried out using carboxyl group-containing polyhydric alcohols such as dimethylolpropionic acid and dimethylolbutanoic acid.
  • One of the methods for producing polyurethane resin is by reacting a hydroxyl group-containing compound with isocyanate.
  • hydroxyl group-containing compound used as a raw material polyols are preferably used, and examples thereof include polyester polyols, polyether polyols, polycarbonate polyols, polyolefin polyols, and acrylic polyols.
  • polyester polyols are preferable from the viewpoint of excellent adhesion to the polyester film. These compounds may be used alone or in combination.
  • polyester polyols include those obtained from the reaction of polyhydric carboxylic acids or their acid anhydrides with polyhydric alcohols.
  • polycarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, and isophthalic acid.
  • Polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol , 2-methyl-2-propyl-1,3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2 ,5-dimethyl-2,5-hexanediol, 1,9-n
  • Polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and the like.
  • Polycarbonate-based polyols include polycarbonate diols obtained by a dealcoholization reaction from polyhydric alcohols and dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc., such as poly(1,6-hexylene) carbonate, poly(3 -methyl-1,5-pentylene) carbonate and the like. Among the above, polyester polyols are preferred.
  • Polyisocyanate compounds used to obtain polyurethane resins include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate; - Aliphatic diisocyanates having aromatic rings such as tetramethylxylylene diisocyanate; aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate and hexamethylene diisocyanate; Alicyclic diisocyanates such as methane diisocyanate and isopropylidene dicyclohexyl diisocyanate are exemplified. These may be used alone or in combination of multiple types.
  • a chain extender may be used when synthesizing the polyurethane resin, and the chain extender is not particularly limited as long as it has two or more active groups that react with isocyanate groups. Alternatively, a chain extender having two amino groups can be mainly used.
  • chain extenders having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; ester glycols such as neopentyl glycol hydroxypivalate.
  • Glycols such as
  • chain extenders having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine and diphenylmethanediamine; ethylenediamine, propanediamine, hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, etc.
  • aromatic diamines such as tolylenediamine, xylylenediamine and diphenylmethanediamine
  • ethylenediamine propanediamine, hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine
  • Alicyclic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, 1,4-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, etc. mentioned.
  • Polyvinyl alcohol is a compound having a polyvinyl alcohol moiety.
  • conventionally known polyvinyl alcohols including modified compounds obtained by partially acetalizing or butyralizing polyvinyl alcohol can be used.
  • the degree of polymerization of polyvinyl alcohol is not particularly limited, it is usually 100 or more, preferably in the range of 300 to 40,000. When the polymerization degree is 100 or more, it becomes easy to improve the water resistance of the resin layer.
  • the degree of saponification of polyvinyl alcohol is not particularly limited, but is usually 70 mol% or more, preferably in the range of 70 to 99.9 mol%, more preferably 80 to 97 mol%, particularly preferably 86 to 99.9 mol%.
  • a saponified polyvinyl acetate of 95 mol % is used in practice.
  • the cross-linking agent selected as the compound (A) is not particularly limited, and conventionally known cross-linking agents can be used. Examples include melamine compounds, oxazoline compounds, epoxy compounds, carbodiimide compounds, isocyanate compounds, silane coupling compounds and the like. Among them, in the first aspect, it is preferable to contain a melamine compound from the viewpoint of increasing the strength of the coating film and from the viewpoint of improving the adhesion to the polyester film. In the second aspect, from the same point of view, it preferably contains one or more selected from the group consisting of melamine compounds, isocyanate compounds and oxazoline compounds, particularly one or more selected from the group consisting of melamine compounds and isocyanate compounds. preferably included. Moreover, the resin layer can be easily formed into a cured resin layer by using a cross-linking agent.
  • a melamine compound is a compound having a melamine skeleton in the compound, and examples thereof include alkylolated melamine derivatives, compounds obtained by reacting alkylolated melamine derivatives with alcohol to partially or completely etherify them, and mixtures thereof. can be used.
  • alkylolation include methylolation, ethylolation, isopropylolation, n-butyrolation, and isobutyrolation. Among these, methylolation is preferable from the viewpoint of reactivity.
  • the alcohol used for etherification methanol, ethanol, isopropanol, n-butanol, isobutanol and the like are preferably used, and among these, methanol is more preferable.
  • the melamine compound may be either a monomer or a polymer of dimers or higher, or a mixture thereof. Further, melamine may be partially co-condensed with urea or the like, and a catalyst may be further used in the present composition in order to increase the reactivity of the melamine compound.
  • oxazoline compound is a compound having an oxazoline group in its molecule, and a polymer containing an oxazoline group is particularly preferred, and can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer.
  • Addition polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like can be mentioned, and one or a mixture of two or more thereof can be used.
  • 2-isopropenyl-2-oxazoline is suitable because it is easily available industrially.
  • Other monomers are not limited as long as they are copolymerizable with addition-polymerizable oxazoline group-containing monomers.
  • n-butyl group isobutyl group, t-butyl group, 2-ethylhexyl group and cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, Unsaturated carboxylic acids such as styrenesulfonic acid and salts thereof (sodium salts, potassium salts, ammonium salts, tertiary amine salts, etc.); Unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth)acrylamide, N-alkyl (Meth)acrylamide and N,N-dialkyl(meth)acrylamide (as alkyl groups, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl vinyl esters such
  • the oxazoline compound may have a polyalkylene oxide chain such as a polyethylene oxide chain, and for example, a (meth)acrylate having a polyalkylene oxide chain may be used as another monomer.
  • the oxazoline group content of the oxazoline compound is preferably in the range of 0.5 to 10 mmol/g, more preferably 1 to 9 mmol/g, and still more preferably 3 to 8 mmol/g. is.
  • Epoxy compounds are compounds having an epoxy group in the molecule, and include condensates with hydroxyl groups and amino groups such as epichlorohydrin, ethylene glycol, polyethylene glycol, glycerin, polyglycerin and bisphenol A, and polyepoxy compounds. , diepoxy compounds, monoepoxy compounds and glycidylamine compounds.
  • polyepoxy compounds include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris(2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether and trimethylolpropane poly glycidyl ether and the like.
  • diepoxy compounds include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Ether and polytetramethylene glycol diglycidyl ether and the like.
  • Examples of monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether and phenyl glycidyl ether, and examples of glycidylamine compounds include N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N,N-diglycidylamino)cyclohexane and the like.
  • a polyether-based epoxy compound is preferred.
  • the amount of epoxy groups a polyepoxy compound having a polyfunctionality of 3 or more is preferable to a bifunctional one.
  • a carbodiimide compound is a compound having a carbodiimide structure, and is a compound having one or more carbodiimide structures in the molecule. More preferred are polycarbodiimide compounds having one or more carbodiimide structures.
  • a carbodiimide compound can be synthesized by a conventionally known technique, and generally a condensation reaction of a diisocyanate compound is used.
  • the diisocyanate compound is not particularly limited, and both aromatic and aliphatic compounds can be used. Specifically, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate and dicyclohexylmethane 4,4'-diisocyanate.
  • a surfactant may be added, polyalkylene oxide, quaternary ammonium salt of dialkylamino alcohol, and Hydrophilic monomers such as hydroxyalkylsulfonates may be added and used.
  • the isocyanate compound is a compound having an isocyanate derivative structure represented by an isocyanate or a blocked isocyanate having a structure in which the isocyanate group of the isocyanate compound as a precursor is protected with a blocking agent.
  • isocyanates include aliphatic isocyanate compounds, alicyclic isocyanate compounds, and aromatic isocyanate compounds. These isocyanate compounds are more preferably compounds having a plurality of isocyanate groups, i.e., polyisocyanate compounds, from the viewpoint of being able to react to a higher degree and improve the durability of the resin layer.
  • a blocked isocyanate when using a water-based coating liquid, it is more preferable to use a blocked isocyanate.
  • aliphatic polyisocyanate compounds include those derived from aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, and lysine diisocyanate.
  • polyisocyanate compound, lysine triisocyanate, 4-isocyanatomethyl-1,8-octamethylene diisocyanate, bis(2-isocyanatoethyl) 2-isocyanatoglutarate, or compounds derived from these isocyanate compounds, etc. can be mentioned.
  • hexamethylene diisocyanate is preferred because of its industrial availability.
  • alicyclic polyisocyanate compounds include isophorone diisocyanate, (1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, hydrogenated xylylene diisocyanate, or these isocyanates.
  • isophorone diisocyanate is preferable from the viewpoint of weather resistance and industrial availability.
  • aromatic polyisocyanate compounds examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, or derivatives derived from these isocyanate compounds. compound etc. can be mentioned.
  • polyisocyanate compounds aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds are preferable because of their excellent weather resistance. Furthermore, among aliphatic polyisocyanate compounds, aliphatic polyisocyanate compounds derived from aliphatic diisocyanates are preferred. Among these, hexamethylene diisocyanate is particularly preferred. Moreover, these isocyanate compounds may be used alone, or two or more of them may be used in combination.
  • a blocked polyisocyanate compound can be synthesized by reacting the isocyanate group of the polyisocyanate compound with a blocking agent.
  • blocking agents include active methylene-based, oxime-based, pyrazole-based, alcohol-based, alkylphenol-based, phenol-based, mercaptan-based, acid amide-based, acid imide-based, imidazole-based, urea-based, amine-based, imine-based, heavy sulfite blocking agents and the like.
  • active methylene-based blocking agents are preferable from the viewpoint of improving the adhesion between the resin layer and the polyester film. Two or more of these blocking agents may be used in combination.
  • Active methylene-based blocking agents include, for example, isobutanoyl acetate, n-propanoyl acetate, n-butanoyl acetate, n-pentanoyl acetate, n-hexanoyl acetate, 2-ethylheptanoyl acetate, malonic acid ester, Acetoacetate, acetylacetone and the like can be mentioned.
  • isobutanoyl acetate, n-propanoyl acetate, n-butanoyl acetate, n-pentanoyl acetate, n-hexanoyl acetate, 2- Ethylheptanoyl acetate is preferred, more preferably isobutanoyl acetate, n-propanoyl acetate, n-pentanoyl acetate, and still more preferably isobutanoyl acetate.
  • isobutanoyl acetate esters include, for example, methyl isobutanoyl acetate, ethyl isobutanoyl acetate, n-propyl isobutanoyl acetate, isopropyl isobutanoyl acetate, n-butyl isobutanoyl acetate, isobutyl isobutanoyl acetate, t-butyl isobutanoyl acetate, and isobutanoyl acetic acid.
  • Examples include n-pentyl, n-hexyl isobutanoylacetate, 2-ethylhexyl isobutanoylacetate, phenyl isobutanoylacetate, and benzyl isobutanoylacetate. Among them, methyl isobutanoyl acetate and ethyl isobutanoyl acetate are preferable.
  • n-propanoyl acetate examples include methyl n-propanoyl acetate, ethyl n-propanoyl acetate, isopropyl n-propanoyl acetate, n-butyl n-propanoyl acetate, and t-butyl n-propanoyl acetate. Among them, methyl n-propanoylacetate and ethyl n-propanoylacetate are preferred.
  • n-pentanoyl acetic acid esters examples include methyl n-pentanoyl acetate, ethyl n-pentanoyl acetate, isopropyl n-pentanoyl acetate, n-butyl n-pentanoyl acetate, and t-butyl n-pentanoyl acetate. Among them, methyl n-pentanoylacetate and ethyl n-pentanoylacetate are preferred.
  • the active methylene-based blocking agents shown above can be used alone, or two or more of them can be used in combination.
  • Dimethyl malonate and diethyl malonate are preferable as the active methylene-based blocking agent to be used in combination, since they have excellent low-temperature curability and excellent durability of the formed resin layer.
  • Examples of oxime-based blocking agents include formaldoxime, acetaldoxime, acetone oxime, methylethylketoxime, cyclohexanone oxime, and the like.
  • Examples of pyrazole blocking agents include pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole and the like.
  • Examples of alcohol-based blocking agents include methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol. be done.
  • alkylphenol-based blocking agents include monoalkylphenols such as n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, t-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol and n-nonylphenol. , di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-t-butylphenol, di-sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di-n- Examples include dialkylphenols such as nonylphenol.
  • phenol-based blocking agents include phenol, cresol, ethylphenol, styrenated phenol, and hydroxybenzoic acid esters.
