WO2017200056A1 - 離型フィルム - Google Patents
離型フィルム Download PDFInfo
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- WO2017200056A1 WO2017200056A1 PCT/JP2017/018726 JP2017018726W WO2017200056A1 WO 2017200056 A1 WO2017200056 A1 WO 2017200056A1 JP 2017018726 W JP2017018726 W JP 2017018726W WO 2017200056 A1 WO2017200056 A1 WO 2017200056A1
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- Prior art keywords
- release
- film
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Classifications
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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
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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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- 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
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static 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
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
Definitions
- the present invention relates to a release film.
- a release film based on a polyester film is bonded through an adhesive layer for various uses (capacitive touch panel, polarizing plate for LCD, retardation plate, PDP component, organic EL component, Used in various display components, various optical applications, etc.).
- the substrate-less double-sided PSA sheet consists of a laminate structure in which a light release film with a relatively low peel strength and a heavy release film with a relatively high peel strength are laminated on both sides of the adhesive layer. After the removal, the double-sided pressure-sensitive adhesive sheet becomes only the pressure-sensitive adhesive layer having no supporting substrate.
- the light release film is peeled off, and one surface of the exposed pressure-sensitive adhesive layer is bonded to the object surface of the other side to be bonded.
- a processing step in which the other surface of the exposed pressure-sensitive adhesive layer is bonded to a different object surface, whereby the objects are surface-bonded is exemplified.
- the baseless double-sided pressure-sensitive adhesive sheet has attracted attention because of its good workability, and its application is expanding. It is also used for members for various optical applications such as mobile phones.
- a capacitive touch panel is rapidly expanding its application as an information terminal by a multi-touch operation in which a screen operation is performed with two fingers. Since the capacitive touch panel tends to have a thicker printing step than the resistive film method, a proposal has been made to eliminate the printing step by thickening the adhesive layer.
- the pressure-sensitive adhesive layer is made thick, when the release film is peeled off, a part of the pressure-sensitive adhesive layer adheres to the release film, or air bubbles are mixed into the part of the pressure-sensitive adhesive layer transferred to the release film.
- Patent Documents 1 to 3 propose that the release rate of the release layer be set to a certain level or less.
- the release films described in Patent Documents 1 to 3 have a problem that light release is insufficient and cannot be handled at all.
- Patent Document 4 and Patent Document 5 propose an antistatic layer containing a ⁇ -electron conjugated conductive polymer.
- the antistatic property is good, but when a release layer is provided on the antistatic layer, the adhesion between the release layer and the antistatic layer may not always be sufficient. is there.
- the present invention has been made in view of the above circumstances, and the first problem to be solved is that the releasability from the pressure-sensitive adhesive is good regardless of the peeling speed during use, and the pressure-sensitive adhesive is transferred to a member. It is in providing a release film with little property.
- the second problem to be solved by the present invention is that the release property from the pressure-sensitive adhesive is good, the transfer property of the pressure-sensitive adhesive to the member is small, and the antistatic property is good regardless of the peeling speed at the time of use. To provide a film.
- the present invention provides a first polydimethylsiloxane having a weight average molecular weight of 500 or more and 30000 or less and having at least one alkenyl group in one molecule on at least one surface of a polyester film, and a weight average molecular weight.
- Silicone release layer comprising a release agent composition containing 150 to 10,000 and a second polydimethylsiloxane having at least one hydrosilyl group in one molecule and a platinum catalyst. It is a release film characterized by having (1st invention).
- the present invention is a release film in which an application layer and a release layer are sequentially provided on at least one surface of a polyester film, and the application layer comprises a conductive compound (A) and a binder polymer (B). And the release layer has a weight average molecular weight of 500 or more and 30000 or less, a first polydimethylsiloxane having at least one alkenyl group in one molecule, and a weight average molecular weight of 150 or more and 10,000 or less.
- a polyester film comprising a silicone-based release layer comprising a release agent composition containing a second polydimethylsiloxane having at least one hydrosilyl group in one molecule and a platinum-based catalyst. (Second invention).
- the peeling force between the surface of the silicone-based release layer and the adhesive tape at a peeling speed of 300 mm / min is 9 g / 25 mm or less.
- the release film of the present invention is, for example, a substrate-less double-sided pressure-sensitive adhesive sheet for touch panel manufacturing, a capacitive touch panel manufacturing, and the like, for manufacturing LCD components such as polarizing plates and retardation plates used in liquid crystal displays (LCD).
- LCD components such as polarizing plates and retardation plates used in liquid crystal displays (LCD).
- the first invention of the present application has a layer structure of polyester film / silicone release layer
- the second invention of the present application has a layer structure of polyester film / coating layer / silicone release layer.
- the polyester film, the coating layer, and the silicone release layer will be described in this order.
- polyester film When using a release film for adhesive protection applications, a part of the adhesive layer may adhere to the release film during peeling. If the pressure-sensitive adhesive adheres to the release film, the surface shape of the pressure-sensitive adhesive layer becomes rough, and there is a possibility that the adhesiveness with other members such as an optical member may be adversely affected.
