CN116761723A - Laminated film and method for producing laminated film - Google Patents
Laminated film and method for producing laminated film Download PDFInfo
- Publication number
- CN116761723A CN116761723A CN202280011332.2A CN202280011332A CN116761723A CN 116761723 A CN116761723 A CN 116761723A CN 202280011332 A CN202280011332 A CN 202280011332A CN 116761723 A CN116761723 A CN 116761723A
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- Prior art keywords
- resin sheet
- film
- less
- resin
- release layer
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- 239000004447 silicone coating Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
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- 150000003863 ammonium salts Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 2
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- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
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- 239000004645 polyester resin Substances 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/022—Mechanical properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
[ problem ] to provide: a laminated film of resin sheets having high smoothness and good slidability can be provided. [ solution ] A laminated film is provided with: a polyester-based base film, a release layer disposed on at least one side of the base film, and a resin sheet disposed on the side of the release layer opposite to the base, wherein the laminated film satisfies the following conditions: the resin sheet is obtained by curing a resin sheet-forming composition containing at least a resin component (A) and a crosslinking agent (B), the resin sheet contains substantially no particles, the film thickness (t 1) of the resin sheet is 1 [ mu ] m or more and 20 [ mu ] m or less, the arithmetic average height (Sa) of the surface (1) of the resin sheet is 2nm or more and 30nm or less, the maximum section height (St) of the surface (1) of the resin sheet is 80nm or more and 1000nm or less, and the static friction coefficient measured by overlapping the surface (1) of the resin sheet on the side opposite to the release layer side with the surface (2) of the resin sheet on the release layer side is 1.5 or less.
Description
Technical Field
The present invention relates to a laminated film in which resin sheets are laminated. In particular, the present invention relates to a laminated film in which resin sheets for electronic components and optical applications are laminated.
Background
Conventionally, a release film using a polyester film as a base material has high heat resistance and mechanical properties, and is used as an engineering film for film formation from a solution of a resin sheet such as an adhesive sheet, a protective film, a polymer electrolyte membrane, and a dielectric resin sheet. In recent years, particularly, resin sheets used for electronic parts such as dielectric resin sheets used for film capacitors and optical applications are required to have high smoothness and transparency, and therefore, a release film used as an engineering film is also required to have high smoothness on its surface. Accordingly, techniques described in patent documents 1 to 3 have been disclosed, and a technique for reducing the surface roughness of the release layer surface has been proposed.
However, for example, in optical applications, high smoothness is required to improve transparency and the like, and if the smoothness is high, the slidability is deteriorated, and scratches may be introduced in a conveying process and the like, and the yield may be lowered. In addition, in electronic component applications such as film capacitor applications, smoothness is required to improve electrical characteristics such as dielectric breakdown voltage, and if the smoothness is too high, the smoothness is poor, and winding misalignment, mixing of wrinkles, and the like occur when a dielectric resin sheet is wound around a roll, and there is a concern that the performance of the film capacitor is degraded.
To improve these, patent document 4 proposes: specific particles are added to a resin sheet for optical use such as a polarizing plate, and the resin sheet is provided with slidability. Patent document 5 proposes a method of transferring particles on a base film to a resin sheet used for a film capacitor or the like.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2012-144021
Patent document 2: japanese patent laid-open publication No. 2014-154273
Patent document 3: japanese patent laid-open No. 2015-182261
Patent document 4: japanese patent application laid-open No. 2019-95661
Patent document 5: international publication No. 2020/039638
Disclosure of Invention
Problems to be solved by the invention
However, in the method of patent document 4, since particles are contained in the resin sheet, there is a concern that transparency such as an increase in internal haze becomes insufficient. In addition, in the method of patent document 5, there is a concern that the amount of particles transferred to the resin sheet becomes uneven, and there is a concern that slidability becomes unstable.
The present invention is to solve the above problems, and proposes: a laminated film having a resin sheet with high smoothness and good slidability and substantially no particles added to the inside of the resin sheet can be provided.
Solution for solving the problem
The present inventors have conducted intensive studies and as a result found that: the smooth base film is coated with a coating liquid containing at least a specific resin and a crosslinking agent under specific conditions and dried/cured, whereby irregularities derived from a phase separation structure are formed on the surface of the laminated film, and good slidability is successfully imparted without containing particles or the like.
That is, the present invention includes the following constitution.
[1] A laminated film, comprising: a polyester base film, a release layer disposed on at least one side of the base film, and a resin sheet disposed on the opposite side of the release layer from the base,
the laminated film satisfies the following (1) to (6):
(1) The resin sheet is obtained by curing a resin sheet-forming composition comprising at least a resin component (A) and a crosslinking agent (B),
(2) The resin sheet is substantially free of particles,
(3) The film thickness (t 1) of the resin sheet is 1 μm or more and 20 μm or less,
(4) The arithmetic average height (Sa) of the surface (1) of the resin sheet is 2nm or more and 30nm or less,
(5) The maximum section height (St) of the surface (1) of the resin sheet is 80nm to 1000nm,
(6) The coefficient of static friction measured by overlapping the surface (1) of the resin sheet on the side opposite to the release layer with the surface (2) of the resin sheet on the side of the release layer is 1.5 or less.
[2] In one embodiment, the crosslinking agent (B) contained in the resin sheet-forming composition is liquid at 30 ℃.
[3] In one embodiment, the proportion of the crosslinking agent (B) contained in the resin sheet is 10 mass% or more based on the entire resin sheet.
[4] In one embodiment, the weight average molecular weight of the resin component (a) contained in the resin sheet is 10000 or more.
[5]In one mode, the surface free energy of the release layer surface is 40mJ/m 2 The adhesion energy is 3.5mJ/m 2 The above.
[6] In one embodiment, the arithmetic average height (Sa) of the release layer side surface of the base film is 20nm or less and the maximum protrusion height (P) is 500nm or less.
[7] In another embodiment, the present invention provides a method for producing a laminated film according to any one of the above, comprising the steps of: the resin sheet was coated and formed on the base film by a solution film-forming method.
ADVANTAGEOUS EFFECTS OF INVENTION
The laminated film of the present invention can provide a resin sheet having both high smoothness and good sliding properties, and the resin sheet molded in the present invention can provide a good product for various applications.
Drawings
Fig. 1 is a schematic cross-sectional view showing the constitution of the present invention.
Fig. 2 is a schematic cross-sectional view illustrating the constitution of the present invention in one embodiment.
Detailed Description
As shown in fig. 1, the laminated film of the present invention comprises a polyester base film 10, a release layer 11 disposed on at least one side of the base film 10, and a resin sheet 12 disposed on the side of the release layer 11 opposite to the base film 10.
The present invention may provide, for example, in optical applications: a resin sheet capable of improving transparency and the like, and a resin sheet exhibiting high smoothness. In addition, it is possible to achieve both high smoothness and high sliding properties which have been difficult to achieve in the past, and for example, it is possible to suppress the introduction of scratches in the conveying process and the like, and it is possible to avoid a reduction in yield.
In addition, for example, in electronic component applications such as thin film capacitor applications, a resin sheet exhibiting high smoothness can be provided, and the resin sheet can improve electrical characteristics such as dielectric breakdown voltage. In addition, it is possible to achieve both high smoothness and high slip properties which have been difficult to achieve in the past, and for example, winding misalignment, mixing of wrinkles, and the like can be suppressed when a dielectric resin sheet is wound around a roller, and good winding properties can be exhibited. Therefore, transportation or the like can be performed while maintaining excellent capacitor performance.
Further, in the present invention, the resin sheet contains substantially no particles, and it is possible to avoid insufficient transparency such as an increase in internal haze. In addition, the problem that the amount of particles transferred to the resin sheet becomes uneven can be avoided, and good slidability can be exhibited.
(substrate film)
The present invention provides a polyester-based base film. The polyester constituting the polyester film used as the base material of the present invention is not particularly limited, and a polyester generally used as a base material film can be formed using a film. The crystalline linear saturated polyester preferably comprises an aromatic dibasic acid component and a diol component, and for example, polyethylene terephthalate, 2, 6-polyethylene naphthalate, polybutylene terephthalate, polypropylene terephthalate, or a copolymer containing these resins as a main component is further preferable. Particularly suitable are polyester films formed from polyethylene terephthalate.
The polyethylene terephthalate may be: the repeating unit of ethylene terephthalate is preferably 90 mol% or more, more preferably 95 mol% or more, and is copolymerized with a small amount of other dicarboxylic acid component or diol component. For cost reasons, it is preferred to be manufactured from terephthalic acid and ethylene glycol alone. In addition, known additives such as antioxidants, light stabilizers, ultraviolet absorbers, crystallization agents, and the like may be added within a range that does not hinder the effects of the film of the present invention. For reasons such as the high degree of bidirectional elastic modulus, biaxially oriented polyester films are preferred.