  • Mercaptan-based blocking agents include, for example, butyl mercaptan and dodecyl mercaptan.
  • Acid amide blocking agents include, for example, acetanilide, acetic amide, ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam and the like.
  • acid imide-based blocking agents include succinimide and maleic imide.
  • imidazole-based blocking agents include imidazole and 2-methylimidazole.
  • Urea-based blocking agents include, for example, urea, thiourea, ethylene urea, and the like.
  • Amine-based blocking agents include, for example, diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, isopropylethylamine and the like.
  • imine-based blocking agents include ethyleneimine and polyethyleneimine.
  • the blocked isocyanate compound used in the present invention preferably contains a hydrophilic site in order to improve compatibility with a water-based paint.
  • a method of reacting an isocyanate group with a hydrophilic compound having an active hydrogen can be mentioned.
  • hydrophilic compounds having active hydrogen used in the blocked isocyanate compound used in the present invention include polyethylene glycol compounds, carboxylic acid group-containing compounds, sulfonic acid group-containing compounds, and amine-containing compounds. These hydrophilic compounds may be used alone or in combination of two or more.
  • polyethylene glycol compounds include monoalkoxypolyethylene glycol, polyethylene glycol, polyoxypropylene polyoxyethylene copolymer diol, polyoxypropylene polyoxyethylene block polymer diol and the like. Monoalkoxy polyethylene glycols such as ethoxy polyethylene glycol are preferred.
  • carboxylic acid group-containing compounds examples include monohydroxycarboxylic acids, dihydroxycarboxylic acids, derivatives thereof, and the like. Among the carboxylic acid group-containing compounds, monohydroxycarboxylic acids or dihydroxycarboxylic acids are preferred, and monohydroxycarboxylic acids are more preferred.
  • carboxylic acid group-containing compounds include hydroxypivalic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and polycaprolactone diols and polyether polyols using these as initiators. and salts thereof.
  • Sulfonic acid group-containing compounds include aminoethylsulfonic acid, ethylenediamino-propyl- ⁇ -ethylsulfonic acid, 1,3-propylenediamine- ⁇ -ethylsulfonic acid, N,N-bis(2-hydroxyethyl)-2 - aminoethanesulfonic acid, and salts thereof.
  • Amine-containing compounds include hydroxyl-containing amino compounds. Specific examples include dimethylethanolamine and diethylethanolamine.
  • silane coupling compound is an organosilicon compound having an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule.
  • a silane coupling compound is an organosilicon compound having an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule.
  • Vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane;
  • Styryl group-containing compounds such as p-styryltrimethoxysilane and p-styryltriethoxysilane; - (meth)
  • ( meth) acrylic group-containing compounds 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3 -aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N- Amino group-containing compounds such as (1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane; tris(trimethoxysilylpropyl)isocyanate Nurate,
  • the content of compound (A) in the composition is preferably 10 to 80% by mass, more preferably 25 to 70% by mass, as a proportion of the total nonvolatile components in the composition. More preferably, it is in the range of 40 to 60% by mass.
  • the content is preferably 10 to 80% by mass, more preferably 25 to 70% by mass, as a proportion of the total nonvolatile components in the composition. More preferably, it is in the range of 40 to 60% by mass.
  • the content of compound (A) in the composition is preferably 10 to 95% by mass, more preferably 25 to 90% by mass, as a proportion of the total nonvolatile components in the composition. %, more preferably 30 to 80 mass %, particularly preferably 40 to 60 mass %.
  • the content is preferably 10 to 95% by mass, more preferably 25 to 90% by mass, as a proportion of the total nonvolatile components in the composition. %, more preferably 30 to 80 mass %, particularly preferably 40 to 60 mass %.
  • the compound (A) contains one or more selected from a binder resin and a cross-linking agent, and from the viewpoint of obtaining better film-forming properties, it is preferable to contain a binder resin. Furthermore, it is more preferable to contain a binder resin and a cross-linking agent from the viewpoint of further improving the coating film strength and adhesion to the polyester film.
  • composition contains (B) particles.
  • the stretching aptitude of the coating film is lowered, and an uneven structure is likely to be formed.
  • by increasing the hardness of the formed concave-convex structure it is possible to effectively improve the air release property.
  • the particles (B) include inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, zirconium oxide, aluminum oxide and titanium oxide, and crosslinked silicone resin particles. , crosslinked acrylic resin particles, crosslinked styrene-acrylic resin particles, crosslinked polymers such as crosslinked polyester particles, and organic particles such as calcium oxalate and ion exchange resins. Among these, zirconium oxide, titanium oxide and silica are preferred.
  • the particles (B) may be used singly or in combination of two or more.
  • the shape of the (B) particles to be used includes spherical, massive, rod-like, flattened, chain-like, and the like. Among these, a spherical shape is preferable from the viewpoint of facilitating uniform distribution in the compound (A).
  • the average particle diameter of the particles (B) is preferably 1 to 100 nm, more preferably 4 to 60 nm, still more preferably 8 to 40 nm. When the average particle diameter is within such a range, it is possible to suppress the generation of coarse projections due to particle aggregation and contamination of the process due to falling off of particles, making it easier to obtain a desired fine uneven structure.
  • the method of measuring the average particle diameter of the fine particles is a method of calculating from the specific surface area and the density of the particles measured by a specific surface area measuring device, or by observing with a transmission electron microscope (TEM) or a scanning electron microscope (SEM). There are a method of calculating the diameter of particles and a method of determining the diameter from measurement by a dynamic light scattering method.
  • the content of compound (B) in the present composition is 20% by mass or more as a proportion of all non-volatile components in the present composition.
  • the content is preferably 90 mass % or less, more preferably 30 to 75 mass %, still more preferably 40 to 60 mass %.
  • the content of compound (B) in the composition is preferably 5 to 90% by mass, more preferably 10 to 75% by mass as a proportion of the total nonvolatile components in the composition. %, more preferably 20 to 70 mass %, particularly preferably 40 to 60 mass %.
  • the content by setting the content to 90% by mass or less, it is possible to include necessary amounts of other components, and it is possible to form an uneven film and obtain adhesion to a polyester film. Also, by setting the content of the compound (B) to a certain value or less, it becomes easier to prevent the coating film from coming off.
  • cross-linking catalysts In addition to the components described above, cross-linking catalysts, antifoaming agents, coatability improvers, surfactants, thickeners, organic lubricants, ultraviolet absorbers, and antioxidants are used within the scope of the present invention. , foaming agents, dyes, pigments, and other additives may be added as appropriate.
  • the composition may be diluted with a solvent to form a coating liquid. That is, the present composition may be applied as a liquid coating liquid, for example, to the present polyester film, dried and cured as necessary to form a resin layer.
  • Each component (compounds (A) and (B), other components, etc.) constituting the present composition may be dissolved in a solvent or dispersed in a solvent.
  • the concentration of all non-volatile components in the present composition in the coating liquid is preferably 0.1 to 50% by mass. If it is 0.1% by mass or more, a resin layer having a desired thickness can be efficiently formed. On the other hand, if it is 50% by mass or less, the appearance of the resin layer can be improved by suppressing the viscosity during coating, and the stability in the coating liquid can be enhanced.
  • the solvent is not particularly limited, and both water and organic solvents can be used. From the viewpoint of environmental protection, it is preferable to use water as the main solvent (50% by mass or more of the total solvent) to form an aqueous coating solution.
  • the water content is preferably 60% by mass or more, more preferably 70% by mass or more.
  • the aqueous coating liquid may contain a small amount of organic solvent.
  • a specific amount of the organic solvent is preferably equal to or less than the amount of water on a mass basis, for example, 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less in the solvent.
  • Organic solvents used in combination with water include alcohols such as ethanol, isopropanol, ethylene glycol and glycerin; ethers such as ethyl cellosolve, t-butyl cellosolve, propylene glycol monomethyl ether and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; ethyl acetate. and amines such as dimethylethanolamine. These can be used singly or in combination. By appropriately selecting and including these organic solvents in the aqueous coating liquid as necessary, the stability and coatability of the coating liquid can be improved in some cases.
  • alcohols such as ethanol, isopropanol, ethylene glycol and glycerin
  • ethers such as ethyl cellosolve, t-butyl cellosolve, propylene glycol monomethyl ether and tetrahydrofuran
  • ketones such as acetone and methyl ethyl
  • the organic solvent includes aromatic hydrocarbons such as toluene; aliphatic hydrocarbons such as hexane, heptane and isooctane; esters such as ethyl acetate and butyl acetate. ketones such as ethyl methyl ketone and isobutyl methyl ketone; alcohols such as ethanol and 2-propanol; ethers such as diisopropyl ether and dibutyl ether. These may be used singly or in combination of two or more in consideration of solubility, coatability, boiling point, and the like.
  • each component compound (compounds (A) and (B), other components, etc.) constituting the present composition, compounds after reaction, or mixtures thereof are present.
  • the analysis of each component in the resin layer can be performed by, for example, TOF-SIMS, ESCA, fluorescent X-rays, and the like.
  • the present resin layer may be formed by applying the present composition to a polyester film and, if necessary, performing treatments such as drying, curing, heat treatment, etc. on the applied present composition, and at least heat treatment. is preferred.
  • the method of applying the resin composition is not particularly limited, and conventionally known coating methods such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating and curtain coating can be used.
  • the resin layer there are in-line coating and off-line coating.
  • the method of heat-treating the applied resin composition is not particularly limited. It is preferable to perform the heat treatment for 40 seconds as a guideline. On the other hand, when the resin layer is provided by in-line coating, it is generally preferable to perform heat treatment at 70 to 280° C. for 3 to 200 seconds.
  • the heat treatment may be performed in two or more stages with different temperatures within the above temperature range. At least part of the heat treatment may be performed by heating during stretching. Drying and curing are preferably performed together by heating in the heat treatment.
  • the resin layer is preferably formed by in-line coating, which treats the film surface during the process of forming the polyester film.
  • In-line coating is a method of coating within the polyester film manufacturing process. Specifically, it is a method of coating at any stage from melt extrusion of polyester to stretching, heat setting and winding. . Usually, it is coated on an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, or a film after heat setting and before winding up.
  • a method of coating a uniaxially stretched film stretched in the longitudinal direction (machine direction) and then stretching it in the transverse direction is excellent.
  • film formation and resin layer formation can be performed simultaneously, there is an advantage in terms of manufacturing cost, and since stretching is performed after coating, the thickness of the resin layer can be changed by the stretching ratio. It is possible to perform thin film coating more easily compared to off-line coating films.
  • the resin layer can be stretched together with the polyester film, thereby firmly adhering the resin layer to the polyester film.
  • the film in the production of biaxially stretched polyester film, the film can be restrained in the vertical and horizontal directions by stretching while holding the ends of the film with a clip or the like. High temperature can be applied while maintaining flatness without entering etc. Therefore, since the heat treatment applied after coating can be performed at a high temperature that cannot be achieved by other methods, the film-forming property of the resin layer is improved, and the resin layer and the polyester film can be adhered more firmly. Furthermore, a strong resin layer can be formed, and performances such as resistance to migration to various functional layers that can be formed on the resin layer and resistance to moist heat can be improved.
  • such a method is optimal as a manufacturing method for forming cracks in the coating film.
  • the content of each of the compounds (A) and (B) in the present composition is adjusted to make the stretchability of the present composition inferior.
  • by adopting a production method in which the present composition is coated and then stretched it is possible to form an uneven structure on the surface of the resin layer due to cracks in the coating film caused by stretching a film with poor stretchability. .
  • Those skilled in the art have conventionally considered coating film cracking to be one form of coating defects, and have sought to form a uniform coating film that minimizes the occurrence of coating film cracking.
  • One of the causes of coating film cracking is insufficient stretchability of the resin composition, so the resin composition is designed to have sufficient stretchability.
  • the present inventors have come to utilize such cracks in the coating film as one of means for forming a fine uneven structure on the surface of the resin layer.
  • polyester film constituting the present laminated polyester film may be previously subjected to a surface treatment such as corona treatment or plasma treatment.
  • the coating amount of the nonvolatile component of the resin layer is preferably 0.005 to 0.95 g/m 2 , more preferably 0.02 to 0.5 g/m 2 , still more preferably 0.04 to 0.3 g/m 2 . 2 , particularly preferably 0.06 to 0.2 g/m 2 . If the coating amount is within such a range, a fine uneven structure can be formed due to coating film cracks and the like.