- the base material of the release film is paper
- a polyester film is used in the present invention because not only adhesion of the adhesive during peeling but also migration is insufficient.
- the polyester film referred to in the present invention is a film obtained by stretching a sheet melt-extruded from an extrusion die according to a so-called extrusion method.
- the polyester constituting the above film refers to a polymer containing an ester group obtained by polycondensation from dicarboxylic acid and diol or from hydroxycarboxylic acid.
- Dicarboxylic acids include terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc.
- diols include ethylene glycol, 1,4-butane. Examples include diol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, and polyethylene glycol.
- hydroxycarboxylic acid examples include p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. be able to.
- Typical examples of such polymers include polyethylene terephthalate and polyethylene-2,6-naphthalate.
- particles are preferably blended mainly for the purpose of imparting slipperiness and preventing the occurrence of scratches in each step.
- the kind of the particle to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness. Specific examples thereof include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, and phosphoric acid. Examples of the particles include magnesium, kaolin, aluminum oxide, and titanium oxide. Further, heat-resistant organic particles as described in JP-B-59-5216, JP-A-59-217755 and the like may be used.
- thermosetting urea resins examples include thermosetting urea resins, thermosetting phenol resins, thermosetting epoxy resins, benzoguanamine resins, and the like.
- 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 not particularly limited, and any of a spherical shape, a block shape, a rod shape, a flat shape, and the like may be used. Moreover, there is no restriction
- the average particle size of the particles used is usually in the range of 0.01 to 3 ⁇ m, preferably 0.1 to 2 ⁇ m.
- the slipperiness may not be sufficiently imparted.
- the thickness exceeds 3 ⁇ m, transparency may be lowered due to the aggregate of the particles when the film is formed, and it is easy to cause breakage, which causes a problem in terms of productivity. There is.
- the particle content in the polyester is usually 0.001 to 5% by weight, preferably 0.005 to 3% by weight.
- the slipperiness of the film may be insufficient.
- the content exceeds 5% by weight the transparency of the film is insufficient. There is a case.
- the method for adding particles to the polyester layer is not particularly limited, and a conventionally known method can be adopted.
- it can be added at any stage for producing the polyester constituting each layer, but it is preferably added after completion of esterification or transesterification.
- a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material, or a blending of dried particles and a polyester raw material using a kneading extruder is done by methods.
- antioxidants In addition to the above-mentioned particles, conventionally known antioxidants, antistatic agents, thermal stabilizers, lubricants, dyes, pigments, and the like can be added to the polyester film in the present invention as necessary.
- the thickness of the polyester film in the present invention is not particularly limited as long as it can be formed as a film, but is usually in the range of 10 to 350 ⁇ m, preferably 15 to 100 ⁇ m.
- the manufacture example of the polyester film in this invention is demonstrated concretely, it is not limited to the following manufacture examples at all.
- the polyester raw material described above is used, and the molten sheet extruded from the die is cooled and solidified with a cooling roll to obtain an unstretched sheet.
- a cooling roll In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum, and an electrostatic application adhesion method and / or a liquid application adhesion method is preferably employed.
- the obtained unstretched sheet is stretched in the biaxial direction. In that case, first, the unstretched sheet is stretched in one direction by a roll or a tenter type stretching machine.
- the stretching temperature is usually 90 to 140 ° C., preferably 95 to 120 ° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times.
- the film is stretched in the direction perpendicular to the first stretching direction.
- the stretching temperature is usually 90 to 170 ° C.
- the stretching ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times. is there.
- heat treatment is performed at a temperature of 180 to 270 ° C. under tension or relaxation within 30% to obtain a biaxially oriented film.
- a method in which stretching in one direction is performed in two or more stages can be employed. In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges.
- a simultaneous biaxial stretching method is a method in which the above-mentioned unstretched sheet is stretched and oriented in the machine direction and the width direction at a temperature controlled usually at 90 to 140 ° C., preferably 80 to 110 ° C. Is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times in terms of area magnification. Subsequently, heat treatment is performed at a temperature of 170 to 250 ° C. under tension or under relaxation within 30% to obtain a stretched oriented film.
- a conventionally known stretching method such as a screw method, a pantograph method, or a linear driving method can be employed.
- a so-called coating stretching method for treating the film surface during the above-described polyester film stretching step can be performed.
- coating stretching method in-line coating
- coating can be performed simultaneously with stretching and the thickness of the coating layer can be reduced according to the stretching ratio, producing a film suitable as a polyester film. it can.
- the coating layer constituting the release film of the present invention will be described.
- the said coating layer makes it an essential requirement to contain a conductive compound (A) and a binder polymer (B).
- the coating layer constituting the release film of the present invention contains the conductive compound (A) in order to improve the antistatic property and the oligomer precipitation preventing property.