The intrinsic viscosity of the polyethylene terephthalate film is preferably 0.50 to 0.70dl/g, more preferably 0.52 to 0.62dl/g. When the intrinsic viscosity is 0.50dl/g or more, the stretching step is not preferable because of multiple breakage. In contrast, if the ratio is 0.70dl/g or less, the cutting property is good when the sheet is cut into a predetermined product width, and the sheet is preferably not defective in size. In addition, the raw material pellets are preferably sufficiently vacuum dried.
The method for producing the polyester film of the present invention is not particularly limited, and a conventionally generally used method can be used. For example, the polyester is melted in an extruder, extruded into a film shape, cooled on a rotary cooling drum to obtain an unstretched film, and the unstretched film is stretched to obtain the polyester film. The stretching is preferably biaxial stretching because of mechanical properties and the like. The biaxially stretched film may be obtained by a method of biaxially stretching a uniaxially stretched film in the machine direction or the transverse direction in that order or a method of biaxially stretching an unstretched film simultaneously in the machine direction and the transverse direction.
In the present invention, the stretching temperature at the time of stretching the polyester film is preferably set to be equal to or higher than the second transition point (Tg) of the polyester. The stretching is preferably performed 1 to 8 times, particularly preferably 2 to 6 times, in the longitudinal and transverse directions.
The thickness of the polyester film is preferably 6 μm or more and 50 μm or less, more preferably 8 μm or more and 31 μm or less, still more preferably 10 μm or more and 28 μm or less. If the thickness of the film is 6 μm or more, the film is preferably produced, the step of processing the release layer, the step of molding the resin sheet, and the like, because of no concern about thermal deformation. On the other hand, if the film thickness is 50 μm or less, the roll diameter at the time of winding the roll is small, and the roll length of the molded resin sheet can be extended, so that it is preferable.
When the polyester film as the base film has a multilayer structure described later, the film thickness as the whole of the base film falls within the above-described range.
The polyester film may be a single layer or a plurality of layers of 2 or more layers. It is preferable to have a surface layer a substantially free of particles on at least one side. In one embodiment, the polyester film as the base film has a surface layer a on one surface of the resin sheet side. When the base film is a laminated polyester film formed of 2 or more layers, it is preferable that the surface layer B containing particles or the like is provided on the opposite side of the surface layer a containing substantially no particles. When the layer on the side where the resin sheet is disposed is a surface layer a, the layer on the opposite side is a surface layer B, and the core layers other than the surface layer are layers C, the laminated structure may be a/B, a/C/B, or the like.
Layer C may be a multi-layer construction. The surface layer B may not contain particles. In this case, in order to impart slidability for winding up the film into a roll, it is preferable to provide a coating layer containing particles and a binder on the surface layer B.
In the polyester film of the present invention, the surface layer a located on the surface on which the resin sheet is molded preferably contains substantially no particles. The arithmetic average height (Sa) of the surface layer a of the polyester film, that is, the arithmetic average height (Sa) of the release layer side surface of the base film is preferably 20nm or less. Further, the arithmetic mean height (Sa) is particularly preferably 10nm or less. If Sa is 20nm or less, the occurrence of voids and local thickness unevenness in the molding of the resin sheet is less likely to occur, which is preferable. The arithmetic average height (Sa) of the surface layer A is preferably smaller but may be 0.1nm or more. Here, in the case where a release layer or the like described later is provided on the surface layer a, the release layer preferably contains substantially no particles, and the arithmetic average height (Sa) after the release layer is preferably within the aforementioned range. In the present invention, the term "substantially free of particles" means a content of 50ppm or less, preferably 10ppm or less, and most preferably a detection limit or less in the case of quantifying inorganic elements by fluorescent X-ray analysis, for example, in the case of inorganic particles. This is because even if particles are not positively added to the film, the contamination component derived from foreign matters, the raw material resin, or dirt adhering to a pipeline or a device in the process of producing the film may be peeled off and mixed into the film.
The maximum protrusion height (P) of the surface layer a of the polyester film, that is, the maximum protrusion height (P) of the release layer side surface of the base film is, for example, 500nm or less, preferably 200nm or less, more preferably 150nm or less, still more preferably 100nm or less, for example, 85nm or less, particularly preferably 50nm or less. If the maximum protrusion height (P) is 500nm or less, no pinholes, localized filming and other defects will occur during the formation of the resin sheet, and the yield is good.
The smaller the P of the surface layer A of the polyester film is, the more preferable, but may be 1nm or more, and may be 3nm or more. Here, in the case where a release layer or the like described later is provided on the surface layer a, it is preferable that the maximum protrusion height (P) after lamination of the release layer falls within the aforementioned range.
In the polyester film of the present invention, the surface layer B forming the opposite surface of the surface layer a preferably contains particles, and particularly preferably silica particles and/or calcium carbonate particles are used, from the viewpoints of slidability of the film and easiness of removal of air. The particle content contained in the surface layer B is preferably 5000 to 15000ppm in total of particles contained therein. At this time, the arithmetic mean height (Sa) of the thin film of the surface layer B is preferably in the range of 1 to 40 nm. More preferably in the range of 5 to 35 nm. When the total amount of silica particles and/or calcium carbonate particles is 5000ppm or more and Sa is 1nm or more, air can be uniformly released when the film is wound up in a roll shape, and the winding posture and flatness are good, so that the film is suitable for manufacturing a resin sheet. In addition, when the total amount of silica particles and/or calcium carbonate particles is 15000ppm or less and Sa is 40nm or less, aggregation of the lubricant is less likely to occur, and coarse protrusions are not likely to occur, so that the quality is stable and preferable when the resin sheet is molded.
As the particles contained in the surface layer B, non-active inorganic particles and/or heat-resistant organic particles, etc. may be used in addition to silica and/or calcium carbonate. From the viewpoints of transparency and cost, silica particles and/or calcium carbonate particles are more preferably used, but alumina & #8722 is exemplified as the inorganic particles that can be used in addition; silica composite oxide particles, hydroxyapatite particles, and the like. Examples of the heat-resistant organic particles include crosslinked polyacrylic acid particles, crosslinked polystyrene particles, and benzoguanamine particles. In addition, in the case of using silica particles, porous colloidal silica is preferable, and in the case of using calcium carbonate particles, light calcium carbonate surface-treated with a polyacrylic polymer compound is preferable from the viewpoint of preventing lubricant from falling off.
The average particle diameter of the particles added to the surface layer B is preferably 0.1 μm or more and 2.0 μm or less, particularly preferably 0.5 μm or more and 1.0 μm or less. If the average particle diameter of the particles is 0.1 μm or more, the substrate film is preferable because of good sliding properties. If the average particle diameter is 2.0 μm or less, it is preferable that the resin sheet has no fear of pinholes due to coarse particles of the surface layer B.
The surface layer B may contain 2 or more kinds of particles of different materials. The particles may contain the same kind of particles and have different average particle diameters.
In the case where no particles are contained in the surface layer B, it is preferable that the surface layer B has slipperiness by a coating layer containing particles. The coating layer is not particularly limited, and is preferably an in-line coating device in which coating is performed during film formation of the polyester film. When the surface layer B contains no particles and has a coating layer containing particles thereon, the arithmetic average height (Sa) of the surface of the coating layer is preferably in the range of 1 to 40nm for the same reason as the arithmetic average height (Sa) of the surface layer B described above. More preferably in the range of 5 to 35 nm.
In order to prevent the mixing of particles such as lubricant, it is preferable not to use a recycling material or the like from the viewpoint of reducing pinholes in the surface layer a which is the layer on the resin sheet side.
The thickness ratio of the surface layer a, which is a layer on the side where the resin sheet is provided, is preferably 20% to 50% of the total layer thickness of the base film. If it is 20% or more, the film is less susceptible to particles contained in the surface layer B or the like from the inside, and the arithmetic average height (Sa) is preferably easily satisfied in the above range. If the total layer thickness of the base film is 50% or less, the use ratio of the regeneration raw material in the surface layer B can be increased, and the environmental load is preferably reduced.
In addition, from the viewpoint of economy, 50 to 90 mass% of film scraps and a recycled material of a plastic bottle can be used for the layer other than the surface layer a (the surface layer B or the intermediate layer C). In this case, too, it is preferable that the kind, amount, particle diameter, and arithmetic mean height (Sa) of the lubricant contained in the surface layer B satisfy the above-described ranges.
In order to improve adhesion of a release layer or the like to be applied later, to prevent electrification, or the like, a coating layer may be provided on the surface of the surface layer a and/or the surface layer B before stretching or after uniaxial stretching in the film-forming step, or corona treatment or the like may be performed. In the case where the coating layer is provided on the surface layer a, the coating layer preferably contains substantially no particles.