  • the coating amount can be obtained by calculation from the non-volatile component concentration of the coating liquid, the coating amount before drying derived from the consumption of the coating liquid, the transverse stretching ratio, and the like.
  • the coating amount of the non-volatile component is the coating amount in the present laminated polyester film, for example, when drying and stretching are performed, it is the coating amount after drying and stretching.
  • Kurtosis (Sku) of the surface of the resin layer of the present laminated polyester film in the first embodiment is less than 3.0.
  • Kurtosis (Sku) is a parameter related to the tip shape of unevenness
  • the height distribution is sharp, that is, the shape has many sharp unevenness on the surface. If it is 3, it can be evaluated that the height distribution of surface unevenness is collapsed, that is, the surface is relatively flat.
  • the kurtosis is preferably 2.9 or less, more preferably 2.8 or less, still more preferably 2.6 or less, particularly preferably 2.4 or less, and particularly preferably 2.2 or less.
  • the lower limit is not particularly limited and is 0.1.
  • Kurtosis is one of the surface roughness parameters (ISO 25178), can evaluate the sharpness (kurtosis) of a histogram of height distribution, and is obtained from the following equation (1).
  • A the defined area (the entire image)
  • Z (x, y) the height of the image point (x, y) from the plane of 0 Height
  • Sq root mean square height (equivalent to standard deviation of height distribution), is expressed as follows.
  • the kurtosis (Sku) of the resin layer surface in the second aspect is preferably less than 3.0. If the kurtosis (Sku) is less than 3.0, since the protrusions have a flat surface, the apexes of the protrusions are less likely to be crushed when the films are stacked, and the air release property can be efficiently maintained. From such a viewpoint, the kurtosis is more preferably 2.9 or less, more preferably 2.8 or less, particularly preferably 2.6 or less, particularly preferably 2.4 or less, and most preferably 2.2 or less. is. The lower limit is not particularly limited and is 0.1.
  • the arithmetic mean roughness (Ra) of the resin layer surface of the laminated polyester film is preferably 10 nm or more, more preferably 20 nm or more, even more preferably 50 nm or more, and particularly preferably 80 nm or more.
  • the upper limit is not particularly limited, it is preferably 600 nm, more preferably 400 nm, and still more preferably 200 nm.
  • the arithmetic mean roughness (Ra) is 10 nm or more, it can be said that the present resin layer has a fine uneven structure, and the handleability of the present laminated polyester film is improved.
  • the arithmetic mean roughness (Ra) is 600 nm or less, the concave-convex structure of the present resin layer can be said to have a sufficiently fine shape.
  • the ten-point average roughness (Rzjis) of the surface of the resin layer is preferably 60 nm or more, more preferably 150 nm or more, and still more preferably 250 nm or more.
  • the upper limit is not particularly limited, it is preferably 800 nm, more preferably 600 nm, and still more preferably 450 nm.
  • the ten-point average roughness (Rzjis) is 60 nm or more, it can be said that the present resin layer has a sufficient uneven structure.
  • the ten-point average roughness (Rzjis) is 800 nm or less, it can be said that the concave-convex structure of the present resin layer has a sufficiently fine shape.
  • the ten-point average roughness (Rzjis) is one of the line roughness parameters (JIS B 0601). It represents the sum of the average of the deepest valley depths (Zv) to the fifth, and is obtained from the following equation (3).
  • the load length ratio (Rmr(70)) of the roughness curve at a cutting level of 70% on the surface of the resin layer is preferably 82% or less, more preferably 65% or less, and still more preferably 60%. % or less.
  • the lower limit is not particularly limited, and is about 1%, preferably 10% or more, more preferably 15% or more.
  • the inventor considered that the load length ratio (Rmr(70)) is effective as an index representing the uneven distribution of the uneven structure. For example, when the concave distribution is large, the numerical value of the load length ratio (Rmr(70)) is small, and when the convex distribution is large, the numerical value of the load length ratio (Rmr(70)) is large. If the load length ratio (Rmr(70)) is 82% or less, an appropriate fine uneven structure is formed, and when the film is wound into a roll, the gap between the films becomes large, and air It is possible to improve the easiness of coming off, and improve winding characteristics and the like.
  • the load length ratio (Rmr(70)) of the roughness curve at a cutting level of 70% on the resin layer surface of the present laminated polyester film in the second embodiment is 80% or less. If the load length ratio (Rmr(70)) is 80% or less, an appropriate fine uneven structure is formed, and when the film is wound into a roll, the gap formed between the films becomes large, and air It is possible to improve the easiness of coming off, and improve winding characteristics and the like. From this point of view, the load length ratio (Rmr(70)) is preferably 70% or less, more preferably 65% or less, and even more preferably 60% or less. The lower limit is not particularly limited, and is about 1%, preferably 10% or more, more preferably 15% or more.
  • the load length ratio (Rmr (c)) is one of the line roughness parameters (JIS B 0601), and the load length ML (c) of the contour element at the cutting level c (height % or ⁇ m) It represents the ratio to the evaluation length Ln and is obtained from the following equation (4).
  • the root-mean-square gradient (Sdq) of the resin layer surface of the laminated polyester film is preferably 0.1 or more, more preferably 0.25 or more, and still more preferably 0.45 or more.
  • the root-mean-square gradient (Sdq) is preferably 3 or less, more preferably 1.0 or less.
  • the root-mean-square gradient (Sdq) is 0.1 or more, the difference between peaks and valleys of the uneven structure is clear, and air release can be enhanced. Further, when the root mean square gradient (Sdq) is 3 or less, coarse projections can be suppressed.
  • the root-mean-square gradient (Sdq) is one of surface roughness parameters (ISO 25178) and is obtained from the following formula (5).
  • the root-mean-square gradient (Sdq) represents the average magnitude of the local gradient (inclination) of the uneven shape of the surface, and the larger the value, the steeper the surface.
  • the developed interface area ratio (Sdr) of the resin layer surface is preferably 0.5% or more, more preferably 3% or more, and still more preferably 9% or more.
  • the developed interface area ratio (Sdr) is preferably 60% or less, more preferably 50% or less. If the developed interface area ratio (Sdr) is 0.5% or more, the winding characteristics can be improved by forming a fine uneven structure. Further, when the developed interface area ratio (Sdr) is 60% or less, undulations are moderately suppressed, and coarse projections can be prevented.
  • the developed interface area ratio (Sdr) is one of the surface roughness parameters (ISO 25178) and is obtained from the following expression (6) expressed in %.
  • the developed interface area ratio (Sdr) represents how much the developed area (surface area) of the defined region increases with respect to the area of the defined region, that is, the increase rate of the surface area. value increases.
  • the kurtosis (Sku), arithmetic mean roughness (Ra), ten-point mean roughness (Rzjis), load length ratio (Rmr (70)), root mean square gradient (Sdq) and developed interface area ratio (Sdr) are , the composition and content in the present composition, the method of forming the resin layer and various conditions in the forming process.
  • kurtosis Sku
  • arithmetic mean roughness Ra
  • ten point mean roughness Rzjis
  • load length ratio Rmr (70)
  • root mean square gradient Sdq
  • developed interface area of resin layer surface The modulus (Sdr) is measured by the method described in Examples using an atomic force microscope (scanning probe microscope). Measurement by an atomic force microscope (scanning probe microscope) can capture a finer structure of the surface, and it is possible to obtain numerical values that strongly reflect the effect of the resin layer.
  • the surface arithmetic mean roughness (Sa) of the resin layer surface of the laminated polyester film is preferably in the range of 1 to 70 nm, more preferably 2 to 50 nm, still more preferably 3 to 30 nm. If the arithmetic mean roughness (Sa) is in the range, extremely large unevenness can be reduced while having fine unevenness. Therefore, for example, it is possible to ensure the handleability of the present laminated polyester film, suppress wrinkles when winding it into a roll, and use it as a support for a ceramic green sheet in the manufacturing process of a laminated ceramic capacitor. When a mold release layer or a ceramic layer is provided on the film surface opposite to the provided surface, it is possible to prevent projection transfer to the ceramic layer due to projections on the surface of the resin layer and breakage of the ceramic layer.
  • Average surface roughness (Sa) is one of the surface roughness parameters (ISO 25178), and is a three-dimensional expansion of two-dimensional Ra (arithmetic mean roughness of lines). It is obtained by dividing the volume of the portion surrounded by the plane by the measurement area, and is obtained from the following formula (7).
  • A the defined area (the entire image)
  • Z (x, y) the height of the image point (x, y) from the plane of 0
  • the height is expressed as follows.
  • the surface maximum peak height (Sp) of the resin layer surface is preferably 800 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less.
  • the maximum peak height (Sp) is preferably 10 nm or more, more preferably 20 nm or more. If the maximum peak height (Sp) is 800 nm or less, protrusions can be reduced. Therefore, for example, when the present laminated polyester film is used as a support for a ceramic green sheet in the manufacturing process of a laminated ceramic capacitor, and a release layer or a ceramic layer is provided on the film surface opposite to the surface provided with the present resin layer.
  • the maximum peak height (Sp) is 10 nm or more, it is possible to ensure the handleability of the present laminated polyester film, and it is possible to suppress wrinkles when wound into a roll.
  • the maximum peak height (Sp) is one of the surface roughness parameters (ISO 25178), represents the maximum height from the average surface of the surface, and is represented by the following formula (8).
  • the surface arithmetic mean roughness (Sa) of the surface opposite to the resin layer surface of the laminated polyester film is preferably 15 nm or less, more preferably 9 nm or less, and even more preferably 5 nm or less.
  • the arithmetic mean roughness (Sa) is preferably 0.3 nm or more from the viewpoint of film handleability.
  • the surface maximum peak height (Sp) on the surface opposite to the resin layer surface is preferably 800 nm or less, more preferably 500 nm or less, and even more preferably 100 nm or less.
  • the lower limit of the maximum peak height (Sp) is not particularly limited, it is preferably 5 nm or more, more preferably 10 nm or more, and still more preferably 20 nm or more from the viewpoint of film handleability.
  • this laminated polyester film As a release film for molding the green sheets of laminated ceramic capacitors, as a base material for releasing interlayer insulating resin, as a base material for dry film resist, etc., processing using the smoothness of the film is required. done.
  • at least one side of the laminated polyester film is preferably smooth, and the surface opposite to the surface on which the resin layer is formed. In this case, the transfer of irregularities and protrusions on the film surface is small, and good processing is possible.
  • the present laminated polyester film is used as a support for a ceramic green sheet in the manufacturing process of a laminated ceramic capacitor, and a release layer or a ceramic layer is provided on the film surface opposite to the surface provided with the present resin layer, If the arithmetic mean roughness (Sa) and the maximum peak height (Sp) are within the above ranges, it will be an extremely smooth film, and it is also useful for thinning ceramic green sheets when miniaturizing and increasing the capacity of laminated ceramic capacitors. Correspondence becomes possible.
  • the arithmetic mean roughness (Sa) and maximum peak height (Sp) of the resin layer surface can be adjusted by the composition and content in the present composition.
  • the arithmetic mean roughness (Sa) and the maximum peak height (Sp) of the surface opposite to the resin layer surface can be adjusted by the type, average particle diameter and content of the particles contained in the surface layer of the present polyester film. can.
  • the arithmetic average roughness (Sa) and the maximum peak height (Sp) of the resin layer surface and the surface opposite to the resin layer surface can be measured by a non-contact surface roughness meter using light interference, and specific can be measured by the method described in Examples. If measured by this method, a numerical value reflecting a wider area of the present laminated polyester film can be obtained.
  • the coating film retention rate of the present resin layer is preferably 60% or more, more preferably 70% or more, and still more preferably 90% or more.
  • the upper limit of the coating film retention rate is not particularly limited, and is 100% or less. If the coating film retention is within such a range, it is possible to suppress contamination in the process due to the dropped coating film.
  • the said coating-film retention rate can be measured by the method as described in an Example.
  • the coefficient of static friction between the resin layer surface and the opposite surface of the laminated polyester film is preferably 1.0 or less, more preferably 0.7 or less, still more preferably 0.6 or less.
  • the friction coefficient between the resin layer surface and the opposite surface is important because the resin layer surface and the opposite surface are in contact with each other. Therefore, if the coefficient of static friction is within the range, the rugged structure of the present resin layer improves the slipperiness and the handleability of the present laminated polyester film.
  • the static friction coefficient can be measured by the method described in Examples.