- the conductive compound (A) a polymer obtained by singly or copolymerizing thiophene or a thiophene derivative is preferable, and in particular, a compound made of thiophene or a thiophene derivative is doped with another anionic compound or A compound which has an anionic group in the compound and is self-doped is preferable because it exhibits excellent conductivity.
- a compound obtained by polymerizing the following chemical compound 1 or chemical compound 2 in the presence of a polyanion can be exemplified.
- R 1 and R 2 each independently represents a hydrogen element, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, such as a methyl group, an ethyl group, (Propyl group, isopropyl group, butyl group, cyclohexylene group, benzene group, etc.)
- polythiophene or polythiophene derivatives include compounds in which a functional group is bonded to positions 3 and 4 of the thiophene ring. As described above, a compound in which an oxygen atom is bonded to the 3rd and 4th carbon atoms is preferable.
- the release film of this invention it is preferable that it is a composition containing the said polythiophene and a polyanion in a coating layer, or a composition containing the said polythiophene derivative and a polyanion.
- the polyanion used at the time of polymerization include poly (meth) acrylic acid, polymaleic acid, polystyrene sulfonic acid and the like. These acids may be partially or completely neutralized.
- the binder polymer (B) constituting the coating layer in the present invention is a gel permeation chromatography (GPC) measurement according to a polymer compound safety evaluation flow scheme (November 1985, sponsored by the Chemical Substances Council). It is defined as a polymer compound having a number average molecular weight (Mn) of 1000 or more and having film-forming properties.
- GPC gel permeation chromatography
- the binder polymer (B) constituting the coating layer in the present invention may be a thermosetting resin or a thermoplastic resin as long as it is compatible or mixed and dispersible with thiophene or a thiophene derivative.
- polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate
- polyimides such as polyimide and polyamideimide
- polyamides such as polyamide 6, polyamide 6,6, polyamide 12, and polyamide 11
- polyvinylidene fluoride polyvinyl fluoride, poly Fluorine resin such as tetrafluoroethylene, ethylenetetrafluoroethylene copolymer, polychlorotrifluoroethylene
- vinyl resin such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride
- epoxy resin oxetane resin
- xylene resin Polyurea
- Polyamide silicone Polyure
- the binder polymer (B) may be dissolved in an organic solvent, or may be made into an aqueous solution by adding a functional group such as a sulfo group or a carboxy group. Moreover, you may use together hardening
- curing agents such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc.
- binder polymers (B) at least one selected from polyester resins, acrylic resins, and polyurethane resins is preferable because mixing at the time of preparing the coating liquid is easy.
- a polyurethane resin is particularly preferable.
- the polyester resin used in the present invention is defined as a linear polyester having a dicarboxylic acid component and a glycol component as constituent components.
- Dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, phenylindanedicarboxylic acid, A dimer acid etc. can be illustrated. Two or more of these components can be used.
- a small proportion of unsaturated polybasic acids such as maleic acid, fumaric acid and itaconic acid, and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- ( ⁇ -hydroxyethoxy) benzoic acid.
- the proportion of the unsaturated polybasic acid component or the hydroxycarboxylic acid component is at most 10 mol%, preferably 5 mol% or less.
- glycol component examples include ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, dimethylolpropionic acid.
- polyester resin can be copolymerized with a small amount of a compound having a sulfonate group or a compound having a carboxylic acid group in order to facilitate aqueous liquefaction, which is preferable.
- Examples of the compound having a sulfonate group include 5-sodium sulfoisophthalic acid, 5-ammonium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-methylammonium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, 5-potassium
- Preferable examples include sulfonic acid alkali metal salts such as sulfoisophthalic acid, 4-potassium sulfoisophthalic acid, 2-potassium sulfoisophthalic acid, and sodium sulfosuccinic acid, and sulfonic acid amine salt compounds.
- Examples of the compound having a carboxylate group include trimellitic anhydride, trimellitic acid, pyromellitic anhydride, pyromellitic acid, trimesic acid, cyclobutanetetracarboxylic acid, dimethylolpropionic acid, and monoalkali metal salts thereof.
- Etc. The free carboxyl group is converted into a carboxylate group by allowing an alkali metal compound or an amine compound to act after copolymerization.
- a polyester obtained by selecting one or more compounds from these compounds and synthesizing them by a conventional polycondensation reaction can be used.
- the glass transition temperature (hereinafter sometimes abbreviated as Tg) is preferably 40 ° C. or higher, more preferably 60 ° C. or higher.
- Tg is less than 40 ° C., for the purpose of improving adhesiveness, when the coating thickness of the coating layer is increased, problems such as easy blocking may occur.
- the acrylic resin is a polymer composed of a polymerizable monomer having a carbon-carbon double bond, as typified by acrylic and methacrylic monomers. These may be either a homopolymer or a copolymer. Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) is also included. For example, a block copolymer or a graft copolymer. Furthermore, a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyester solution or a polyester dispersion is also included.
- a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyurethane solution or polyurethane dispersion is also included.