(Release layer)
The present invention has a release layer disposed on at least one side of a base film, for example, a release layer is provided between the base film and a resin sheet. The resin constituting the release layer is not particularly limited, and silicone resin, fluororesin, alkyd resin, various waxes, aliphatic olefin, etc. may be used alone or in combination of 2 or more kinds of resins. When the cross-linking agent is contained in the resin sheet described later, the silicone resin is contained, and thus the release property is improved, which is preferable.
In the present specification, the laminate of the base material and the release layer may be simply referred to as a release film.
The release layer may comprise, for example, a silicone resin. The silicone resin is a resin having a silicone structure in a molecule, and examples thereof include a curable silicone, a silicone graft resin, a modified silicone resin such as an alkyl modified silicone resin, and the like, but from the viewpoint of migration and the like, a reactive curable silicone resin is preferably used. As the reactive cured silicone resin, an addition reaction system, a condensation reaction system, an ultraviolet ray or electron beam curing system, or the like can be used. More preferably, the composition may be a low-temperature curable addition reaction system capable of being processed at a low temperature, or an ultraviolet or electron beam curable system. By using these, the polyester film can be processed at a low temperature in the coating process. Therefore, a polyester film having less thermal damage to the polyester film during processing and high flatness can be obtained, and the occurrence of defects such as pinholes can be reduced even when the resin sheet of the film is manufactured.
Examples of the silicone resin of the addition reaction system include a reaction between polydimethylsiloxane having vinyl groups introduced into the terminal or side chain thereof and hydrosiloxane with a platinum catalyst, and curing the reaction product. In this case, when a resin curable at 120℃for 30 seconds or less is used, the resin can be processed at a low temperature, and more preferably. Examples thereof include low-temperature addition curable type (LTC 1006L, LTC1056L, LTC300B, LTC303E, LTC310, LTC314, LTC350G, LTC450A, LTC371G, LTC750A, LTC755, LTC760A, etc.) and thermal UV curable type (LTC 851, BY24-510, BY24-561, BY24-562, etc.), solvent addition+UV curable type (X62-5040, X62-5065, X62-5072T, KS5508, etc.) manufactured BY Xin Yue chemical Co., ltd., and Dual-cure curable type (X62-2835, X62-2834, X62-1980, etc.).
Examples of the silicone resin in the condensation reaction system include a three-dimensional crosslinked structure formed by condensation reaction of polydimethylsiloxane having an OH group at the terminal and polydimethylsiloxane having an H group at the terminal with an organotin catalyst.
Examples of the ultraviolet-curable silicone resin include a silicone resin obtained by curing an unsaturated group by introducing a radical reaction similar to that of a general silicone rubber of the most basic type, a silicone resin obtained by photocuring an unsaturated group, a silicone resin obtained by decomposing an onium salt under ultraviolet light to generate a strong acid, and an epoxy group thereof by cleavage and crosslinking, and a silicone resin obtained by crosslinking an addition reaction of a vinyl siloxane with a thiol. In addition, electron beams may be used instead of the ultraviolet rays. The electron beam has a higher energy than ultraviolet rays, and, in the case of ultraviolet ray curing, a radical-based crosslinking reaction can be performed even without using an initiator. Examples of the resin used include UV curable silicones (X62-7028A/B, X62-7052, X62-7205, X62-7622, X62-7629, X62-7660, etc.) manufactured by Kagaku corporation, UV curable silicones (TPR 6502, TPR6501, TPR6500, UV9300, UV9315, XS56-A2982, UV9430, etc.) manufactured by MOMENTIVE PERFORMANCE MATERIALS KK, and UV curable silicones (SILCOLEASE UV POLY, POLY215, POLY201, KF-UV265AM, etc.) manufactured by Kagaku chemical Co., ltd.
As the ultraviolet-curable silicone resin, polydimethyl siloxane modified with acrylate or glycidoxy group may be used. These modified polydimethylsiloxanes can also exhibit good release properties when used in the presence of an initiator by mixing with multifunctional acrylate resins, epoxy resins, and the like.
Examples of the resin to be used include alkyd resins, acrylic resins, which have been modified with stearyl group or lauryl group, alkyd resins, acrylic resins, and olefin resins, which have been obtained by reaction of methylated melamine.
Examples of the amino alkyd resin obtained by the reaction of methylated melamine include Tesfine 303, tesfine 305, tesfine 314, which are manufactured by Hitachi chemical industries Co., ltd. Examples of the amino acrylic resin obtained by the reaction of methylated melamine include Tesfine 322 manufactured by Hitachi chemical industries Co., ltd.
In the case where the above resin is used in the release layer of the present invention, 1 kind of the resin may be used, or 2 or more kinds may be mixed and used. In order to adjust the peeling force, additives such as a light peeling additive and a heavy peeling additive may be mixed.
Additives such as adhesion improvers and antistatic agents may be added to the release layer of the present invention. In order to improve adhesion to the substrate, it is also preferable to perform pretreatment such as anchor coating, corona treatment, plasma treatment, and atmospheric pressure plasma treatment on the surface of the polyester film before providing the release layer.
In the present invention, the thickness of the release layer is not particularly limited as long as it is set according to the purpose of use, and the thickness of the release layer after curing is preferably in the range of 0.005 to 2.0. Mu.m. If the thickness of the release layer is 0.005 μm or more, the release property is preferably maintained. In addition, if the thickness of the release layer is 2.0 μm or less, the curing time is not excessively long, and there is no concern that the thickness of the resin sheet is uneven due to the lowering of the planarity of the release film. Further, since the curing time is not excessively long, there is no concern that the resin constituting the release coating layer is aggregated and there is no concern that projections are formed, and thus pinhole defects of the resin sheet are less likely to occur, which is preferable.
The surface free energy of the release layer provided on the substrate film of the present invention is preferably 12mJ/m 2 The above. More preferably 18mJ/m 2 The above, further preferably 20mJ/m 2 The above. If it is 12mJ/m 2 In this way, the resin sheet is preferably coated with the solution because the resin sheet is less likely to rebound.
The surface free energy of the release layer provided on the substrate film of the present invention is preferably 40mJ/m 2 The following is given. More preferably 35mJ/m 2 The following is more preferable 30mJ/m 2 The following is given. If it is 40mJ/m 2 Hereinafter, the molded resin sheet is preferable because of good releasability.
In the present invention, the surface free energy means: at least the surface free energy of the surface of the release layer in contact with the resin sheet.
The water adhesion energy of the surface of the release layer in contact with the resin sheet of the present invention is, for example, 3.0mJ/m 2 Above, preferably 3.5mJ/m 2 The above.More preferably 4.0mJ/m 2 The above, more preferably 5.5mJ/m 2 The above. If it is 3.0mJ/m 2 In the above manner, the swelling of the coated end portion is preferably suppressed when the solution of the resin sheet is coated. When the bulge of the coating end portion at the time of coating is suppressed, the standing ear (japanese text: standing ear) is suppressed when the laminated film is wound into a roll shape, and the winding posture becomes good, so that the flatness of the laminated film becomes good, and is preferable.
In order to improve the water adhesion energy of the release layer surface, it can be achieved by adding additives to the release layer or adjusting the polymer composition. For example, if the silicone resin is a silicone resin, a silicone resin having a phenyl group in a side chain, a silicone resin having a T unit (3 functions) and a Q unit (4 functions) added thereto, or the like is introduced into the polydimethylsiloxane skeleton, and the improvement is possible.
In order to improve the water adhesion energy of the release layer surface, other methods than the above method may be realized by changing the composition of the silicone resin. For example, in the case of an organic silicone resin of an addition reaction system, a polydimethylsiloxane and a hydrosiloxane having vinyl groups introduced into the terminal or side chain thereof are heated under a platinum catalyst to be cured, and the molar amount of si—h groups of the hydrosiloxane can be changed with respect to the molar amount of vinyl groups (si—vy) at the terminal, thereby changing the water attachment energy. For example, if Si-H is more than Si-Vy, water adhesion can be easily increased, and the Si-H/Si-Vi ratio is preferably 1.0 or more, more preferably 1.5 or more, and still more preferably 2.0 or more.
The arithmetic average height (Sa) of the release layer of the present invention is preferably 20nm or less in addition to the polyester base material. Further, the arithmetic mean height (Sa) is particularly preferably 10nm or less. If Sa is 20nm or less, pinholes and local thickness unevenness are less likely to occur during molding of the resin sheet, and this is preferable. The arithmetic average height (Sa) of the release layer may be preferably smaller but may be 0.1nm or more.