  • the air leakage index can be used as an index for evaluating the handling properties such as the windability of this laminated polyester film. If the air leakage index is low, air trapped in the laminated polyester film when it is rolled up can be easily released, and defects in the appearance of the roll such as wrinkles and uneven edges can be prevented. In addition, when the air leakage index is high, the trapped air escapes after a sufficient period of time, especially during transportation, causing problems such as displacement of the film in the winding core direction and scratches due to displacement.
  • the air leakage index may be, for example, 130,000 seconds or less. If it is 130,000 seconds or less, it can be said that it has a certain handleability.
  • the surface opposite to the surface on which the resin layer is formed that is, when used for a release film for molding green sheets of laminated ceramic capacitors, a base material for releasing interlayer insulating resin, a base material for dry film resist, etc.
  • the smooth surface of the film used for processing preferably has an arithmetic mean roughness (Sa) of 9 nm or less, or a maximum peak height (Sp) of 500 nm or less.
  • the air leakage index is preferably 130,000 seconds or less, more preferably 50,000 seconds or less, and even more preferably 30,000 seconds or less.
  • the smooth surface of the film is extremely smooth, more precise processing can be performed by utilizing the smoothness of the film, and the uneven structure of the resin layer improves the air leakage index within the above range.
  • the air leakage index can be measured by the method described in Examples.
  • the present resin layer in the first embodiment is characterized in that it is composed of a resin composition containing a certain amount of a specific compound, and has a specific roughness structure, so that it can develop a fine uneven structure. In addition, it is also characterized by focusing on the degree of sharpness (kurtosis), which can evaluate the tip shape of unevenness as an index representing the roughness structure.
  • the present resin layer in the second aspect is characterized in that it is composed of a resin composition containing a specific compound and has a specific roughness structure, thereby being able to develop a fine uneven structure.
  • the laminated polyester film can be used for various purposes for the purpose of improving handling properties, and the uses are not particularly limited. Among them, as described above, since it has a fine uneven structure, if it is used for sheet molding, it exhibits good winding properties even when winding a highly smooth film into a roll, and wrinkles are less likely to occur. It can be suitably used as a polyester film for sheet molding.
  • a polyester film for sheet molding for example, for multi-layer ceramic capacitor (MLCC) green sheet molding, for interlayer insulating resin, for dry film resist (DFR), for multilayer circuit boards, etc. process applications.
  • This laminated polyester film is used, for example, as a support in mold release/process applications.
  • the sheet-forming polyester film may be used, for example, in a step of forming various sheets such as a green sheet by coating or laminating various materials on at least one side of the film.
  • various materials are preferably applied or laminated on the film surface opposite to the surface provided with the resin layer. It may be coated or laminated on the face side.
  • a release layer or the like may be appropriately provided on the film surface opposite to the surface provided with the resin layer.
  • this laminated polyester film can form a uniform thin dielectric layer when used as a support for a ceramic green sheet in the manufacturing process of MLCC, and the switching frequency of polyester film rolls due to lengthening can be reduced. can contribute to the improvement of productivity due to the reduction of In particular, it can be suitably used as a support for semi-green sheets used in MLCCs for automobiles.
  • the laminated polyester film of the present invention can also be a release film having a release layer on the surface of the polyester film opposite to the resin layer.
  • the laminated polyester film of the present invention has the first mode and the second mode, and the release film has the first mode and the second mode corresponding to each mode.
  • a 1st aspect and a 2nd aspect may be collectively called a 3rd aspect.
  • a 1st aspect has the following structures.
  • the resin composition contains the following compounds (A) and (B).
  • Kurtosis (Sku) of the surface of the resin layer is less than 3.0.
  • the second aspect has the following configuration.
  • the resin composition contains the following compounds (A) and (B).
  • the ratio (Rmr(70)) should be 74% or less.
  • a release film equips the other surface side of a polyester film with a release layer.
  • the release layer is laminated directly or via another layer on the polyester film as described above.
  • Other layers include, for example, an easy-adhesion coating layer for improving adhesion to the present polyester film, an antistatic layer, an antiblocking layer, and the like.
  • the release layer is formed from a release agent composition.
  • the release agent composition contains a release agent.
  • the release agent is not particularly limited, and conventionally known release agents can be used. Examples include silicone compounds, long-chain alkyl group-containing compounds, waxes, and fluorine compounds. Among them, at least one of a silicone compound and a long-chain alkyl group-containing compound is preferable. In the release agent composition, one release agent may be used alone, or two or more release agents may be used in combination.
  • a silicone compound is a compound having a silicone structure in its molecule, in other words, a compound having a main skeleton formed by siloxane bonds.
  • the silicone compound or the main skeleton constituting the silicone compound include organopolysiloxane such as polydimethylsiloxane, acrylic-grafted silicone, silicone-grafted acrylic, amino-modified silicone, perfluoroalkyl-modified silicone, and alkyl-modified silicone. .
  • organopolysiloxane such as polydimethylsiloxane is preferable from the viewpoint of excellent releasability.
  • a silicone compound having a functional group capable of reacting with the (meth)acryloyl group in the compound containing the (meth)acryloyl group described below is preferable, and among these, a silicone compound containing a Si—H group is particularly preferable.
  • the Si—H group of the silicone compound has the property of enhancing adhesion with the present polyester film.
  • a silicone compound having an Si—H group and an alkenyl group is preferable from the viewpoint of forming a crosslinked structure having a skeleton derived from the silicone compound in the release layer.
  • the molecular weight of the silicone compound is not particularly limited. Among them, the number average molecular weight is preferably 5,000 or more, more preferably 10,000 or more, from the viewpoint of adhesion between the present polyester film and the release layer. Although the upper limit is not particularly limited, it is usually 1,000,000 or less.
  • the number average molecular weight of the silicone compound can be measured, for example, by gel permeation chromatography (GPC) and calculated as a polystyrene equivalent value.
  • silicone compounds it is preferable to include a curable silicone compound in consideration of heat resistance and stain resistance as the silicone compound used in the release agent composition.
  • a curable silicone compound any type of curing reaction such as addition curing type, condensation curing type, ultraviolet curing type, and electron beam curing type can be used.
  • an addition-curable silicone compound is more preferable from the viewpoint that it can increase the cohesive strength of the coating film.
  • An addition-curable silicone compound is a silicone compound having an unsaturated hydrocarbon group and a hydrogen group as functional groups in its structure, and an addition curing reaction is carried out by the reaction of these functional groups. That is, it is a mixture of a silicone compound having an Si—H group and a silicone compound containing an alkenyl group, or a silicone compound containing an Si—H group and a vinyl group in its molecule. From the viewpoint of pot life, it is preferable that the unsaturated hydrocarbon group and the hydrogen group are not present in the same molecule, and it is preferable to include the functional groups in separate silicone molecules and use a mixture thereof. Therefore, it is preferable to use a mixture of a silicone compound having an unsaturated hydrocarbon group as a functional group and a silicone compound having a hydrogen group as a functional group.
  • silicone compound having an unsaturated hydrocarbon group as a functional group examples include unsaturated hydrocarbon group-containing polydimethylsiloxane. At least two unsaturated hydrocarbon groups must be contained in the polydimethylsiloxane molecule.
  • unsaturated hydrocarbon groups include alkenyl groups having 2 to 8 carbon atoms such as vinyl, propenyl, butenyl and pentenyl groups. Among these, a vinyl group is preferable in terms of industrial availability.
  • Alkenyl groups containing at least two may contain alkenyl groups with different carbon numbers.
  • the unsaturated hydrocarbon group-containing polydimethylsiloxane has an alkenyl group and a methyl group as functional groups directly linked to silicon atoms, and may also have various other functional groups.
  • functional groups other than methyl include alkyl groups such as ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and methylphenyl; and alkoxy groups such as groups. From the viewpoint of adhesion to the polyester film, it preferably contains a phenyl group or a methoxy group.
  • examples of the silicone compound having a hydrogen group as a functional group include hydrogen group-containing polydimethylsiloxane.
  • a hydrogen group-containing polydimethylsiloxane is a polydimethylsiloxane having hydrogen atoms bonded to silicon atoms. At least two silicon-bonded hydrogen atoms must be contained in one molecule, and preferably three or more are contained from the viewpoint of curing properties.
  • the silicon-bonded hydrogen atoms can be terminal or side chains of the polydimethylsiloxane molecular chain.
  • Hydrogen group-containing polydimethylsiloxane has hydrogen groups and methyl groups as functional groups directly linked to silicon atoms, but may have various other functional groups.
  • Examples of functional groups other than methyl include alkyl groups such as ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and methylphenyl; and alkoxy groups such as groups.
  • the polydimethylsiloxane skeleton of the unsaturated hydrocarbon group-containing polydimethylsiloxane and the hydrogen group-containing polydimethylsiloxane may be linear or branched.
  • the molar ratio of all Si—H groups to all alkenyl groups is 1.0 to 5.0. is preferably If the molar ratio is 1.0 or more, the curability can be maintained, and if it is 5.0 or less, the amount of remaining Si—H groups is not too large, and the peeling force against the adhesive becomes heavy. It is preferable because it is not overdone. From this point of view, it is preferably 1.0 to 5.0, more preferably 1.6 or more or 4.8 or less, and particularly preferably 2.0 or more or 4.6 or less.
  • the silicone compound used in the release agent composition may be a solvent curable silicone or a non-solvent curable silicone. It is also possible to use a mixture of a solvent curable silicone and a non-solvent curable silicone. In addition, both solvent-type curable silicones and non-solvent curable silicones are curable silicones with releasability, and include addition reactions between vinyl groups and groups having silicon-hydrogen bonds during the curing process. (so-called addition type silicone) is preferred.
  • a surfactant component can be used as an emulsion stabilizer.
  • Nonionic surfactants include polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers, polyoxyalkylene phenyl ethers such as polyoxyethylene phenyl ethers, glycerin alkyl ethers, glycerin fatty acid esters and alkylene glycol adducts thereof, polyglycerin. Fatty acid esters and their alkylene glycol adducts, propylene glycol fatty acid esters and their alkylene glycol adducts, polyalkylene glycol fatty acid esters and the like can be mentioned.
  • anionic surfactants include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and their salts, alkyl sulfonic acids, alkenyl sulfonates, fatty acid ester sulfonates, and alkyl sulfate ester salts. , secondary higher alcohol sulfates, alkyl and allyl ether sulfates, fatty acid ester sulfates, polyoxyethylene alkyl sulfates, funnel oil and other sulfates, alkyl phosphates, ether phosphates, Alkyl allyl ether phosphates, amide phosphates and the like can be mentioned. Among these, nonionic surfactants are preferred, and polyoxyalkylene alkyl ethers and polyoxyalkylene phenyl ethers are more preferred from the viewpoint of the stability of the silicone emulsion.
  • polyoxyalkylene alkyl ethers examples include polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxybutylene alkyl ethers, and the like. Among these, polyoxyethylene alkyl ether is preferred.
  • the alkyl group is preferably a straight or branched alkyl group having 8 to 30 carbon atoms, more preferably a straight or branched alkyl group having 8 to 16 carbon atoms.
  • polyoxyalkylene phenyl ether examples include polyoxyethylene phenyl ether, polyoxypropylene phenyl ether, and polyoxybutylene phenyl ether. Among these, polyoxyethylene phenyl ether is preferred.
  • the phenyl group is an unsubstituted or substituted phenyl group, preferably a styrenated phenyl group in which a hydrogen atom of the phenyl group is substituted with a styryl group.
  • a long-chain alkyl group-containing compound is a compound having a linear or branched alkyl group having 6 or more carbon atoms, preferably 8 or more carbon atoms, more preferably 12 or more carbon atoms.
  • Examples of the alkyl group include alkyl groups having about 6 to 30 carbon atoms such as hexyl group, octyl group, decyl group, lauryl group, octadecyl group and behenyl group.
  • Examples of compounds having an alkyl group include various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, long-chain alkyl group-containing quaternary ammonium salts, and the like. .
  • a polymer compound is preferred. Further, from the viewpoint of obtaining releasability effectively, a polymer compound having a long-chain alkyl group in a side chain is more preferable.
  • a polymer compound having a long-chain alkyl group in its side chain can be obtained by reacting a polymer having a reactive group with a compound having an alkyl group capable of reacting with the reactive group.
  • the reactive groups include hydroxyl groups, amino groups, carboxyl groups, acid anhydrides, and the like.