- a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in another polymer solution or dispersion is also included.
- the polymerizable monomer having a carbon-carbon double bond is not particularly limited, but representative compounds such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid.
- Various carboxyl group-containing monomers and their salts 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydroxyl fumarate, monobutylhydroxy
- Various hydroxyl-containing monomers such as itaconate; various (meth) acrylic such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate Acid esters; (meth) a Riruamido, various nitrogen-containing vinyl monomers such as diacetone acrylamide, N- methylol acryl
- polymerizable monomers as shown below can be copolymerized. That is, various styrene derivatives such as styrene, ⁇ -methylstyrene, divinylbenzene and vinyltoluene, various vinyl esters such as vinyl acetate and vinyl propionate; ⁇ -methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, Various silicon-containing polymerizable monomers such as methacryloyl silicon macromer; phosphorus-containing vinyl monomers; vinyl chloride, biliden chloride, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, chlorotrifluoroethylene And various vinyl halides such as hexafluoropropylene; and various conjugated dienes such as butadiene.
- styrene derivatives such as styrene, ⁇ -methylstyrene, divinylbenzene and vinyl
- the glass transition temperature (hereinafter sometimes abbreviated as Tg) is preferably 40 ° C. or higher, more preferably 60 ° C. or higher.
- Tg is less than 40 ° C., for the purpose of improving adhesiveness, when the coating thickness of the coating layer is increased, problems such as easy blocking may occur.
- the polyurethane resin in the present invention refers to a polymer compound having a urethane bond in the molecule.
- a water-dispersible or water-soluble urethane resin is preferable.
- a hydrophilic groups a carboxylic acid group or a sulfonic acid group is preferably used from the viewpoint of improving the physical properties and adhesion of the coating film.
- polyol is preferably used, and examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination.
- polyether polyols examples include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.
- 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 alcohol 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- , 3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexane Diol, 1,9-nonanediol
- polycarbonate polyols examples include polycarbonate diols obtained by dealcoholization reaction from polyhydric alcohols and dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and the like, such as poly (1,6-hexylene) carbonate, poly ( And 3-methyl-1,5-pentylene) carbonate.
- polyisocyanate compound used for obtaining the urethane resin examples include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′.
- 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, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl Methanzi Isocyanate, alicyclic diisocyanates such as isopropylidene dicyclohexyl diisocyanates. These may be used alone or in combination.
- chain extender When synthesizing a urethane resin, a conventionally known chain extender may be used, and the chain extender is not particularly limited as long as it has two or more active groups that react with an isocyanate group.
- a chain extender having two hydroxyl groups or amino groups is generally used.
- chain extender having two hydroxyl groups examples include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. It can be mentioned that glycols such as glycol are exemplified.
- chain extender having two amino groups examples include aromatic diamines such as tolylenediamine, xylylenediamine, diphenylmethanediamine, ethylenediamine, propylenediamine, 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- Aliphatic diamines such as decane diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidine cyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1 , 3-Bisaminomethylcyclohexa And alicyclic diamines such as
- the coating layer constituting the release film preferably contains a polyurethane resin for the purpose of improving the adhesion to the release layer.
- the coating liquid for providing the coating layer in the present invention is further selected from the group of glycerin (C1), polyglycerin (C2), glycerin or an alkylene oxide adduct (C3) of polyglycerin as component (C). It is preferred to contain more than one compound or derivative thereof. The average number of glycerin units in the molecule is more preferably in the range of 2-20.
- the alkylene oxide adduct of glycerin or polyglycerin has a structure obtained by addition polymerization of alkylene oxide or a derivative thereof to the hydroxyl group of glycerin or polyglycerin.
- the structure of the alkylene oxide to be added or its derivative may be different for each hydroxyl group of the glycerin or polyglycerin skeleton. Moreover, it is sufficient that it is added to at least one hydroxyl group in the molecule, and it is not necessary that alkylene oxide or a derivative thereof is added to all hydroxyl groups.
- a preferable alkylene oxide or derivative thereof is a structure containing an ethylene oxide or propylene oxide skeleton. If the alkyl chain in the alkylene oxide structure becomes too long, the hydrophobicity becomes strong, the uniform dispersibility in the coating solution deteriorates, and the antistatic property and transparency of the coating film tend to deteriorate. Particularly preferred is ethylene oxide.
- the copolymerization ratio of alkylene oxide or its derivative to the glycerin or polyglycerin skeleton is not particularly limited, but when the glycerin or polyglycerin moiety is 1 in molecular weight ratio, The alkylene oxide moiety is preferably 20 or less, more preferably 10 or less. When the ratio of the alkylene oxide or its derivative to the glycerin or polyglycerin skeleton is larger than this range, the characteristics of the ordinary polyalkylene oxide are close to those obtained, and the effects of the present invention may not be sufficiently obtained. is there.
- particularly preferred embodiments include polyglycerol (C2) and glycerol or an alkylene oxide adduct of polyglycerol (C3).