The maximum protrusion height (P) of the release layer is, for example, 500nm or less, preferably 200nm or less, more preferably 150nm or less, still more preferably 100nm or less, for example, 85nm or less, particularly preferably 50nm or less. If the maximum protrusion height (P) is 500nm or less, no pinholes or local defects such as filming will occur during the formation of the resin sheet, and the yield is preferably good.
In the present invention, the method for forming the release layer is not particularly limited, and the following method is used: the coating liquid in which the releasable resin is dissolved or dispersed is spread on one surface of the polyester film of the base material by coating or the like, and the solvent or the like is removed by drying, and then heated, thermally cured or ultraviolet cured.
As the coating method of the release layer, any known coating method can be applied, and for example, conventionally known methods such as a roll coating method such as a gravure coating method or a reverse coating method, a bar coating method such as a bar coating method, a die coating method, a spray coating method, and an air knife coating method can be used.
When a thermosetting material is used for the release layer, the drying temperature at the time of solvent drying and thermosetting is preferably 180 ℃ or lower, more preferably 160 ℃ or lower, further preferably 140 ℃ or lower, and most preferably 120 ℃ or lower. The heating time is preferably 30 seconds or less, more preferably 20 seconds or less, and most preferably 10 seconds or less. In the case of 180 ℃ or lower, it is preferable to maintain the flatness of the film, because it is less likely that the thickness of the resin sheet will be uneven. If the temperature is 120℃or lower, the film can be processed without impairing the planarity of the film, and the possibility of causing uneven thickness of the resin sheet is further reduced, which is particularly preferred.
The lower limit of the drying temperature is not particularly limited, but is preferably 60℃or higher. The release film is preferably obtained by leaving no solvent in the release layer at 60℃or higher.
When an ultraviolet curable material is used for the release layer, the drying temperature at the time of solvent drying and heat curing is preferably 120 ℃ or less, more preferably 100 ℃ or less, and most preferably 90 ℃ or less. The heating time is preferably 30 seconds or less, more preferably 20 seconds or less, and most preferably 10 seconds or less. In the case of 120 ℃ or lower, it is preferable to maintain the flatness of the film, because it is less likely that the thickness of the resin sheet will be uneven. If the temperature is 90℃or lower, the film can be processed without impairing the flatness of the film, and the possibility of causing uneven thickness of the resin sheet is further reduced, which is particularly preferred.
The lower limit of the drying temperature is not particularly limited, but is preferably 60℃or higher. The release film is preferably obtained without leaving a solvent in the release layer at 60℃or higher.
When an ultraviolet-curable material is used for the release layer, it is preferable to perform the curing reaction by irradiation with active energy rays after the solvent is dried. As the active energy ray to be used, known techniques such as ultraviolet rays and electron beams can be used, and ultraviolet rays are preferably used. The cumulative light amount when ultraviolet rays are used can be expressed as the product of illuminance and irradiation time. For example, it is preferably 10 to 500mJ/cm 2 . When the lower limit is not less than the above-mentioned lower limit, the release layer can be sufficiently cured, which is preferable. When the upper limit is less than or equal to the above-described upper limit, thermal damage to the film due to heat during irradiation can be suppressed, and smoothness of the surface of the release layer can be maintained, which is preferable.
(resin sheet)
The laminated film of the present invention has a resin sheet disposed on the side of the release layer opposite to the base material.
For example, the resin sheet laminated on the release film of the present invention is obtained by curing a resin sheet-forming composition containing at least a resin component (a) and a crosslinking agent (B).
As a result of intensive studies on the resin sheet of the present invention, it has been found that the resin component (a) and the crosslinking agent (B) can be cured in a phase-separated state or that moderate irregularities are formed on the surface of the resin sheet under specific conditions, for example, the resin sheet-forming composition of the present invention, which will be described later, and that the slidability of the resin sheet can be exhibited without causing particles or the like to be contained in the resin sheet.
The mass ratio of the resin component (a) to the crosslinking agent (B) is preferably 80 mass% or more, more preferably 90 mass% or more, and still more preferably 95 mass% or more of the solid content of the entire resin sheet. When the content is 80 mass% or more, the physical properties such as strength and heat resistance of the resin sheet are improved, which is preferable.
The mass ratio of the resin component (a) to the crosslinking agent (B) is preferably (a)/(B) =90/10 to 50/50. If the blending ratio of the crosslinking agent (B) is 10 mass% or more, the irregularities after phase separation are likely to increase and the slidability is improved, so that it is preferable. If the blending ratio of the crosslinking agent (B) is 50 mass% or less, the film strength of the resin sheet is not lowered, and the sheet handling property is excellent, so that it is preferable that the adhesion of the unreacted crosslinking agent to the back surface of the laminated film during winding can be prevented. For example, the ratio of the crosslinking agent (B) contained in the resin sheet is preferably 10 mass% or more and 50 mass% or less in the entire resin sheet. In one embodiment, the proportion of the crosslinking agent (B) contained in the resin sheet is 10 mass% or more and less than 50 mass%, for example, 15 mass% or more and 45 mass% or less, based on the entire resin sheet. The above-described effects can be more favorably exhibited by containing the crosslinking agent (B) under such conditions.
The resin component (a) is not particularly limited, and known resins can be used. For example, an epoxy resin, a phenoxy resin, a polyester resin, a urethane resin, a fluorine resin, an acrylic resin, an olefin resin, an imide resin, a sulfone resin, or the like may be used, and 1 kind or 2 or more kinds may be mixed and used. The weight average molecular weight (Mw) of the resin component (a) used in the present invention is 10000 or more, preferably 10000 or more and 200000 or less, more preferably 30000 or more and 100000 or less. If the resin is 10000 or more, the strength of the resin sheet is high, and the handleability is good, so that the resin sheet is preferable. If the viscosity is 200000 or less, the viscosity of the solution becomes low and the productivity becomes good in the case of film formation with the solution, which is preferable. The method for measuring the weight average molecular weight (Mw) is not particularly limited, and can be measured by GPC or the like.
The crosslinking agent (B) is not particularly limited, and known crosslinking agents can be used. For example, a crosslinking agent such as isocyanate, melamine, carbodiimide, or oxazoline may be used, and 1 kind may be used, or 2 or more kinds may be mixed and used. Preferably with functional groups contained in the resin component (A). The crosslinking agent (B) contained in the resin sheet-forming composition is preferably liquid at 30 ℃. In the present invention, the liquid may have fluidity, and for example, the viscosity may be 10000 mPas or less. The liquid at 30℃is preferable because phase separation from the resin component (A) during drying of the solution film of the resin sheet can be effectively promoted, and surface irregularities of the resin sheet can be easily formed.
The resin sheet may contain additives and the like in addition to the resin component (a) and the crosslinking agent (B) as long as the above-mentioned ranges are satisfied. However, the resin sheet is substantially free of particles. The resin sheet of the present invention is preferably used for optical applications because it contains substantially no particles, and therefore, for example, it has an effect of improving transparency of the resin sheet after molding, an effect of improving electrical characteristics of an electronic component such as a dielectric sheet used in a film capacitor, and the like. For example, if the resin sheet is used for optical purposes, the haze of the resin sheet may be 2% or less. In addition, the haze may be 1% or less. In one embodiment, the resin sheet has a haze of 0.1% or more. In addition, for example, if the resin sheet is an electronic component such as a film capacitor, the dielectric breakdown voltage of the resin sheet may be 200V/μm or more. In addition, the dielectric breakdown voltage may be 300V/μm or more. In one embodiment, the dielectric breakdown voltage is 500V/μm or less.
The resin sheet of the present invention has fine irregularities due to phase separation of the resin component (a) and the crosslinking agent (B) on the surface even if it does not substantially contain particles, and therefore can have good slidability. The static friction coefficient of the resin sheet peeled from the base film is preferably 1.5 or less, more preferably 1.0 or less, and still more preferably 0.8 or less. Since the static friction coefficient is 1.5 or less, the resin sheet is preferable because it is excellent in winding property, traveling property and the like and easy to handle when used in optical applications and electronic component applications. The static friction coefficient of the resin sheet may be 0.1 or more.
In one embodiment, in fig. 2, the static friction coefficient measured by overlapping the surface (1) of the resin sheet shown by reference numeral 13 on the side opposite to the release layer with the surface (2) of the resin sheet shown by reference numeral 14 is 1.5 or less. The static friction coefficient measured under the aforementioned conditions is more preferably 1.0 or less, and still more preferably 0.8 or less. The static friction coefficient may be 0.1 or more.
In this way, the resin sheet of the present invention can achieve both high smoothness and excellent windability and travelling properties by having the static friction coefficient measured by overlapping both surfaces of the resin sheet in the above range.