  • compounds having these reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, reactive group-containing polyester resins, and reactive group-containing poly(meth)acrylic resins.
  • polyvinyl alcohol is preferable in consideration of releasability and ease of handling.
  • the degree of polymerization of the polyvinyl alcohol used is not particularly limited, but is usually 100 or more, preferably in the range of 300-40,000.
  • the degree of saponification of polyvinyl alcohol is not particularly limited, but is usually 70 mol% or more, preferably in the range of 70 to 99.9 mol%, more preferably 80 to 97 mol%, further preferably 86 to 99.9 mol%. 95 mol % is used.
  • the compound having an alkyl group capable of reacting with the reactive group includes, for example, hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, behenyl isocyanate and other long-chain alkyl group-containing isocyanates, hexanoyl chloride, octanoyl long-chain alkyl group-containing acid chlorides such as chloride, decanoyl chloride, lauroyl chloride, octadecanoyl chloride and behenoyl chloride; long-chain alkyl group-containing amines; long-chain alkyl group-containing alcohols; Among these, long-chain alkyl group-containing isocyanates are preferred, and octadecyl isocyanate is particularly preferred, in view of ease of handling.
  • Polymer compounds having long-chain alkyl groups in side chains can also be obtained by polymerizing long-chain alkyl (meth)acrylates or by copolymerizing long-chain alkyl (meth)acrylates with other vinyl group-containing monomers.
  • long-chain alkyl (meth)acrylates include hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, and behenyl (meth)acrylate.
  • the content of the silicone compound in the release agent composition is preferably 50 to 100% by mass, as a proportion of the total nonvolatile components in the release agent composition, and more The range is preferably 70 to 100% by mass, more preferably 90 to 99% by mass, and particularly preferably 95 to 99% by mass. If the release layer contains 50% by mass or more of the silicone compound, sufficient release properties can be obtained, which is preferable. By setting the content to 99% by mass or less, a compound containing a (meth)acryloyl group, which will be described later, can be included, so that the adhesion to the present polyester film can be further enhanced.
  • the content of the release agent other than the silicone compound in the release agent composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and particularly preferably 50 to 70% by mass, as a proportion of all non-volatile components in the release agent composition. % range.
  • the content is 10% by mass or more, releasability is improved.
  • sufficient solvent resistance can be obtained by setting the content to 90% by mass or less.
  • the release agent composition preferably contains a cross-linking agent when a release agent other than a silicone compound is used as the release agent.
  • the cross-linking agent is not particularly limited, and conventionally known cross-linking agents can be used. By using a cross-linking agent, the strength of the release layer can be increased, and the release component can be prevented from being transferred to the layer.
  • cross-linking agents include melamine compounds, oxazoline compounds, epoxy compounds, carbodiimide compounds, isocyanate compounds, silane coupling compounds, and the like.
  • the cross-linking agent preferably contains a melamine compound from the viewpoint of enhancing the strength of the release layer and improving the adhesion to the polyester film.
  • the cross-linking agents may be used singly or in combination of two or more. Specific aspects and preferred aspects of the cross-linking agent that can be contained in the release agent composition are the same as those of the above-described cross-linking agent that can be contained in the resin composition, and all of these can be used. That is, examples of the cross-linking agent in the release agent composition are the same as those in the above resin composition.
  • the content of the cross-linking agent in the release agent composition is preferably 10 to 90% by mass, more than The range is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and particularly preferably 30 to 50% by mass.
  • the strength of the release layer can be improved.
  • the content is set to 90% by mass or less, sufficient releasability can be ensured.
  • the release agent composition may further contain a compound containing a (meth)acryloyl group.
  • a silicone compound is used as a release agent
  • the release agent composition may further contain a compound containing a (meth)acryloyl group.
  • the compound containing the (meth)acryloyl group includes a polymer (meth)acrylate compound and a monomer (meth)acrylate compound, any of which may be used. Moreover, these can also be used together.
  • polymeric (meth)acrylate compounds mean macromonomers.
  • Examples of (meth)acrylate compounds include urethane (meth)acrylate compounds, epoxy (meth)acrylate compounds, polyester (meth)acrylate compounds, polyalkylene (meth)acrylate compounds, and other (meth)acrylate compounds. can be mentioned.
  • the compound containing a (meth)acryloyl group is a urethane (meth)acrylate or a mixture of a combination of a urethane (meth)acrylate and a (meth)acrylate compound other than a urethane (meth)acrylate. preferable.
  • urethane (meth)acrylate compound conventionally known compounds can be used, and there is no particular limitation.
  • a compound obtained by reacting a (meth)acrylate compound having a hydroxyl group with an isocyanate compound )
  • a compound obtained by reacting an acrylate compound, a polyol and an isocyanate compound may be a polymer or a monomer, but is preferably a polymer from the viewpoint of adhesion to the polyester film.
  • (Meth)acrylate compounds having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin mono(meth)acrylate, glycerin di( meth)acrylate, diglycerin mono(meth)acrylate, diglycerin tri(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate ) acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, sorbito
  • diglycerin tri(meth)acrylate pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentatri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, and dipentaerythritol tri(meth)acrylate.
  • the number of (meth)acryloyl groups in one molecule such as erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate Three or more are preferred, and dipentaerythritol penta(meth)acrylate, sorbitol penta(meth)acrylate and the like having five or more (meth)acryloyl groups per molecule are more preferred.
  • An isocyanate compound is a compound having an isocyanate or isocyanate derivative structure represented by a blocked isocyanate.
  • isocyanates include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate and naphthalene diisocyanate, and aromatic rings such as ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate.
  • Aliphatic isocyanates such as aliphatic isocyanate, methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, Alicyclic isocyanates such as methylenebis(4-cyclohexyl isocyanate) and isopropylidene dicyclohexyl diisocyanate can be exemplified.
  • Reaction products of these isocyanates and various polymers and compounds may also be used.
  • Polymers and derivatives of these isocyanates such as buret products, isocyanurate products, uretdione products and carbodiimide modified products can also be used. These may be used alone or in combination of multiple types.
  • aliphatic isocyanates or alicyclic isocyanates are preferred, and alicyclic isocyanates are more preferred, from the viewpoint of improving the adhesion of the release layer to the polyester film.
  • polyols examples include polycarbonate polyols, polyester polyols, and polyether polyols, and high-molecular-weight polyols and low-molecular-weight polyols can be used.
  • the high molecular weight polyol is not particularly limited, but preferably has a number average molecular weight of 400 to 8,000, more preferably 400 to 4,000. When the number average molecular weight is within this range, the viscosity is appropriate and a good appearance of the release layer can be obtained.
  • high-molecular-weight polyols include polycarbonate polyols, polyester polyols, polyether polyols, and the like. Polycarbonate polyol is preferred in order to improve adhesion to the polyester film.
  • Polycarbonate polyols are obtained from polyhydric alcohols and carbonate compounds through a dealcoholization reaction.
  • Polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane diol, neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-naphthalenedimethanol, 3 , 4
  • Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate.
  • Examples of polycarbonate polyols obtained from these reactions include polyhexamethylene carbonate diol and polycyclohexylene carbonate diol. be able to. Among these, polyhexamethylene carbonate diol is preferable from the viewpoint of adhesion of the release layer to the polyester film.
  • Polyester polyols include polycarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) or their acid anhydrides.
  • polycarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.
  • polyhydric alcohols ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2 -methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2, 5-dimethyl-2,5-hexanediol, 1,9-nonane
  • Polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and the like.
  • the low-molecular-weight polyol is not particularly limited, for example, those having a number-average molecular weight of 60 or more and less than 400 can be mentioned.
  • Examples of (meth)acrylate compounds include monofunctional (meth)acrylates, bifunctional (meth)acrylates, polyfunctional (meth)acrylates, and the like.
  • the polyfunctional (meth)acrylate refers to a compound having three or more (meth)acrylate groups in one molecule.
  • a (meth)acrylate compound may be a polymer or a monomer. A monomer is preferable from the viewpoint of reactivity with the silicone compound.
  • the monofunctional (meth)acrylate is not particularly limited.
  • alkyl (meth)acrylate such as methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, etc.
  • Hydroxyalkyl (meth)acrylates such as meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypropyl ( Alkoxyalkyl (meth)acrylates such as meth)acrylate and ethoxypropyl (meth)acrylate, aromatic (meth)acrylates such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate, diaminoethyl (meth)acrylate, diethylaminoethyl ( Amino group-containing (meth)acrylates such as meth)acrylate, methoxyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, ethylene oxide-modified (meth)acrylates such as phenylphenol
  • bifunctional (meth)acrylates include, but are not limited to, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth) alkanediol di(meth)acrylate such as acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, bisphenol A ethylene oxide modified di(meth)acrylate, bisphenol F ethylene oxide modified Bisphenol-modified di(meth)acrylate such as di(meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, polyethylene glycol Di(meth)acrylate, polypropylene glycol di(meth)
  • polyfunctional (meth)acrylates include, but are not limited to, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, and propylene oxide.
  • Isocyanuric acid-modified tri(meth)acrylate pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate Acrylates, tetramethylolmethane ethylene oxide-modified tetra(meth)acrylate, alkylenoxide-modified pentaerythritol tetra(meth)acrylate such as ethylene oxide-modified pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipenta Erythritol hexa(meth)acrylate and the like can be mentioned.
  • bifunctional (meth)acrylates or polyfunctional (meth)acrylates are preferred, and polyfunctional (meth)acrylates are more preferred.
  • trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipenta Erythritol hexa(meth)acrylate is preferred, and trimethylolpropane tri(meth)acrylate and dipentaerythritol hexa(tri)acrylate are more preferred.
  • the content of the compound containing a (meth)acryloyl group in the release agent composition is is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, still more preferably 2 to 30% by mass, and particularly preferably 2 to 10% by mass.
  • the content is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, still more preferably 2 to 30% by mass, and particularly preferably 2 to 10% by mass.
  • the release layer preferably contains a silicone compound as the release agent.
  • the release layer contains a compound containing a (meth)acryloyl group when the release agent composition contains a silicone compound as the release agent.
  • the release agent composition preferably further includes a cross-linking agent.
  • the release layer contains a long-chain alkyl group-containing compound as the release agent from the viewpoint of lowering the air leakage index described later and further improving handling properties such as winding properties of the present release film. is preferred.
  • the particularly preferable form described above may be appropriately selected.
  • binder resins In addition to the above components, binder resins, particles, antifoaming agents, coatability improvers, surfactants, thickeners, organic lubricants, ultraviolet absorbers, oxidation Additives such as inhibitors, foaming agents, dyes, and pigments may be added as appropriate. Specific aspects of the binder resin that can be contained in the release agent composition are the same as those of the binder resin that can be contained in the resin composition described above, and all of these can be used. Further, when a silicone compound is used as a release agent, a catalytic amount of a platinum group metal catalyst, a reactive heavy release modifier, or the like may be blended as appropriate.
  • the release agent composition may be diluted with a solvent to form a coating liquid. That is, the release agent composition may be applied as a liquid coating liquid, for example, to the present polyester film, dried and cured as necessary to form a release layer.
  • Each component constituting the release agent composition (a release agent, an optionally added cross-linking agent, a compound containing a (meth)acryloyl group, other components, etc.) may be dissolved in a solvent, It may be dispersed in a solvent.
  • the concentration of all non-volatile components in the release agent composition in the coating liquid is preferably 0.1 to 50% by mass. If it is 0.1% by mass or more, a release layer having a desired thickness can be efficiently formed. On the other hand, if it is 50% by mass or less, the appearance of the release layer can be improved by suppressing the viscosity at the time of coating, and the stability in the coating liquid can be enhanced.
  • solvent capable of diluting the release agent composition are the same as those of the solvent capable of diluting the resin composition described above, and all of these can be used.
  • each component constituting the release agent composition (release agent, optionally added cross-linking agent, compound containing (meth)acryloyl group, other components, etc.) It can be assumed that the latter compounds, or mixtures thereof, are present.
  • the analysis of each component in the release layer can be performed, for example, by TOF-SIMS, ESCA, fluorescent X-rays, and the like.
  • the release layer is preferably formed by in-line coating, which treats the film surface during the process of forming the polyester film.
  • in-line coating treats the film surface during the process of forming the polyester film.