- polyglycerin (C2) those in which n is 2 to 20 in the following chemical formula 3 are particularly preferred.
- the blending ratio of component (C) in the coating layer is in the range of 10 to 90% by weight, more preferably in the range of 20 to 80% by weight. When the said range is less than 10 weight%, applicability
- the weight of the conductive compound (A) in the coating layer is preferably 0.5 mg / m 2 or more, more preferably 1 mg / m 2 or more. Good. When the amount of the conductive compound (A) is 0.5 mg / m 2 or more, sufficient antistatic properties can be obtained.
- the ratio of the conductive compound (A) in the coating layer constituting the release film is not limited, but is preferably 90% by weight or less, more preferably 80% by weight or less, and most preferably with respect to the upper limit. 60% by weight or less. If the ratio of the conductive compound (A) exceeds 90% by weight, the transparency of the coating layer may be insufficient, or the antistatic performance may be insufficient. On the other hand, the lower limit is preferably 1% by weight or more, more preferably 2% by weight or more. When the weight ratio of the conductive compound (A) is less than 1% by weight, the antistatic performance may be insufficient.
- the ratio of the conductive compound (A) to the binder polymer (B) is preferably in the range of 90/10 to 1/99 by weight.
- the range is preferably 70/30 to 1/99, most preferably 50/50 to 2/98. Outside this range, the antistatic performance or the appearance of the coating film tends to deteriorate.
- the coating liquid used in the present invention includes an antifoaming agent, a coating property improver, a thickener, an organic lubricant, a release agent, organic particles, inorganic particles, an antioxidant, an ultraviolet absorber, a foaming agent, a dye, You may contain additives, such as a pigment. These additives may be used alone or in combination of two or more as necessary.
- the coating liquid in the present invention is preferably an aqueous solution or a water dispersion from the viewpoint of handling, working environment, and stability of the coating liquid composition, but water is the main medium, exceeding the gist of the present invention. If it is not within the range, an organic solvent may be contained.
- the coating layer in the present invention is provided by applying a coating solution containing a specific compound to a film, and in particular in the present invention, it is preferably provided by in-line coating in which coating is performed during film formation.
- the silicone release layer is formed by using the following release agent composition.
- the release agent composition in the present embodiment has, as an addition reaction type silicone resin, a first polydimethylsiloxane having at least one alkenyl group in one molecule and at least one hydrosilyl group in one molecule. Containing a second polydimethylsiloxane.
- alkenyl group contained in the first polydimethylsiloxane used in the present invention examples include a monovalent hydrocarbon group such as vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, and octenyl group. Among them, a vinyl group and a hexenyl group are preferable. *
- the alkenyl group (a) is preferably contained in 3 to 90 mmol, more preferably 6 to 45 mmol in 30 g of the first polydimethylsiloxane.
- the hydrosilyl group (b) is preferably contained in 6 to 450 mmol, more preferably 15 to 450 mmol in 30 g of the second polydimethylsiloxane.
- the molar ratio (b / a) of the hydrosilyl group (b) to the alkenyl group (a) is preferably 1.5 to 5.0, more preferably 1.5 to 3.0.
- the weight average molecular weight of the first polydimethylsiloxane must be 500 or more and 30000 or less, preferably 1000 or more and 20000 or less, and more preferably 2000 or more and 10,000 or less. If the weight average molecular weight of the first polydimethylsiloxane is less than 500, the reactivity is high, and the reaction proceeds in the blending solution, so that the desired light peeling force is not expressed, and if it exceeds 30000, the reactivity is poor. Thus, the desired light peeling force is not expressed.
- the content of the first polydimethylsiloxane in the release agent composition is preferably 40 to 90% by weight, and more preferably 50 to 80% by weight.
- the weight average molecular weight of the second polydimethylsiloxane must be 120 or more and 10000 or less, preferably 150 or more and 5000 or less, and more preferably 200 or more and 2000 or less.
- the weight average molecular weight of the second polydimethylsiloxane is less than 120, the reactivity is high, and the reaction proceeds in the compounded solution. Therefore, the desired light peeling force is not expressed, and when it exceeds 10,000, the reactivity is poor. Thus, the desired light peeling force is not expressed.
- the weight average molecular weight in this invention is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
- the content of the second polydimethylsiloxane in the release agent composition is preferably 10 to 60% by weight, more preferably 20 to 50% by weight.
- a platinum-based catalyst that promotes an addition-type reaction is used to make the silicone-based release layer clean and robust.
- chloroplatinic acid alcohol solution of chloroplatinic acid, a complex of chloroplatinic acid and olefin, a platinum compound such as a complex of chloroplatinic acid and alkenylsiloxane, platinum black, platinum-supported silica, platinum-supported activated carbon Is exemplified.
- the platinum-based catalyst content in the silicone-based release layer is usually 0.3 to 3.0% by weight, preferably 0.5 to 2.0% by weight.
- an unreactive organopolysiloxane may be further added as one of unreacted silicone resins in order to impart light release properties.