The surface (1) (the surface opposite to the surface contacting the release layer) of the resin sheet of the laminated film of the present invention has an arithmetic average roughness (Sa) of 2nm to 30nm, more preferably 2nm to 20nm, still more preferably 2.5nm to 15 nm. If the particle size is 2nm or more, the resin sheet is preferable because the sliding property is excellent. If the thickness is 30nm or less, the resin sheet is peeled from the laminated film, and if the resin sheet is wound into a roll, the risk of occurrence of defects such as pinholes is preferably reduced.
The maximum section height (St) of the surface (1) (the surface opposite to the surface contacting with the release layer) of the resin sheet of the laminated film of the present invention is 80nm or more and 1000nm or less, more preferably 100nm or more and 600nm or less, still more preferably 150nm or more and 500nm or less. If the particle size is 80nm or more, the resin sheet is preferable because the resin sheet has good sliding properties. If the thickness is 1000nm or less, the resin sheet is peeled from the laminated film, and if the resin sheet is wound into a roll, the risk of occurrence of defects such as pinholes is preferably reduced.
The maximum section height (St) is a value obtained by adding the absolute value of the maximum protrusion height (P) and the maximum valley depth (V).
The maximum protrusion height (P) of the surface (1) (the surface opposite to the surface in contact with the release layer) of the resin sheet of the laminated film of the present invention is preferably 500nm or less, more preferably 250nm or less, further preferably 200nm or less, and may be 185nm or less, for example 150nm or less, particularly preferably 135nm or less. For example, the wavelength may be 100nm or less.
If the maximum protrusion height (P) is 500nm or less, the resin sheet is peeled from the laminated film, and even when the resin sheet is wound into a roll, it is preferable that no dead spots such as pinholes occur. The smaller the maximum protrusion height P, the more preferable it can be, but it may be 1nm or more, 3nm or more, for example, 35nm or more.
By setting the arithmetic average roughness (Sa) and the maximum section height (St) of the surface (1) of the resin sheet of the laminated film of the present invention to the above-described ranges, good slidability can be obtained even on a surface having high smoothness. It is particularly preferable to control the maximum section height (St) to the above range.
In one embodiment, the maximum valley depth (V) of the surface (1) of the resin sheet of the laminated film is preferably 45nm to 350nm, for example, 45nm to 300nm, preferably 45nm to 250 nm. The maximum valley depth (V) is preferably in such a range that the maximum protrusion height (P) is not more than 250nm, since the maximum section height (St) can be easily controlled to the above range, and the sliding property of the resin sheet can be improved.
The arithmetic average roughness (Sa) of the surface (2) (surface in contact with the release layer) of the resin sheet of the laminated film of the present invention is preferably 10nm or less, more preferably 8nm or less, and still more preferably 5nm or less. If the thickness is 10nm or less, the resin sheet is peeled from the laminated film, and if the resin sheet is wound into a roll, the risk of occurrence of defects such as pinholes is preferably reduced.
The film thickness (t 1) of the resin sheet of the present invention is 1 μm or more and 20 μm or less. More preferably 1 μm or more and 10 μm or less, still more preferably 2 μm or more and 8 μm or less. When the film thickness (t 1) of the resin sheet is 1 μm or more, the resin sheet is preferably not liable to crack after being peeled from the base film, and can be handled easily. If the film thickness (t 1) of the resin sheet is 20 μm or less, the wet coating film thickness becomes excessively thick during solution film formation, and molding is easy, so that it is preferable.
The film thickness (t 1) of the resin sheet is not particularly limited, and can be measured by a known method. For example, the cross section can be measured by a contact film thickness meter, an optical interference film thickness meter, a scanning electron microscope, a transmission electron microscope, or the like.
As a method for laminating the resin sheet of the present invention on the base film, a coating solution containing at least the resin component (a) and the crosslinking agent (B) and dissolved or dispersed in an organic solvent, water or the like is preferably molded on the release layer by a solution film-forming method, and the resin sheet can be coated by a known method similar to the coating method of the release layer. For example, conventionally known methods such as a roll coating method such as a gravure coating method or a reverse coating method, a bar coating method such as a bar coating method, a die coating method, a spray coating method, and an air knife coating method can be used.
The release layer is preferably coated with the coating liquid, and then a heating step is preferably provided for drying and curing the solvent. The heating method is not particularly limited, and the coated laminated film may be heated by hot air, infrared rays, or the like. The laminated film of the present invention is preferably coated and dried by a roll-to-roll method, and the drying furnace is particularly preferably dried by hot air using a floating method, a roll supporting method, or the like.
The temperature at the time of drying was as follows: the maximum temperature of the drying furnace is preferably 60 ℃ to 160 ℃, more preferably 70 ℃ to 140 ℃, still more preferably 70 ℃ to 130 ℃. If the temperature is 60 ℃ or higher, the residual solvent in the dried resin sheet is small, and there is no concern that the performance of the resin sheet (for example, the electric characteristics in the case of use as a dielectric layer) will be lowered. If the temperature is 160 ℃ or lower, there is no fear of wrinkling of the laminated film due to heat, and therefore it is preferable. If the temperature is higher than 160 ℃, the phase separation between the resin component in the resin sheet and the crosslinking agent is excessively advanced, and there is a concern that the crosslinking density of the resin sheet is lowered, and therefore, the temperature is preferably 160 ℃ or lower.
The time from the application of the coating liquid to the substrate film to the entry of the coating liquid into the drying furnace is preferably 5 seconds or less, more preferably 3 seconds or less, and still more preferably 2 seconds or less. If the amount is less than 5 seconds, the phase separation between the resin component in the coating liquid and the crosslinking agent does not proceed excessively, and there is no fear that the crosslinking density of the resin sheet is lowered.
After the coating liquid is applied to the base film, the heating is performed in a drying furnace at a maximum temperature for a time of preferably 1 second or more, more preferably 2 seconds or more. If it is 1 second or more, the reaction of the crosslinking agent proceeds, so that it is preferable. The upper limit of the heating time is preferably 60 seconds or less, more preferably 40 seconds or less, and still more preferably 20 seconds or less. If the amount is 60 seconds or less, segregation of the crosslinking agent to the surface of the resin sheet can be suppressed from extremely proceeding, and the performance of the resin sheet is not lowered, which is preferable.
By setting the resin sheet of the present invention to the above-described drying condition, the phase separation between the resin component (a) and the crosslinking agent (B) is appropriately performed, and the arithmetic average roughness (Sa) and the maximum section height (St) of the resin sheet surface (1) can be controlled to the above-described ranges, whereby good slidability of the resin sheet can be exhibited without adding particles to the resin sheet.
(laminated film)
The laminated film of the present invention is used in the following steps and thereafter, the resin sheet is peeled from the base film. Therefore, if the peeling force from the base film is 800mN/25mm wide or less, the resin sheet can be peeled without breaking or the like, which is preferable. More preferably 500mN/25mm wide or less, still more preferably 300mN/25mm wide or less, still more preferably 200mN/25mm wide or less. The peeling force varies depending on the resin sheets to be laminated, and thus can be adjusted depending on the type of the release layer of the base film.
Examples
The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. The evaluation method used in the present invention is as follows.
(arithmetic mean height (Sa), maximum protrusion height (P), maximum valley depth (V), maximum section height (St))
Is a value measured by a non-contact surface shape measuring system (Ryoka Systems Inc. manufactured by VertScan R550H-M100) under the following conditions. The arithmetic average height (Sa) was determined by measuring the maximum protrusion height (P) and the maximum valley depth (V) 7 times using an average value of 5 measurements, and using a maximum value of 5 times excluding the maximum value and the minimum value. The maximum section height (St) takes a value that adds the absolute value of the maximum protrusion height (P) and the maximum valley depth (V).
(measurement conditions)
Measurement mode: WAVE mode
Objective lens: 10 times of
0.5 Tube lens
Measurement area 936. Mu.m.times.702. Mu.m
(analysis conditions)
Face correction: correction for 4 times
Supplementary treatment: complete replenishment of
Filter processing: gaussian cut-off value 50 μm
(surface free energy)
The contact angle was measured by forming droplets of water (droplet amount: 1.8. Mu.L) and diiodomethane (droplet amount: 0.9. Mu.L) on the release surface of the release film with a contact angle meter (fully automatic contact angle meter DM-701, manufactured by Kyowa interface Co., ltd.) at 25℃and 50% RH. The contact angle was the contact angle after 10 seconds after each liquid was dropped on the release film. The contact angle data of water and diiodomethane obtained by the above method was calculated according to the theory "Owens and Wendt", and the component γh was obtained based on the dispersed component γd of the free energy of the surface of the release film, the hydrogen bond, and the dipole-dipole interaction, and the total of the components was taken as the free energy γs of the surface. In this calculation, analysis software within the present contact angle meter software (FAMAS) was used.