  • the non-volatile component coating amount of the release layer is preferably 0.001 to 1.0 g/m 2 , more preferably 0.005 to 0.5 g/m 2 , still more preferably 0.01 to 0.2 g/m 2 . 2 . If the coating amount is 0.001 g/m 2 or more, sufficient releasability can be obtained. Further, when the coating amount is 1.0 g/m 2 or less, it is possible to suppress deterioration of the coating film appearance and insufficient curing of the coating film.
  • the coating amount can be calculated from the non-volatile component concentration of the coating liquid, the coating amount before drying derived from the consumption of the coating liquid, the transverse stretching ratio, and the like. Further, the coating amount of the non-volatile component is the coating amount on the release film, for example, when drying and stretching are performed, it is the coating amount after drying and stretching.
  • Kurtosis (Sku) of the resin layer surface of the release film in the first embodiment is less than 3.0. If the kurtosis (Sku) is less than 3.0, since the projections have a flat surface, the apexes of the projections are less likely to be crushed when the films are stacked, and the air release property can be efficiently maintained. From such a viewpoint, the kurtosis is preferably 2.9 or less, more preferably 2.8 or less, still more preferably 2.6 or less, particularly preferably 2.4 or less, and particularly preferably 2.2 or less. be. The lower limit is not particularly limited and is 0.1.
  • Kurtosis (Sku) of the surface of the resin layer of the release film in the second aspect is preferably less than 3.0. If the kurtosis (Sku) is less than 3.0, since the protrusions have a flat surface, the apexes of the protrusions are less likely to be crushed when the films are stacked, and the air release property can be efficiently maintained. From such a viewpoint, the kurtosis is more preferably 2.9 or less, more preferably 2.8 or less, particularly preferably 2.6 or less, particularly preferably 2.4 or less, and most preferably 2.2 or less. is. The lower limit is not particularly limited and is 0.1. The definition of kurtosis (Sku) is as described above.
  • the load length ratio (Rmr(70)) of the roughness curve at a cut level of 70% on the resin layer surface of the release film in the first aspect is preferably 82% or less, more preferably 65% or less, and still more preferably is 60% or less.
  • the lower limit is not particularly limited, and is about 1%, preferably 10% or more, more preferably 15% or more. If the load length ratio (Rmr(70)) is 82% or less, an appropriate fine uneven structure is formed, and when the film is wound into a roll, the gap between the films becomes large, and air It is possible to improve the easiness of coming off, and improve winding characteristics and the like.
  • the load length ratio (Rmr(70)) of the roughness curve at a cut level of 70% on the resin layer surface of the release film in the second embodiment is 74% or less. If the load length ratio (Rmr(70)) is 74% or less, an appropriate fine uneven structure is formed, and when the film is wound into a roll, the gap between the films becomes large, and air It is possible to improve the easiness of coming off, and improve winding characteristics and the like. From this point of view, the load length ratio (Rmr(70)) is preferably 70% or less, more preferably 65% or less, and even more preferably 60% or less. The lower limit is not particularly limited, and is about 1%, preferably 10% or more, more preferably 15% or more. The definition of the load length ratio (Rmr(70)) is as described above.
  • the arithmetic mean roughness (Ra) of the resin layer surface of the release film is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 50 nm or more, and particularly preferably 80 nm or more.
  • the upper limit is not particularly limited, it is preferably 600 nm, more preferably 400 nm, and still more preferably 200 nm. If the arithmetic mean roughness (Ra) is 10 nm or more, it can be said that the resin layer has a fine uneven structure, and the handleability of the release film is improved.
  • the concave-convex structure of the resin layer has a sufficiently fine shape.
  • the definition of the arithmetic mean roughness (Ra) is as described above.
  • the ten-point average roughness (Rzjis) of the resin layer surface of the release film is preferably 60 nm or more, more preferably 150 nm or more, and still more preferably 250 nm or more.
  • the upper limit is not particularly limited, it is preferably 800 nm, more preferably 600 nm, and still more preferably 450 nm. If the ten-point average roughness (Rzjis) is 60 nm or more, it can be said that the resin layer has a sufficient concave-convex structure. Further, when the ten-point average roughness (Rzjis) is 800 nm or less, it can be said that the concave-convex structure of the resin layer has a sufficiently fine shape.
  • the definition of the ten-point average roughness (Rzjis) is as described above.
  • the root-mean-square gradient (Sdq) of the resin layer surface of the release film is preferably 0.1 or more, more preferably 0.25 or more, and still more preferably 0.45 or more.
  • the root-mean-square gradient (Sdq) is preferably 3 or less, more preferably 1.0 or less.
  • the root-mean-square gradient (Sdq) is 0.1 or more, the difference between peaks and valleys of the uneven structure is clear, and thus the air release property can be enhanced. Further, when the root mean square gradient (Sdq) is 3 or less, coarse projections can be suppressed.
  • the definition of the root-mean-square gradient (Sdq) is as described above.
  • the developed interface area ratio (Sdr) of the resin layer surface of the release film is preferably 0.5% or more, more preferably 3% or more, and still more preferably 9% or more.
  • the developed interface area ratio (Sdr) is preferably 60% or less, more preferably 50% or less. If the developed interface area ratio (Sdr) is 0.5% or more, the winding characteristics can be improved by forming a fine uneven structure. Further, when the developed interface area ratio (Sdr) is 60% or less, undulations are moderately suppressed, and coarse projections can be prevented.
  • the definition of the developed interface area ratio (Sdr) is as described above.
  • the surface arithmetic mean roughness (Sa) of the resin layer surface of the release film is preferably in the range of 1 to 70 nm, more preferably in the range of 2 to 50 nm, and still more preferably in the range of 3 to 30 nm. If the arithmetic mean roughness (Sa) is in the range, extremely large unevenness can be reduced while having fine unevenness. Therefore, for example, it is possible to ensure the handleability of the release film, suppress wrinkles when winding it into a roll, use it as a support for the ceramic green sheet in the manufacturing process of the laminated ceramic capacitor, and provide the resin layer.
  • the surface maximum peak height (Sp) of the resin layer surface of the release film is preferably 1000 nm or less, more preferably 800 nm or less, still more preferably 500 nm or less, particularly preferably 300 nm or less, and particularly preferably 200 nm or less. is.
  • the maximum peak height (Sp) is preferably 10 nm or more, more preferably 20 nm or more. If the maximum peak height (Sp) is 1000 nm or less, protrusions can be reduced.
  • the resin It is possible to prevent projection transfer to the ceramic layer and destruction of the ceramic layer due to projections on the layer surface.
  • the maximum peak height (Sp) is 10 nm or more, the release film can be easily handled, and wrinkles can be suppressed when the release film is wound into a roll.
  • the definition of the maximum peak height (Sp) is as described above.
  • the release layer of the release film preferably has a tape peeling force of 500 mN/cm or less, more preferably 400 mN/cm or less, still more preferably 300 mN/cm or less, and particularly preferably 200 mN/cm or less. If the tape peeling force is 500 mN/cm or less, it can be said that the release film has sufficient releasability.
  • the lower limit is not particularly limited, and is about 0.1 mN/cm.
  • the tape peel strength of the release layer can be measured by the method described in Examples.
  • the coefficient of static friction between the resin layer surface and the release layer surface of the release film is preferably 1.0 or less, more preferably 0.8 or less, still more preferably 0.6 or less, and particularly preferably 0.4. It is below.
  • the coefficient of friction between the resin layer surface and the release layer surface is important because the resin layer surface and the release layer surface come into contact with each other. Therefore, if the coefficient of static friction is within the range, the uneven structure of the resin layer improves the slipperiness and the handleability of the release film.
  • the static friction coefficient can be measured by the method described in Examples.
  • the air leakage index can be used as an index for evaluating the handling properties such as the ease of winding the release film. If the air leakage index is low, the air caught in when the release film is rolled up can be easily released, and defects in the appearance of the roll such as wrinkles and uneven edges can be prevented. On the other hand, when the air leakage index is high, trapped air escapes after a sufficient period of time, especially during transportation, which may cause problems such as the film shifting in the direction of the winding core or scratches caused by the shifting. A release film does not cause such problems.
  • the air leakage index may be, for example, 150,000 seconds or less. It is more preferably 100,000 seconds or less, still more preferably 70,000 seconds or less, and particularly preferably 30,000 seconds or less. If it is 150,000 seconds or less, it can be said that it has a certain handleability.
  • the air leakage index can be improved not only by the uneven structure of the resin layer, but also by the roughness of the smooth surface of the polyester film.
  • the polyester film surface opposite to the surface on which the resin layer is formed that is, the smooth surface
  • the opposite surface when used for various applications such as a release film for molding a green sheet of a laminated ceramic capacitor, an interlayer insulating resin release film, and a release film for dry film resist, It is preferably a film surface used for processing, and for example, various materials may be coated or laminated as described later. Also, when more precise processing is required, the arithmetic mean roughness (Sa) of the polyester film surface on the opposite surface (that is, the smooth surface of the film used for processing) is 9 nm or less, and the maximum peak height (Sp) is It is more preferable to satisfy either or both of 500 nm or less.
  • Sa arithmetic mean roughness of the polyester film surface on the opposite surface
  • Sp maximum peak height
  • the air leakage index depends on the degree of smoothness of the surface of the polyester film opposite to the surface on which the resin layer is formed. Even when the polyester film is required to have smoothness, it is possible to obtain the effect of improving the handleability due to the concave-convex structure of the resin layer.
  • the air leakage index can be measured by the method described in Examples.
  • the resin layer in the first embodiment is characterized in that it is composed of a resin composition containing a certain amount of a specific compound and has a specific roughness structure, thereby enabling the development of a fine uneven structure. In addition, it is also characterized by focusing on the degree of sharpness (kurtosis), which can evaluate the tip shape of unevenness as an index representing the roughness structure.
  • the resin layer in the second aspect is characterized in that it is made of a resin composition containing a specific compound, and has a specific roughness structure, so that a fine concave-convex structure can be developed.
  • the release film can be used for various purposes for the purpose of improving handleability, and its use is not particularly limited. Among them, as described above, since it has a fine uneven structure, if it is used for sheet molding, it exhibits good winding properties even when winding a highly smooth film into a roll, and wrinkles are less likely to occur. It can be suitably used as a release film for sheet molding.
  • Release films for sheet molding include, for example, green sheet molding of multi-layer ceramic capacitors (MLCCs), interlayer insulating resins, dry film resists (DFR), various release films for multilayer circuit boards, and the like.
  • Applications include: Release films are used, for example, as supports in release applications.
  • the release film can be suitably used as a support for ceramic green sheets in the manufacturing process of multilayer ceramic capacitors, especially multilayer ceramic capacitors for automobiles.
  • the release film for sheet molding may be used, for example, in a step of forming various sheets such as a green sheet by coating or laminating various materials on at least one side of the film. Various materials are preferably applied or laminated on the release layer side.
  • the term “film” includes “sheet”, and the term “sheet” includes “film”.
  • X to Y X and Y are arbitrary numbers
  • X or more and Y or less and “preferably larger than X” or “preferably Y It also includes the meaning of "less than”.
  • X or more X is an arbitrary number
  • Y is an arbitrary number
  • Average particle diameter of particles contained in the polyester film The average particle diameter of the particles is measured by observing 10 or more particles with a scanning electron microscope (SEM), measuring the diameter of the particles, and averaging the average value. It was obtained as a particle size (average primary particle size). At that time, in the case of non-spherical particles, the average value of the longest diameter and the shortest diameter was measured as the diameter of each particle.
  • SEM scanning electron microscope
  • Arithmetic mean roughness (Sa) and maximum peak height (Sp) of the surface of the resin layer and the surface opposite to the resin layer The film surface is measured using a non-contact surface/layer cross-sectional shape measurement system VertScan (registered trademark) R550GML manufactured by Ryoka Systems Co., Ltd., CCD camera: SONY HR-50 1/3 ', objective lens: 20x, mirror Cylinder: 1X Body, Zoom lens: No Relay, Wavelength filter: 530 white, Measurement mode: Wave, measure an area of 640 ⁇ m ⁇ 480 ⁇ m, use the output by 4th order polynomial correction, arithmetic mean roughness (Sa) And the maximum peak height (Sp) was obtained by averaging 10 points.
  • VertScan registered trademark
  • VertScan registered trademark
  • CCD camera SONY HR-50 1/3 '
  • objective lens 20x
  • mirror Cylinder 1X Body
  • Zoom lens No Relay
  • Wavelength filter 530 white
  • Measurement mode
  • Coating film retention (%) Amount of resin layer components after treatment / Amount of resin layer components before treatment x 100
  • the static friction coefficient between the resin layer surface and the opposite side of the laminated polyester film was obtained by the following method.