- the weight average molecular weight of the unreactive organopolysiloxane is preferably 50,000 or more and 500,000 or less.
- the unreactive silicone resin is preferably an organopolysiloxane represented by the following general formula (I).
- R 3 SiO (R 2 SiO) m SiR 3 (I) (In the formula, R represents the same or different monovalent hydrocarbon group having no aliphatic unsaturated bond, and m represents a positive integer.)
- the content of the unreactive silicone resin used in the release agent composition of the present invention is usually in the range of 1 to 10% by weight, preferably 1 to 5% by weight.
- the content of the unreactive silicone resin is 1% by weight or more, a sufficient light peeling effect is exhibited, and when it is 5% by weight or less, sufficient curability and adhesion can be obtained.
- silicone oil may be added to reduce the peeling force.
- the silicone oil is a silicone oil called a straight silicone oil or a modified silicone oil, and examples thereof include the following.
- the straight silicone include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, and the like.
- modified silicone oil side chain type polyether modified, aralkyl modified, fluoroalkyl modified, long chain alkyl modified, higher fatty acid ester modified, higher fatty acid amide modified, polyether / long chain alkyl modified / aralkyl modified, Examples include phenyl modification, polyether modification at both ends, and polyether / methoxy modification.
- the silicone oil component is usually in the range of 1 to 10% by weight, preferably 1 to 5% by weight. If the content of the silicone oil component is lower than 1% by weight, the speed dependency on the peeling force may be increased. If the content exceeds 5% by weight, the transferability is high, and roll dirt or pressure sensitive adhesive surface is applied during adhesive processing. There is a risk that the adhesive peel strength will be reduced.
- an addition reaction type silicone resin for the release agent composition used in the present invention. Since the addition reaction type is very reactive, acetylene alcohol may be added as a reaction inhibitor in some cases.
- the component is an organic compound having a carbon-carbon triple bond and a hydroxyl group, but preferably 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and phenylbuty It is a compound selected from the group consisting of nor.
- the method for forming the silicone release layer on at least one surface of the polyester film is not particularly limited, but a method of applying a release agent composition (coating liquid) in the process of producing the polyester film is suitably employed. Specifically, a method of applying and drying a coating solution on the surface of an unstretched sheet, a method of applying and drying a coating solution on the surface of a uniaxially stretched film, and a method of applying and drying a coating solution on the surface of a biaxially stretched film Etc. Among these, it is economical to apply a coating solution on the surface of an unstretched film or a uniaxially stretched film, and then simultaneously dry and cure the silicone release layer in the process of heat-treating the film.
- a method for forming the silicone release layer a method using some of the above-described coating methods in combination can be adopted as necessary. Specifically, a method of applying a first layer on the surface of an unstretched sheet and drying, then stretching in a uniaxial direction, and then applying and drying a second layer can be used. As a method of applying the coating solution to the surface of the polyester film, Yuji Harasaki, Tsuji Shoten, published in 1979, reverse roll coater, gravure coater, rod coater, air doctor coater, etc. A coater, a doctor blade coater or the like can be used.
- the coating amount of the silicone release layer in the present invention is usually preferably in the range of 0.01 to 1 g / m 2 , and more preferably 0.15 to 0.70 g / m 2 .
- a coating layer such as an adhesive layer, an antistatic layer or an oligomer precipitation preventing layer may be provided on the surface where the silicone release layer is not provided or between the polyester film and the silicone release layer.
- the polyester film may be subjected to surface treatment such as corona treatment or plasma treatment.
- the residual adhesion rate with a tape is preferably 80% or more, more preferably 85% or more.
- the residual adhesion rate is lower than 80%, the transferability is high, and the adhesive moves to roll dirt or the adhesive surface during the adhesive processing, resulting in a decrease in adhesive peeling force.
- the peeling force of the silicone release layer surface at 300 mm / min with an adhesive tape (“tesa 7475” manufactured by tesa) is preferably 9 g / 25 mm or less, and more preferably 8 g / 25 mm or less.
- the peeling force exceeds 9 g / 25 mm, when the release film is used for protecting the adhesive layer, there may be a problem that the release film does not peel off from the adhesive.
- the lower limit of the peeling force is not particularly limited, but is preferably 1 g / 25 mm or more, and more preferably 3 g / 25 mm or more.
- the peeling force at 30 m / min with an adhesive tape (“tesa 7475” manufactured by tesa) is preferably 250 g / 25 mm or less, and more preferably 200 g / 25 mm or less.
- the release force is 250 g / 25 mm or less
- the release film can be easily peeled cleanly from the adhesive, which is also effective from the viewpoint of productivity.
- the lower limit of the peeling force is not particularly limited, but is preferably 10 g / 25 mm or more, and more preferably 25 g / 25 mm or more.
- the peeling force refers to a pressure-sensitive adhesive tape (“tesa 7475” manufactured by tesa) attached to a silicone release layer surface and left at room temperature for 1 hour, and then with a polyester film and a peeling angle of 180 °, a specific tensile speed.