(Water adhesion energy)
Water (10. Mu.L in drop amount) was dropped onto the release surface of the release film at 25℃and 50% RH using a contact angle meter (fully automatic contact angle meter DM-701, manufactured by Kyowa Kagaku Co., ltd.) and the table was continuously tilted 2 seconds after the drop, and the contact angle was measured at each tilt of 1 degree. Further, the landing energy was calculated by determining that the tilt angle when moving 5 dots from the droplet position of 0 ° was the slip angle. In this calculation, analysis software within the present contact angle meter software (FAMAS) was used.
(film thickness)
Embedding the cut laminated film malformed resin, and carrying out ultrathin slicing by using an ultrathin slicer. Then, the film thickness of each layer of the laminated film was measured from the observed TEM image by observation with a JEM2100 transmission electron microscope manufactured by japan electron system at 20000 times of direct magnification.
(peel force)
The laminated film was cut into a strip shape of Cheng Kuandu mm and 150mm in length, one end of the base film was fixed, one end of the resin sheet was carried, the resin sheet side was stretched at a speed of 300 mm/min, and the T-shaped peel strength was measured. A tensile tester ("AUTOGRAPH AG-X" manufactured by Shimadzu corporation) was used for the measurement. The measurement value was an average value of 5 measurements.
The peelability was evaluated from the measured peeling force on the basis of the following.
And (2) the following steps: can be peeled off with a low peeling force of 100mN/25mm or less, and can be peeled off without cracking in a film
And delta: the peeling can be performed with a peeling force of 300mN/25mm wide or less and more than 100mN/25mm wide.
Delta: the peeling can be performed with a peeling force of more than 300mN/25mm and a width of 800mN/25mm or less. At the extremely thin film thickness portion, a part may be broken
X: peeling cannot be performed.
(static Friction coefficient and sliding evaluation)
The coefficient of static friction of the resin sheet was measured as follows, and the slidability was evaluated.
The resin sheet was peeled from the laminated film and fixed to the bottom surface of a metal rectangular parallelepiped having a weight of 1.4Kg so that the surface (2) of the resin sheet was present. Then, the resin sheet was fixed to the flat metal plate with an adhesive tape so that the surface (1) of the resin sheet appeared. The metallic rectangular parallelepiped was placed so that the surface (1) was in contact with the surface (2), and the static friction coefficient was measured at a tensile speed of 200 mm/min under the condition of 65% RH at 23 ℃.
The sliding property is determined based on the following criteria.
：0.1<μs≤0.8
：0.8<μs≤1.5
X: exceeding 1.5, or having a coefficient of friction too high to be measured
(electric characteristics)
The aluminum deposition layers of the films were provided on both sides of the resin sheet peeled from the base film, and the dielectric breakdown voltage (V/. Mu.m) was measured at room temperature. The average value at 10 points was used for evaluation with the following criteria.
And (2) the following steps: dielectric breakdown voltage (BDV value) of 300V/μm or more
Delta: dielectric breakdown voltage of 200V/μm or more
X: dielectric breakdown voltage lower than 200V/μm
(preparation of polyethylene terephthalate pellets (PET (I))
As the esterification reaction apparatus, a continuous esterification reaction apparatus comprising a 3-stage complete mixing tank having a stirring device, a dephlegmator, a raw material inlet and a product outlet was used. TPA (terephthalamide)Acid) was set to 2 tons/hour, EG (ethylene glycol) was set to 2 moles per 1 mole of TPA, antimony trioxide was set to 160ppm relative to the atoms of PET and Sb produced, and these slurries were continuously fed to the 1 st esterification reactor of the esterification reactor to carry out the reaction at normal pressure with an average residence time of 4 hours and 255 ℃. Then, the reaction product in the 1 st esterification reaction vessel was continuously taken out of the system, supplied to the 2 nd esterification reaction vessel, and EG left from the 1 st esterification reaction vessel at 8 mass% relative to the produced PET was supplied, and EG solution containing magnesium acetate tetrahydrate in an amount of 65ppm relative to the produced PET and Mg atoms and EG solution containing TMPA (trimethyl phosphate) in an amount of 40ppm relative to the produced PET and P atoms were added, and the reaction was carried out at an average residence time of 1 hour and 260 ℃. Next, the reaction product of the 2 nd esterification reaction vessel was continuously taken out of the system, supplied to the 3 rd esterification reaction vessel, and was dispersed under 39MPa (400 kg/cm by Nippon Seiki Co., ltd.) with a high-pressure dispersing machine (Japanese Kogyo Co., ltd.) 2 ) 0.2 mass% of porous colloidal silica having an average particle diameter of 0.9 μm, which had been subjected to dispersion treatment for an average treatment number of 5 passes, and 0.4 mass% of synthetic calcium carbonate having an average particle diameter of 0.6 μm, which had been obtained by adhering 1 mass% of an ammonium salt of polyacrylic acid to unit calcium carbonate, were each added as 10% EG slurry, and reacted at 260℃under normal pressure with an average residence time of 0.5 hours. The esterification reaction product produced in the 3 rd esterification reactor was continuously fed to a 3-stage continuous polycondensation reactor, subjected to polycondensation, filtered by a filter in which 95% of stainless steel fibers having a separation diameter of 20 μm were sintered, subjected to ultrafiltration, extruded into water, cooled, and cut into pellets, to obtain PET pellets having an intrinsic viscosity of 0.60dl/g (hereinafter abbreviated as PET (I)). The lubricant content in the PET pellets was 0.6% by mass.
(preparation of polyethylene terephthalate pellets (PET (II))
On the other hand, in the production of the above PET pellets, PET pellets having an intrinsic viscosity of 0.62dl/g (hereinafter, abbreviated as PET (II)) which do not contain particles such as calcium carbonate and silica were obtained.
(preparation of polyethylene terephthalate pellets (PET (III))
PET pellets (hereinafter abbreviated as PET (III)) were obtained in the same manner as PET (I) except that the type and content of PET (I) particles were changed to 0.75% by mass of synthetic calcium carbonate having an average particle diameter of 0.9 μm, in which 1% by mass of an ammonium salt of polyacrylic acid was attached to the unit calcium carbonate. The lubricant content in the PET pellets was 0.75% by mass.
(production of substrate film X1)
These PET pellets were dried, melted at 285℃and then subjected to a second filtration stage of 95% of a sintered stainless steel fiber filter having a separation diameter of 15 μm and 95% of a sintered stainless steel particle filter having a separation diameter of 15 μm by another melt extruder, melted at 290℃and joined in a feed block, and then laminated so that PET (I) became a surface layer B, PET (II) and became a surface layer A, and extruded (cast) at a rate of 45 m/min into a sheet, and then subjected to an electrostatic sealing/cooling on a casting drum at 30℃to obtain an unstretched polyethylene terephthalate sheet having an intrinsic viscosity of 0.59 dl/g. The layer ratio was adjusted so that the discharge amount of each extruder became PET (I)/PET (II) =60%/40%. Then, the unstretched sheet was heated in an infrared heater and stretched in the machine direction by a factor of 3.5 at a roll temperature of 80℃according to the difference in speed between rolls. Thereafter, the resultant was introduced into a tenter frame, and stretched at 140℃in the transverse direction by 4.2 times. Next, in the heat-setting zone, heat treatment was performed at 210 ℃. Thereafter, a relaxation treatment of 2.3% was performed at 170℃in the transverse direction to obtain a base film X1 of a biaxially stretched polyethylene terephthalate film having a thickness of 25. Mu.m. The obtained substrate film X1 had a Sa of 2nm and a Sa of 29nm in the surface layer B.
(production of substrate film X2 having Release layer)
The surface layer a of the base film X1 obtained in the above was coated with the release coating liquid Y1 described below so that the wet film thickness became 5 μm by the reverse gravure coating method, and dried/cured in a hot air drying oven at 120 ℃ for 30 seconds to obtain a base film X2 with a release layer. The Sa of the release layer surface was 2nm.
(Release coating liquid Y1)
Toluene 48 parts by mass
Methyl ethyl ketone 48 parts by mass
Silicone resin composition (1)
(Heat-curable silicone coating material, si-H/Si-Vy=3.0, solid content 30% by mass)
3 parts by mass
SRX212P Catalyst (Dow Toray Co., ltd. Pt-based immobilized Catalyst)
0.1 part by mass
(production of substrate film X3 having Release layer)
The thickness was adjusted by changing the casting speed without changing the layer constitution and stretching conditions similar to those of the base film X1, and a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was produced, and a release layer similar to X2 was provided, thereby obtaining a base film X3. The Sa of the surface layer A of the obtained film X3 was 3nm, and the Sa of the surface layer B was 29nm.