  • the film was attached to a smooth glass plate having a width of 10 mm and a length of 100 mm so that the surface opposite to the surface provided with the resin layer was the upper surface.
  • a film cut into a width of 18 mm and a length of 120 mm is placed on the film so that the surface provided with the resin layer is the bottom surface, and a metal pin having a diameter of 8 mm is pressed on the film, and the metal pin is placed on the glass plate.
  • the frictional force was measured by sliding in the longitudinal direction at a load of 30 g and 40 mm/min, and the maximum value immediately after sliding was evaluated as the coefficient of static friction.
  • Static friction coefficient ( ⁇ s) Fs/weight load (in the above formula, the unit of Fs is g weight, and the unit of weight load is g weight)
  • the sample size of the test film was 70 mm square, and 20 test films were laminated so that the front and back sides of the test film overlapped to obtain a laminated film for test.
  • a hole with a diameter of 5 mm was made in the center of the laminated film for testing, and the air leakage index was measured as described above. The larger the value of this air leakage index, the longer it takes for air to leak from the gaps between the films, so it indicates that the films are in closer contact, and the risk of wrinkles when made into a roll film. is large.
  • the evaluation method is the same except for the evaluation method of the concave-convex structure.
  • the evaluation method of the uneven structure is as described above.
  • Embodiment 1 Examples of Embodiment 1 will be described below.
  • Polyesters used in Examples and Comparative Examples are as follows.
  • Polymers (A) 100 parts by mass of dimethyl terephthalate and 65 parts by mass of ethylene glycol were charged into a transesterification reactor equipped with a stirrer, a heating device and a distillate separation tower, and heated to 150° C. to melt the dimethyl terephthalate.
  • the oligomer was then transferred to a stirred polycondensation reactor equipped with a distillation tube.
  • An ethylene glycol solution of magnesium acetate tetrahydrate was added to the transferred oligomer so that the amount of magnesium acetate added to the obtained polyester resin content was 0.09% by mass.
  • an ethylene glycol solution of phosphoric acid was added as a heat stabilizer so that the amount of phosphoric acid added to the resulting polyester was 0.017% by mass.
  • polyester (B) 0.75% by mass of alumina particles having an average particle size of 0.05 ⁇ m are added to the polyester (A) and kneaded using a vented twin-screw kneader to obtain a polyester having an intrinsic viscosity (IV) of 0.63 dL / g. (B) was obtained.
  • polyester (C) instead of adding tetrabutyl titanate in polyester (A), polyester (A) except that antimony trioxide is added as a polycondensation catalyst so that the amount of antimony atoms is 300 ppm by mass with respect to the polyester resin content obtained. In the same manner as above, a polyester (C) having an intrinsic viscosity (IV) of 0.63 dl/g was obtained.
  • polyesters (A) to (C) used in each example of the first embodiment and the second embodiment are common.
  • a resin composition obtained by stirring and mixing the composition shown in Table 1-1 below was diluted with water to prepare coating liquids 1-1 to 1-17.
  • the compounds used are as follows.
  • Compound (A): binder resin (1-IA)] Aqueous dispersion of polyester resin copolymerized with the following composition Monomer composition: (acid component) terephthalic acid/isophthalic acid/5-sodium sulfoisophthalic acid // (diol component) ethylene glycol/1,4-butanediol/diethylene glycol 56/40/4//70/20/10 (mol%)
  • Isophorone diisocyanate unit: terephthalic acid unit: isophthalic acid unit: ethylene glycol unit: diethylene glycol unit: dimethylolpropionic acid unit 12:19:18:21:25:5 (mol%).
  • Example 1-1 A mixed raw material obtained by mixing polyesters (A) and (B) at a ratio of 87% by mass and 13% by mass, respectively, is used as a raw material for the outermost layer (A layer) on one side, and polyester (A) alone is used as a raw material for the intermediate layer (B layer). , and polyester (A) alone was used as the raw material for the outermost layer (C layer) on one side.
  • a coating liquid 1-1 having the composition shown in Table 1-1 below was applied to one side (the surface of the C layer) of this uniaxially stretched film in a coating amount (after drying and stretching) of 0.12 g/m 2 , and then the film was coated. is introduced to a tenter stretching machine, stretched 4.5 times in the width direction at 105 ° C., further subjected to heat treatment at 230 ° C., and then subjected to 2% relaxation treatment in the width direction, resin on the surface of the C layer of polyester film A A laminated polyester film having a layer thickness of 31 ⁇ m was obtained. Evaluation results are shown in Table 1-2.
  • Example 1-2 to 1-3 A laminated polyester film was obtained in the same manner as in Example 1-1 except that the coating liquid shown in Table 1-1 was used and the coating amount (after drying and stretching) was changed to the coating amount shown in Table 1-2. . Evaluation results are shown in Table 1-2.
  • Example 1-4 In the same manner as in Example 1-1, except that only the polyester (A) was used as the raw material for the outermost layer (A layer) on one side and only the polyester (C) was used as the raw material for the intermediate layer (B layer), C of the polyester film B was prepared. A laminated polyester film having a resin layer on the layer surface was obtained. Evaluation results are shown in Table 1-2.
  • Examples 1-5 to 1-19 A laminated polyester film was obtained in the same manner as in Example 1-4, except that the coating liquid shown in Table 1-1 was used and the coating amount (after drying and stretching) was changed to the coating amount shown in Table 1-2. . Evaluation results are shown in Table 1-2.
  • Example 1-1 A polyester film was obtained in the same manner as in Example 1-1, except that the resin layer was not provided. Evaluation results are shown in Table 1-2.
  • Example 1-2 A polyester film was obtained in the same manner as in Example 1-4, except that the resin layer was not provided. Evaluation results are shown in Table 1-2.
  • Example 1-4 A laminated polyester film was obtained in the same manner as in Example 1-4, except that the coating liquid shown in Table 1-1 was used and the coating amount (after drying and stretching) was changed to the coating amount shown in Table 1-2. . Evaluation results are shown in Table 1-2.
  • shape 1 is a mesh shape (see FIG. 1)
  • shape 2 is a mixed mesh shape and uneven shape (see FIG. 2)
  • shape 3 is an uneven shape (see FIG. 3). reference).
  • the polyester film A in Table 1-2 is the polyester film of Example 1-1
  • the polyester film B is the polyester film of Example 1-4.
  • Examples 1-1 to 1-19 which are the laminated polyester films of the present invention, formed an uneven structure by containing the compound (A) and a certain amount or more of (B). and the kurtosis (Sku) is less than 3.0, it becomes an appropriate uneven shape, the static friction coefficient is as low as 1.0 or less, the slipperiness is good, and the air leakage index is 130,000 seconds or less. It can be seen that the film is excellent in productivity such as windability because it has excellent properties. In addition, since the arithmetic mean roughness (Sa) and the maximum peak height (Sp) of the opposite surface of the resin layer were low, the film was an excellent film capable of precise processing.
  • Sa arithmetic mean roughness
  • Sp maximum peak height
  • Comparative Examples 1-1 and 1-2 do not have a resin layer, they do not have an uneven structure.
  • Comparative Example 3 contains compound (A) and a certain amount or more of compound (B), it has a high kurtosis (Sku) value and does not have an appropriate concave-convex structure. Therefore, although the coefficient of static friction was low, the film had a high air leakage index and poor handleability.
  • Comparative Examples 1-4 and 1-5 do not contain a certain amount or more of the compound (B), no concave-convex structure is formed. Therefore, these comparative examples were films with high coefficient of friction and air leakage index, poor slip properties and air release properties, and poor handleability.
  • Embodiment 2 Examples of Embodiment 2 will be described below.
  • Compound (A): binder resin (2-IA)] Aqueous dispersion of polyester resin copolymerized with the following composition Monomer composition: (acid component) terephthalic acid/isophthalic acid/5-sodium sulfoisophthalic acid // (diol component) ethylene glycol/1,4-butanediol/diethylene glycol 56/40/4//70/20/10 (mol%)
  • Isophorone diisocyanate unit: terephthalic acid unit: isophthalic acid unit: ethylene glycol unit: diethylene glycol unit: dimethylolpropionic acid unit 12:19:18:21:25:5 (mol%).
  • reaction solution was maintained at 60° C., and 35.8 parts of methyl isobutanoylacetate, 32.2 parts of diethyl malonate, and 0.88 parts of a 28% methanol solution of sodium methoxide were added and maintained for 4 hours.
  • a blocked polyisocyanate obtained by adding 58.9 parts of n-butanol, maintaining the temperature of the reaction mixture at 80° C. for 2 hours, and then adding 0.86 parts of 2-ethylhexyl acid phosphate.
  • Example 2-1 A mixed raw material obtained by mixing polyesters (A) and (B) at a ratio of 87% by mass and 13% by mass, respectively, is used as a raw material for the outermost layer (A layer) on one side, and polyester (A) alone is used as a raw material for the intermediate layer (B layer). , and polyester (A) alone was used as the raw material for the outermost layer (C layer) on one side.
  • a coating liquid 2-1 having the composition shown in Table 2-1 below was applied to one side (the surface of layer C) of this uniaxially stretched film so that the coating amount (after drying and stretching) was 0.12 g/m 2 .
  • this film is guided to a tenter stretching machine, stretched 4.5 times in the width direction at 105 ° C., further heat-treated at 230 ° C., and then subjected to 2% relaxation treatment in the width direction.
  • a laminated polyester film having a thickness of 31 ⁇ m and having a resin layer on the layer surface was obtained. Evaluation results are shown in Table 2-2.
  • Example 2-2 to 2-3 A laminated polyester film was obtained in the same manner as in Example 2-1, except that the coating liquid shown in Table 2-1 was used and the coating amount (after drying and stretching) was changed to the coating amount shown in Table 2-2. . Evaluation results are shown in Table 2-2.
  • Example 2-4 In the same manner as in Example 2-1 except that only the polyester (A) was used as the raw material for the outermost layer (A layer) on one side and only the polyester (C) was used as the raw material for the intermediate layer (B layer), C of the polyester film B was prepared. A laminated polyester film having a resin layer on the layer surface was obtained. Evaluation results are shown in Table 2-2.
  • Examples 2-5 to 2-23 A laminated polyester film was obtained in the same manner as in Example 2-4, except that the coating liquid shown in Table 2-1 was used and the coating amount (after drying and stretching) was changed to the coating amount shown in Table 2-2. . Evaluation results are shown in Table 2-2.
  • Example 2-1 A polyester film was obtained in the same manner as in Example 2-1, except that the resin layer was not provided. Evaluation results are shown in Table 2-2.
  • Example 2-2 A polyester film was obtained in the same manner as in Example 2-4, except that the resin layer was not provided. Evaluation results are shown in Table 2-2.
  • Example 2-3 A laminated polyester film was obtained in the same manner as in Example 2-4, except that the coating liquid shown in Table 2-1 was used and the coating amount (after drying and stretching) was changed to the coating amount shown in Table 2-2. . Evaluation results are shown in Table 2-2.
  • shape 1 is a mesh shape (see FIG. 1)
  • shape 2 is a mixed mesh shape and uneven shape (see FIG. 2)
  • shape 3 is an uneven shape (see FIG. 3). reference).
  • the polyester film A in Table 2-2 is the polyester film of Example 2-1
  • the polyester film B is the polyester film of Example 2-4.
  • Examples 2-1 to 2-23 which are laminated polyester films of the present invention, have an uneven structure by containing the compound (A) and the compound (B),
  • the load length ratio (Rmr(70)) is 80% or less, it has an appropriate irregular shape, a low static friction coefficient of 1.0 or less, good slipperiness, and an air leakage index of 130,000 seconds or less. It can be seen that the film is excellent in productivity such as windability because it has excellent air release properties.
  • the arithmetic mean roughness (Sa) and the maximum peak height (Sp) of the opposite surface of the resin layer were low, the film was an excellent film capable of precise processing.
  • Comparative Examples 2-1 and 2-2 do not have a resin layer, they do not have an uneven structure.
  • Comparative Example 2-3 which contains compound (A) and compound (B), has a high load length ratio (Rmr(70)) and does not have an appropriate uneven structure. Therefore, although the coefficient of static friction was low, the film had a high air leakage index and poor handleability.