- peeling speed The value measured with a tensile tester when the tape is peeled at (peeling speed).
- the method for adjusting the specific peeling force can be achieved by selecting the composition in the silicone-based release layer, but other means can also be employed, mainly the release agent for the silicone release layer. It is preferable to change the type of the release agent according to the desired release force. Furthermore, since the release force largely depends on the application amount of the release agent composition to be used, the application amount of the release agent composition is adjusted. The method is further preferred.
- the release film of this invention is suitable for an adhesive layer and bonding.
- the pressure-sensitive adhesive composition used for the pressure-sensitive adhesive layer is not particularly limited, and specific examples include silicone pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, and epoxy pressure-sensitive adhesives. Among them, an acrylic pressure-sensitive adhesive is preferred from the viewpoint of wide adjustment range of adhesive properties and is used for general purposes, and an acrylic solvent-based pressure-sensitive adhesive is more preferred.
- additives such as a stabilizer, a curing agent, a tackifier, a filler, a colorant, an antioxidant, an antistatic agent, and a surfactant do not impair the gist of the present invention. Can be used as needed.
- the solvent used in the pressure-sensitive adhesive composition is not particularly limited, but it is preferable to use a solvent that can be dissolved or dispersed in a reasonably uniform and stable manner.
- the solvent include alcohols (methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol, diacetone alcohol); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, Cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone, diacetone alcohol); ester (methyl acetate, ethyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, methyl formate, PGMEA); aliphatic hydrocarbon (hexane) Cyclohex
- Residual adhesion rate (%) ⁇ Adhesion force (I) / Adhesion force (II) ⁇ ⁇ 100
- Release characteristics (practical alternative evaluation): An acrylic pressure-sensitive adhesive composition having the following composition was applied to the release film, followed by heat treatment at 100 ° C. for 5 minutes to obtain a pressure-sensitive adhesive having a dried thickness of 200 ⁇ m. Then, after storing the release film and the adhesive-bonded product at room temperature for 1 week, the release film is peeled off, and the release characteristics are evaluated according to the following evaluation criteria from the situation when the release film is peeled off from the adhesive. did. The evaluation results are shown in Tables 2A and 3B.
- Acrylic adhesive composition >> Main agent: AT352 (manufactured by Seiden Chemical) 100 parts by weight Curing agent: AL (manufactured by Seiden Chemical) 0.25 parts by weight Additive: X-301-375SK (manufactured by Seiden Chemical) 0.25 parts by weight Additive: X -301-352S (manufactured by Seiden Chemical Co., Ltd.) 0.4 parts by weight Toluene: 40 parts by weight ⁇ Evaluation criteria >> >> ⁇ : The release film peels cleanly, and the phenomenon that the adhesive adheres to the silicone release layer is not observed. (Triangle
- the polyester used in the examples and comparative examples was prepared as follows.
- Examples 1A to 4A and Comparative Examples 1A to 6A below are for explaining the first invention, and Examples 1B to 4B and Comparative Examples 1B to 6B below are for explaining the second invention.
- Example 1A The polyester (1) described above is used as a raw material, supplied to an extruder with a vent, melt-extruded at 290 ° C, and then cooled and solidified on a cooling roll set at a surface temperature of 40 ° C using an electrostatic application adhesion method. Thus, an amorphous film having a thickness of about 550 ⁇ m was obtained. This film was stretched 3.7 times in the longitudinal direction at 85 ° C., stretched 3.9 times in the transverse direction at 100 ° C., and heat treated at 210 ° C. to obtain a biaxially stretched polyester film having a thickness of 38 ⁇ m.
- the release agent composition shown below was applied to the obtained polyester film by a reverse gravure coating method so that the coating amount (after drying) was 0.200 g / m 2 , the dryer temperature was 150 ° C., and the line speed was 30 m / m. A roll-shaped release film was obtained under the conditions of minutes. The evaluation results of the release film are shown in Table 2A.
- the release film obtained in Example 1A was peeled 180 ° at a tensile rate of 30 m / min. As a result, the peel force was 108 g / 25 mm. The conditions regarding the peeling force were the same as (2) except that the tensile speed was changed to 30 m / min.
- ⁇ Releasing agent composition> As the first polydimethylsiloxane, a vinyl-modified silicone resin (weight average molecular weight: 2000) having at least two vinyl groups in the structure of polydimethylsiloxane, and as the second polydimethylsiloxane, in the structure of polydimethylsiloxane.
- Polymethylhydrogensiloxane having at least two hydrosilyl groups was mixed so that the first polydimethylsiloxane / second polydimethylsiloxane was 77/22, and the solid content was 3% by weight.
- the weight part of the platinum-based catalyst is a value when the total number of the first polydimethylsiloxane and the second polydimethylsiloxane is 100.