(method for producing a substrate film X4 having a mold Release layer)
As the base film X4, a film having a release layer similar to X2 provided on a surface layer a of a4100 (Cosmoshine (registered trademark), manufactured by eastern spinning corporation) having a thickness of 25 μm was used. A4100 is configured as follows: the film contains substantially no particles, and a coating layer containing particles is provided in an in-line coating manner only on the surface layer B side. The Sa of the surface layer A of the base film X4 was 1nm, and the Sa of the surface layer B was 2nm.
(method for producing a substrate film X5 having a mold Release layer)
As the base film X5, a film of E5101 (TOYOBO ESTER (registered trademark) film, manufactured by TOYOBO co., ltd.) having a thickness of 25 μm and having a release layer similar to X2 provided on the surface layer a were used. E5101 is a structure including particles in the surface layers a and B of the film. The Sa of the surface layer A of the base film X5 was 25nm, and the Sa of the surface layer B was 25nm.
(method for producing substrate film X6 having Release layer)
The following release coating liquid Y2 was applied to the surface layer a of the base film X1 by reverse gravure coating so that the wet film thickness became 5 μm, and dried and cured in a hot air drying oven at 120 ℃ for 30 seconds to obtain a base film X6 with a release layer. The Sa of the release layer surface was 2nm.
(Release coating liquid Y2)
Toluene 48 parts by mass
Methyl ethyl ketone 48 parts by mass
Silicone resin composition (2)
(Heat-curable silicone coating material, si-H/Si-Vy=1.0, solid content 30% by mass)
3 parts by mass
SRX212P Catalyst (Dow Toray Co., ltd. Pt-based immobilized Catalyst)
0.1 part by mass
(method for producing a substrate film X7 having a mold Release layer)
The following release coating liquid Y3 was applied to the surface layer a of the base film X1 by the reverse gravure coating method so that the wet film thickness became 5 μm, and dried and cured in a hot air drying oven at 120 ℃ for 30 seconds to obtain a base film X7 with a release layer. The Sa of the release layer surface was 2nm.
(Release coating liquid Y3)
Toluene 48 parts by mass
Methyl ethyl ketone 48 parts by mass
Silicone resin composition (3)
(Heat-curable silicone coating material, si-H/Si-Vy=2.2, solid content 30% by mass)
3 parts by mass
SRX212P Catalyst (Dow Toray Co., ltd. Pt-based immobilized Catalyst)
0.1 part by mass
Example 1
The resin solution Z1 was applied to the surface layer a of the base film X2 by the reverse gravure coating method so that the film thickness of the dried resin sheet became 3 μm, and dried at 120 ℃ for 10 seconds in a hot air drying furnace, whereby the resin sheet was molded to prepare a laminated film. (2 seconds after coating and before entering the drying oven). Details are shown in tables 1 and 2.
(resin solution Z1)
Methyl ethyl ketone 41.3 parts by mass
Tetrahydrofuran 22.5 parts by mass
PKHB lysate (solid content 40% by mass) 30.6 parts by mass
(phenoxy resin manufactured by Gabriel Phenoxies Co., ltd., mw 32000)
* The dissolution solution is prepared by dissolving phenoxy resin in tetrahydrofuran
Milliconate MR-200.3 parts by mass
(manufactured by Tosoh Co., ltd., isocyanate crosslinking agent, viscosity 200 mPas, solid content 99% by mass)
BYK-370.4 parts by mass
(Silicone surfactant manufactured by BYK Japan Co., ltd.)
Examples 2 to 3
A laminated film was produced in the same manner as in example 1, except that the base film was changed to that shown in table 1.
Example 4
A laminated film was produced in the same manner as in example 1, except that the resin component (a) was changed to the resin solution Z6 having a different weight average molecular weight (Mw).
(resin solution Z6)
Methyl ethyl ketone 41.3 parts by mass
Tetrahydrofuran 22.5 parts by mass
PKHJ solution (solid content 40% by mass) 30.6 parts by mass
(phenoxy resin, mw57000, manufactured by Gabriel Phenoxies Co., ltd.)
* The dissolution solution is prepared by dissolving phenoxy resin in tetrahydrofuran
Milliconate MR-200.3 parts by mass
(manufactured by Tosoh Co., ltd., isocyanate crosslinking agent, viscosity 200 mPas, solid content 99% by mass)
BYK-370.4 parts by mass
(Silicone surfactant manufactured by BYK Japan Co., ltd.)
Example 5
A laminated film was produced in the same manner as in example 1, except that the type of the crosslinking agent was changed, and thus, the resin solution Z2 was changed.
(resin solution Z2)
Methyl ethyl ketone 41.3 parts by mass
Tetrahydrofuran 22.5 parts by mass
PKHB lysate (solid content 40% by mass) 30.6 parts by mass
(phenoxy resin manufactured by Gabriel Phenoxies Co., ltd., mw 32000)
* The dissolution solution is prepared by dissolving phenoxy resin in tetrahydrofuran
Milliconate MR-400.3 parts by mass
(manufactured by Tosoh Co., ltd., isocyanate crosslinking agent, viscosity 600 mPas, solid content 99% by mass)
BYK-370.4 parts by mass
(Silicone surfactant manufactured by BYK Japan Co., ltd.)
Example 6
A laminated film was produced in the same manner as in example 1, except that the type of the crosslinking agent was changed, and thus, the resin solution Z3 was changed.
(resin solution Z3)
Methyl ethyl ketone 41.3 parts by mass
Tetrahydrofuran 22.5 parts by mass
PKHB lysate (solid content 40% by mass) 30.6 parts by mass
(phenoxy resin manufactured by Gabriel Phenoxies Co., ltd., mw 32000)
* The dissolution solution is prepared by dissolving phenoxy resin in tetrahydrofuran
Milliconate MTL 5.3 parts by mass
(manufactured by Tosoh Co., ltd., isocyanate crosslinking agent, viscosity 50 mPas, solid content 99% by mass)
BYK-370.4 parts by mass
(Silicone surfactant manufactured by BYK Japan Co., ltd.)
Example 7
A laminated film was produced in the same manner as in example 1, except that the ratio of the resin to the crosslinking agent was changed to the resin solution Z4.
(resin solution Z4)
Methyl ethyl ketone 41.3 parts by mass
Tetrahydrofuran 19.9 parts by mass
35.0 parts by mass of PKHB solvent (solid content 40% by mass)
(phenoxy resin manufactured by Gabriel Phenoxies Co., ltd., mw 32000)
* The dissolution solution is prepared by dissolving phenoxy resin in tetrahydrofuran
Milliconate MR-200.5 parts by mass
(manufactured by Tosoh Co., ltd., isocyanate crosslinking agent, viscosity 200 mPas, solid content 99% by mass)
BYK-370.4 parts by mass
(Silicone surfactant manufactured by BYK Japan Co., ltd.)
Example 8
A laminated film was produced in the same manner as in example 1, except that the ratio of the resin to the crosslinking agent was changed to the resin solution Z5.
(resin solution Z5)
Methyl ethyl ketone 41.3 parts by mass
Tetrahydrofuran 17.3 parts by mass
PKHB lysate (solid content 40% by mass) 39.4 parts by mass
(phenoxy resin manufactured by Gabriel Phenoxies Co., ltd., mw 32000)
* The dissolution solution is prepared by dissolving phenoxy resin in tetrahydrofuran
Milliconate MR-200.8 parts by mass
(manufactured by Tosoh Co., ltd., isocyanate crosslinking agent, viscosity 200 mPas, solid content 99% by mass)
BYK-370.4 parts by mass
(Silicone surfactant manufactured by BYK Japan Co., ltd.)
Examples 9 to 11
A laminated film was produced in the same manner as in example 1, except that the base film described in table 1 was used instead.
Examples 12 to 13
A laminated film was produced in the same manner as in example 1, except that the drying temperature of the resin sheet was changed to the temperature shown in table 1.
Comparative example 1
A laminated film was produced in the same manner as in example 1, except that the base film was changed to X1 without a release layer.
Comparative example 2
A laminated film was produced in the same manner as in example 1, except that the resin solution was changed to the resin solution Z6 containing no crosslinking agent.
(resin solution Z6)
Methyl ethyl ketone 41.3 parts by mass
Tetrahydrofuran 14.7 parts by mass
43.8 parts by mass of PKHB solvent (solid content 40% by mass)
(phenoxy resin manufactured by Gabriel Phenoxies Co., ltd., mw 32000)
* The dissolution solution is prepared by dissolving phenoxy resin in tetrahydrofuran
BYK-370.4 parts by mass
(Silicone surfactant manufactured by BYK Japan Co., ltd.)
Comparative example 3
A laminated film was produced in the same manner as in example 1, except that the resin sheet was formed so that the maximum section height (St) of the surface (1) of the resin sheet became 75 nm.