  • Average particle diameter of particles contained in the polyester film The average particle diameter of the particles is measured by observing 10 or more particles with a scanning electron microscope (SEM), measuring the diameter of the particles, and averaging the average value. It was obtained as a particle size (average primary particle size). At that time, in the case of non-spherical particles, the average value of the longest diameter and the shortest diameter was measured as the diameter of each particle.
  • SEM scanning electron microscope
  • Arithmetic mean roughness (Sa) and maximum peak height (Sp) of the surface of the resin layer and the surface opposite to the resin layer The film surface is measured using a non-contact surface/layer cross-sectional shape measurement system VertScan (registered trademark) R550GML manufactured by Ryoka Systems Co., Ltd., CCD camera: SONY HR-50 1/3 ', objective lens: 20x, mirror Cylinder: 1X Body, Zoom lens: No Relay, Wavelength filter: 530 white, Measurement mode: Wave, measure an area of 640 ⁇ m ⁇ 480 ⁇ m, use the output by 4th order polynomial correction, arithmetic mean roughness (Sa) And the maximum peak height (Sp) was obtained by averaging 10 points.
  • VertScan registered trademark
  • VertScan registered trademark
  • CCD camera SONY HR-50 1/3 '
  • objective lens 20x
  • mirror Cylinder 1X Body
  • Zoom lens No Relay
  • Wavelength filter 530 white
  • Measurement mode
  • the static friction coefficient between the resin layer surface and the release layer surface of the release film was obtained by the following method.
  • the film was attached onto a smooth metal plate having a width of 10 mm and a length of 100 mm so that the surface of the release layer faced upward.
  • a film cut into a width of 18 mm and a length of 120 mm is placed on the film so that the surface provided with the resin layer is the bottom surface, and a metal pin having a diameter of 8 mm is pressed on the film, and the metal pin is placed on the glass plate.
  • the frictional force was measured by sliding in the longitudinal direction at a load of 30 g and 40 mm/min, and the maximum value immediately after sliding was evaluated as the coefficient of static friction.
  • Static friction coefficient ( ⁇ s) Fs/weight load (in the above formula, the unit of Fs is g weight, and the unit of weight load is g weight)
  • Air Leakage Index Using a digibec smoothness tester (manufactured by Toyo Seiki Co., Ltd., "DB-2"), measurements were made in accordance with JIS P8119 at a temperature of 23°C and a humidity of 50% RH.
  • the pressure of the pressurizing device is 100 kPa
  • the vacuum vessel has a volume of 38 mL
  • the time for 1 mL of air to flow that is, the time (seconds) until the pressure inside the vessel changes from 50.7 kPa to 48.0 kPa is measured. 10 times the obtained number of seconds was taken as the air leakage index.
  • the sample size of the test film was 70 mm square, and 20 test films were laminated so that the front and back sides of the test film overlapped to obtain a laminated film for test.
  • a hole with a diameter of 5 mm was made in the center of the laminated film for testing, and the air leakage index was measured as described above. The larger the value of this air leakage index, the longer it takes for air to leak from the gaps between the films, so it indicates that the films are in closer contact, and the risk of wrinkles when made into a roll film. is large.
  • Polyesters used in Examples and Comparative Examples are as follows.
  • Polymers (A) 100 parts by mass of dimethyl terephthalate and 65 parts by mass of ethylene glycol were charged into a transesterification reactor equipped with a stirrer, a heating device and a distillate separation tower, and heated to 150° C. to melt the dimethyl terephthalate.
  • the oligomer was then transferred to a stirred polycondensation reactor equipped with a distillation tube.
  • An ethylene glycol solution of magnesium acetate tetrahydrate was added to the transferred oligomer so that the amount of magnesium acetate added to the obtained polyester resin content was 0.09% by mass.
  • an ethylene glycol solution of phosphoric acid was added as a heat stabilizer so that the amount of phosphoric acid added to the resulting polyester was 0.017% by mass.
  • polyester (B) instead of adding tetrabutyl titanate in polyester (A), polyester (A) except that antimony trioxide is added as a polycondensation catalyst so that the amount of antimony atoms is 300 ppm by mass with respect to the polyester resin content obtained. In the same manner as above, a polyester (B) having an intrinsic viscosity (IV) of 0.63 dL/g was obtained.
  • a resin composition obtained by stirring and mixing the composition shown in Table 3-1 below was diluted with water to prepare coating liquids 3-A1 to 3-A7.
  • the compounds used are as follows.
  • Compound (A): binder resin (3-IA)] Aqueous dispersion of polyester resin copolymerized with the following composition Monomer composition: (acid component) terephthalic acid/isophthalic acid/5-sodium sulfoisophthalic acid // (diol component) ethylene glycol/1,4-butanediol/diethylene glycol 56/40/4//70/20/10 (mol%)
  • Isophorone diisocyanate unit: terephthalic acid unit: isophthalic acid unit: ethylene glycol unit: diethylene glycol unit: dimethylolpropionic acid unit 12:19:18:21:25:5 (mol%).
  • a release agent composition obtained by stirring and mixing the compositions shown in Table 3-2 below was diluted with water to prepare coating liquids 3-B1 to 3-B3.
  • the compounds used are as follows.
  • Release agent (3-IVA) A long-chain alkyl group-containing compound obtained by adding octadecyl isocyanate to polyvinyl alcohol with an average degree of polymerization of 500 and a degree of saponification of 88 mol%.
  • Release agent (3-IVB) Aqueous dispersion of vinyl group-containing polydimethylsiloxane having a vinyl group content of 0.16 mmol/g (emulsifier: nonionic surfactant)
  • Example 3-1 Only the polyester (A) was used as the raw material for the outermost layer (surface layer), and only the polyester (B) was used as the raw material for the intermediate layer.
  • Each of the raw materials for the outermost layer and the intermediate layer was supplied to two extruders, each melted at 280 ° C., and then placed on a cooling roll set at 25 ° C.
  • An unstretched sheet was obtained by co-extrusion with a layer structure of .6/27.8/1.6 and solidification by cooling. Then, this film was stretched 3.5 times in the longitudinal direction while being passed through a group of heating rolls at 86° C. to obtain a uniaxially stretched film.
  • a coating liquid 3-A1 having the composition shown in Table 3-1 below was applied so that the coating amount (after drying and stretching) was 0.05 g/m 2 .
  • Coating solution 3-B1 having the composition shown in Table 3-2 below was applied so that the coating amount (after drying and stretching) was 0.02 g/m 2 , and then this film was led to a tenter stretching machine and heated to 105°C.
  • the film was stretched 4.5 times in the width direction at , further heat-treated at 230°C, and then subjected to a relaxation treatment of 2% in the width direction to obtain a release film having a polyester film thickness of 31 ⁇ m. Evaluation results are shown in Table 3-3.
  • Examples 3-2 to 3-11 Release in the same manner as in Example 3-1, except that the coating liquids shown in Tables 3-1 and 3-2 are used, and the coating amount (after drying and stretching) is set to the coating amount shown in Table 3-3. got the film. Evaluation results are shown in Table 3-3.
  • Example 3-1 A polyester film was obtained in the same manner as in Example 3-1, except that the resin layer and release layer were not provided. Evaluation results are shown in Table 3-3.
  • Example 3-1 except that the coating liquid shown in Table 3-1 was used, the coating amount (after drying and stretching) was set to the coating amount shown in Table 3-3, and the release layer was not provided. Similarly, a polyester film having a resin layer was obtained. Evaluation results are shown in Table 3-3.
  • Example 3-3 Same as Example 3-1 except that the coating liquid shown in Table 3-2 was used, the coating amount (after drying and stretching) was set to the coating amount shown in Table 3-3, and the resin layer was not provided. Then, a polyester film having a release layer was obtained. Evaluation results are shown in Table 3-3.
  • Examples 3-1 to 3-11 which are release films in the first embodiment, contain compound (A) and a certain amount or more of compound (B), and kurtosis ( Sku) of less than 3.0 results in an appropriate uneven shape, a low coefficient of static friction of 1.0 or less, good slipperiness, and an air leakage index of 150,000 seconds or less, which is excellent in air release. It can be seen that the film is excellent in productivity such as removability.
  • Examples 3-1 to 3-11 which are release films in the second aspect, contain compound (A) and compound (B), and have a load length ratio (Rmr (70)) at a cutting level of 70%
  • Rmr (70) load length ratio
  • the laminated polyester film of the present invention can form a fine uneven structure on the surface of the resin layer, for example, if it is used for sheet molding, even when an extremely smooth film is wound into a roll, good windability can be obtained. There is an advantage that it is effective and wrinkles are less likely to occur.
  • the resin layer of the laminated polyester film of the present invention can be made into a thin film, the polyester film can be made thin and long, and it can contribute to productivity improvement by reducing the frequency of switching product rolls during processing. can. Therefore, the laminated polyester film of the present invention can be suitably used as a sheet forming polyester film or the like having excellent surface smoothness, and its industrial utility value is high.
  • the release film of the present invention since the release film of the present invention has a fine uneven structure on the surface of the resin layer, for example, if it is used for sheet molding, even when an extremely smooth film is wound into a roll, it has good winding properties. There is an advantage that wrinkles are less likely to occur. Furthermore, since the release film of the present invention can have a thin resin layer, it is possible to make the release film thin and long, and it contributes to productivity improvement by reducing the frequency of switching product rolls during processing. can be done. Therefore, the release film of the present invention can be suitably used as a release film for sheet molding or the like having excellent surface smoothness, and its industrial utility value is high.

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  • Inorganic Chemistry (AREA)

Abstract

L'invention concerne un film de polyester stratifié qui est équipé d'un film de polyester, et d'une couche de résine formée à partir d'une composition de résine sur au moins une face dudit film de polyester. Plus précisément, l'invention concerne un film de polyester stratifié satisfaisant l'ensemble des conditions (1) à (4) suivantes.　(1) Ladite couche de résine présente une structure irrégulière.　(2) Ladite composition de résine contient les composés (A) et (B) suivants.　Le composant (A) consiste en au moins un élément choisi dans un groupe constitué d'une résine de liant et d'un agent de réticulation. Le composant (B) consiste en des particules. La teneur en particules dudit composant (B), est supérieure ou égale à 20% en masse en termes de proportion par rapport à l'ensemble de tous les composants non-volatiles contenus dans ladite composition de résine.　(4) L'aplatissement (Sku) de la surface de ladite couche de résine est inférieur à 3,0.　Enfin, l'invention permet de fournir un film de polyester stratifié qui se révèle excellent en termes de propriétés de manipulation lors de l'enroulement d'un film sous forme de rouleau, du fait d'une formation de structure irrégulière fine.
PCT/JP2023/002888 2022-01-31 2023-01-30 Film de polyester stratifié WO2023145938A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008238646A (ja) * 2007-03-28 2008-10-09 Toray Ind Inc ハードコートフィルムおよび反射防止フィルム
JP2013167696A (ja) * 2012-02-14 2013-08-29 Dainippon Printing Co Ltd 光学積層体、偏光板及び画像表示装置
WO2019139095A1 (fr) * 2018-01-11 2019-07-18 東洋紡株式会社 Film stratifié, plaque polarisante mettant en œuvre ce dernier, et dispositif d'affichage d'image
WO2020009230A1 (fr) * 2018-07-06 2020-01-09 タツタ電線株式会社 Film de fixation pour carte imprimée
WO2022054645A1 (fr) * 2020-09-14 2022-03-17 大日本印刷株式会社 Article mat

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3684095B2 (ja) 1999-01-21 2005-08-17 帝人株式会社 易滑性複合ポリエステルフイルム
JP6273717B2 (ja) 2013-08-09 2018-02-07 東洋紡株式会社 セラミックシート成形用離型フィルム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008238646A (ja) * 2007-03-28 2008-10-09 Toray Ind Inc ハードコートフィルムおよび反射防止フィルム
JP2013167696A (ja) * 2012-02-14 2013-08-29 Dainippon Printing Co Ltd 光学積層体、偏光板及び画像表示装置
WO2019139095A1 (fr) * 2018-01-11 2019-07-18 東洋紡株式会社 Film stratifié, plaque polarisante mettant en œuvre ce dernier, et dispositif d'affichage d'image
WO2020009230A1 (fr) * 2018-07-06 2020-01-09 タツタ電線株式会社 Film de fixation pour carte imprimée
WO2022054645A1 (fr) * 2020-09-14 2022-03-17 大日本印刷株式会社 Article mat

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