The base film used in each example was cured at 40℃for 3 days after the release layer was processed. The obtained laminated film was also cured at 40℃for 3 days and then evaluated.
TABLE 1
TABLE 2
The laminate sheet of the present invention obtained in the examples can provide a resin sheet which can improve transparency and the like in optical applications, for example, and can also exhibit high smoothness. In addition, the high smoothness and the high sliding property can be combined, for example, scratch can be prevented from being introduced in the conveying process and the like, and the reduction of the yield can be avoided.
In addition, for example, in electronic component applications such as thin film capacitor applications, a resin sheet exhibiting high smoothness can be provided, and the resin sheet can improve electrical characteristics such as dielectric breakdown voltage. In addition, the high smoothness and the high sliding property can be combined, and for example, winding misalignment, mixing of wrinkles, and the like when the dielectric resin sheet is wound on the roller can be suppressed, and excellent winding property can be exhibited. Therefore, transportation or the like can be performed in a state where excellent capacitor performance is maintained.
Further, the resin sheet obtained in the present invention contains substantially no particles, and thus, insufficient transparency such as an increase in internal haze can be avoided. In addition, the problem that the amount of particles transferred to the resin sheet becomes uneven can be avoided, and good slidability can be exhibited.
In contrast, comparative example 1 does not have the release layer of the present invention, and therefore the releasability of the resin sheet is extremely poor, and the evaluation of the resin sheet is not possible. In comparative example 2, since the resin sheet forming composition does not contain a crosslinking agent, it is shown that the slidability of the resin sheet is deteriorated.
In comparative example 3, the maximum section height (St) of the surface (1) of the resin sheet is not within the scope of the present invention, and therefore, in particular, the result of deterioration of the slidability of the resin sheet is shown.
Industrial applicability
The present invention relates to a laminated film in which resin sheets are laminated. In particular, the present invention relates to a laminated film in which resin sheets for electronic components and optical applications are laminated.
Description of the reference numerals
10. Substrate film
11. Release layer
12. Resin sheet
13. Surface of resin sheet (1)
14. Surface of resin sheet (2)
Claims (7)
1. A laminated film, comprising: a polyester base film, a release layer disposed on at least one side of the base film, and a resin sheet disposed on the opposite side of the release layer from the base,
The laminated film satisfies the following (1) to (6):
(1) The resin sheet is obtained by curing a resin sheet-forming composition comprising at least a resin component (A) and a crosslinking agent (B),
(2) The resin sheet is substantially free of particles,
(3) The film thickness (t 1) of the resin sheet is 1 μm or more and 20 μm or less,
(4) The arithmetic average height (Sa) of the surface (1) of the resin sheet is 2nm or more and 30nm or less,
(5) The maximum section height (St) of the surface (1) of the resin sheet is 80nm to 1000nm,
(6) The coefficient of static friction measured by overlapping the surface (1) of the resin sheet on the side opposite to the release layer surface with the surface (2) of the resin sheet on the release layer side is 1.5 or less.
2. The laminated film according to claim 1, wherein the crosslinking agent (B) contained in the resin sheet-forming composition is liquid at 30 ℃.
3. The laminated film according to claim 1 or 2, wherein the cross-linking agent (B) contained in the resin sheet is contained in an amount of 10 mass% or more in the entire resin sheet.
4. The laminated film according to any one of claims 1 to 3, wherein the weight average molecular weight of the resin component (A) contained in the resin sheet is 10000 or more.
5. The laminated film according to any one of claims 1 to 4, wherein the surface free energy of the release layer surface is 40mJ/m 2 The adhesion energy is 3.5mJ/m 2 The above.
6. The laminated film according to any one of claims 1 to 5, wherein an arithmetic average height (Sa) of a release layer side surface of the base film is 20nm or less and a maximum protrusion height (P) is 500nm or less.
7. A method for producing a laminated film according to any one of claims 1 to 6, wherein the resin sheet is coated and formed on the base film by a solution film-forming method.
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| JP2021-010510 | 2021-01-26 | ||
| JP2021010510 | 2021-01-26 | ||
| PCT/JP2022/002388 WO2022163569A1 (en) | 2021-01-26 | 2022-01-24 | Laminated film and method for manufacturing laminated film |
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| CN116761723A true CN116761723A (en) | 2023-09-15 |
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| JP (6) | JP7380910B2 (en) |
| KR (1) | KR20230116054A (en) |
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| WO2022163569A1 (en) * | 2021-01-26 | 2022-08-04 | 東洋紡株式会社 | Laminated film and method for manufacturing laminated film |
| WO2024019038A1 (en) * | 2022-07-20 | 2024-01-25 | 東洋紡株式会社 | Laminated film and method for producing laminated film |
| WO2024019039A1 (en) * | 2022-07-20 | 2024-01-25 | 東洋紡株式会社 | Laminated film and method for producing laminated film |
| WO2024019037A1 (en) * | 2022-07-20 | 2024-01-25 | 東洋紡株式会社 | Laminated film roll and method for manufacturing laminated film roll |
| WO2024058163A1 (en) * | 2022-09-16 | 2024-03-21 | 東洋紡株式会社 | Mold release film and method for producing same |
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| JP2784453B2 (en) * | 1989-02-21 | 1998-08-06 | 藤森工業株式会社 | Adhesive type heat-resistant laminated sheet and method for producing the same |
| JP2009013384A (en) * | 2007-07-09 | 2009-01-22 | Nippon Paint Co Ltd | Easily slipable anti-blocking photocurable resin composition, anti-blocking structure with the same coated and cured on base material, and method of manufacturing the same |
| JP5774857B2 (en) | 2011-01-14 | 2015-09-09 | ユニチカ株式会社 | Slippery polyester film and method for producing the same |
| KR101295705B1 (en) * | 2011-04-25 | 2013-08-16 | 도레이첨단소재 주식회사 | Phenoxy resin composition for transparent plastic substrate and transparent plastic substrate using thereof |
| JP6085185B2 (en) | 2013-02-06 | 2017-02-22 | 株式会社ダイセル | Release film and laminate for manufacturing fuel cell, and method for manufacturing fuel cell |
| KR20150061803A (en) * | 2013-11-28 | 2015-06-05 | 주식회사 삼정산업 | Steel pallet |
| KR101561287B1 (en) * | 2014-02-12 | 2015-10-16 | 도레이첨단소재 주식회사 | Rtm molding method using sueface protecting layer |
| JP6340855B2 (en) | 2014-03-22 | 2018-06-13 | 三菱ケミカル株式会社 | Film laminate |
| KR101653369B1 (en) * | 2014-11-24 | 2016-09-01 | 도레이첨단소재 주식회사 | Thermally conductive adhesive composition and thermally conductive adhesive thin sheet therefrom |
| JP6800129B2 (en) * | 2017-11-07 | 2020-12-16 | 古河電気工業株式会社 | Manufacturing method of semiconductor package using film-like adhesive and film-like adhesive |
| JP6981205B2 (en) | 2017-11-24 | 2021-12-15 | コニカミノルタ株式会社 | Optical film and polarizing plate |
| KR102528364B1 (en) * | 2017-11-30 | 2023-05-03 | 미쯔비시 케미컬 주식회사 | Manufacturing method of release film and laminate |
| JP7312528B2 (en) * | 2018-02-16 | 2023-07-21 | 東洋インキＳｃホールディングス株式会社 | Touch panel device and touch panel |
| TWI848029B (en) * | 2018-12-20 | 2024-07-11 | 日商東洋紡股份有限公司 | Release film, method for producing release film, method for producing ceramic green body, and method for producing ceramic capacitor |
| WO2021005823A1 (en) * | 2019-07-10 | 2021-01-14 | 株式会社村田製作所 | Film capacitor and film for film capacitor |
| KR102190888B1 (en) | 2020-04-07 | 2020-12-15 | 삼성전자 주식회사 | Display apparatus and control method of the same |
| JP7494630B2 (en) * | 2020-07-29 | 2024-06-04 | 東洋紡株式会社 | Laminated Film |
| WO2022163569A1 (en) | 2021-01-26 | 2022-08-04 | 東洋紡株式会社 | Laminated film and method for manufacturing laminated film |
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| JP7380808B2 (en) | 2023-11-15 |
| JP7380940B2 (en) | 2023-11-15 |
| KR20230116054A (en) | 2023-08-03 |
| JP7380910B2 (en) | 2023-11-15 |
| JP2023115323A (en) | 2023-08-18 |
| JP7380807B2 (en) | 2023-11-15 |
| JP7409465B2 (en) | 2024-01-09 |
| WO2022163569A1 (en) | 2022-08-04 |
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| JP2023120439A (en) | 2023-08-29 |
| JP2023001361A (en) | 2023-01-04 |
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