- Example 2A to 4A [Comparative Examples 1A to 6A] A silicone release layer was produced in the same manner as in Example 1A except that the release agent composition shown in Table 1A was changed to obtain a release film. The evaluation results of the release film are shown in Table 2A.
- the release film obtained in Example 4A was peeled 180 ° at a tensile speed of 30 m / min. As a result, the peel force was 112 g / 25 mm. The conditions regarding the peeling force were the same as (2) except that the tensile speed was changed to 30 m / min.
- Example 7A The release film composition was not applied to the biaxially stretched polyester film obtained in Example 1A, and a polyester film without a silicone release layer was used as the release film. The evaluation results of the release film are shown in Table 2A.
- Example 1B The polyester (1) described above is used as a raw material, supplied to an extruder with a vent, melt-extruded at 290 ° C, and then cooled and solidified on a cooling roll set at a surface temperature of 40 ° C using an electrostatic application adhesion method.
- an amorphous film having a thickness of about 550 ⁇ m was obtained.
- This film was stretched 3.7 times in the longitudinal direction at 85 ° C., and a coating layer composed of the following coating composition was applied so that the thickness (after drying) was 0.03 g / m 2 , and then 100 ° C.
- the film was stretched 3.9 times in the transverse direction and heat treated at 210 ° C. to obtain a biaxially stretched polyester film having a thickness of 38 ⁇ m.
- ⁇ Coating composition> A consisting of polyethylene dioxythiophene and polystyrene sulfonic acid, Baytron PAG made by Starck Co., Ltd.
- B Polyurethane resin A polyester polyol comprising 664 parts by weight of terephthalic acid, 631 parts by weight of isophthalic acid, 472 parts by weight of 1,4-butanediol, and 447 parts by weight of neopentyl glycol was obtained. Next, 321 parts by weight of adipic acid and 268 parts by weight of dimethylolpropionic acid were added to the obtained polyester polyol to obtain a pendant carboxyl group-containing polyester polyol A.
- the above-mentioned release agent composition used for explaining the first invention was applied to the obtained polyester film by a reverse gravure coating method so that the coating amount (after drying) was 0.200 g / m 2 , and the dryer temperature A roll-shaped release film was obtained under the conditions of 150 ° C. and a line speed of 30 m / min.
- Example 2B to 5B [Comparative Examples 1B to 10B]
- the coating layer and the release layer were produced in the same manner as in Example 1B except that the coating agent composition and the release agent composition shown in Tables 1B and 2B were changed to obtain a release film.
- Example 10B A release agent was not applied to the biaxially stretched polyester film obtained in Example 1, and a polyester film without a release layer was used as the release film.
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Abstract
Description
そして、本発明の第2の解決課題は、使用時の剥離速度に拘わらず、粘着剤からの離型性が良好で、粘着剤の部材への移行性が少なく、帯電防止性良好な離型フィルムを提供することにある。
本発明の離型フィルムは、例えば、タッチパネル製造用基材レス両面粘着シート、静電容量方式のタッチパネル製造用等、液晶ディスプレイ(LCD)に用いられる偏光板、位相差板等のLCD構成部材製造用、プラズマディスプレイパネル構成部材製造用、有機エレクトロルミネッセンス構成部材製造用等、各種ディスプレイ構成部材製造用のほか、各種粘着剤層保護用途に好適である。
離型フィルムを粘着剤保護用途で用いる際、剥離時に粘着剤層の一部が離型フィルムに付着することがある。離型フィルムに粘着剤が付着すると、粘着剤層の表面形状が粗面化となり、光学部材などの他の部材との密着性に悪影響を及ぼす可能性が考えられる。離型フィルムの基材が紙である場合、剥離時に粘着剤の付着だけでなく、移行性が不十分であることから、本発明ではポリエステルフィルムが用いられる。
本発明でいうポリエステルフィルムとは、いわゆる押出法に従い押出口金から溶融押出されたシートを延伸したフィルムである。
先ず、先に述べたポリエステル原料を使用し、ダイから押し出された溶融シートを冷却ロールで冷却固化して未延伸シートを得る。この場合、シートの平面性を向上させるためシートと回転冷却ドラムとの密着性を高めることが好ましく、静電印加密着法および/または液体塗布密着法が好ましく採用される。
次に、得られた未延伸シートを二軸方向に延伸する。その場合、まず、前記の未延伸シートを一方向にロールまたはテンター方式の延伸機により延伸する。延伸温度は、通常90~140℃、好ましくは95~120℃であり、延伸倍率は通常2.5~7倍、好ましくは3.0~6倍である。次いで、一段目の延伸方向と直交する方向に延伸するが、その場合、延伸温度は通常90~170℃であり、延伸倍率は通常3.0~7倍、好ましくは3.5~6倍である。
そして、引き続き180~270℃の温度で緊張下または30%以内の弛緩下で熱処理を行い、二軸配向フィルムを得る。
上記の延伸においては、一方向の延伸を2段階以上で行う方法を採用することもできる。その場合、最終的に二方向の延伸倍率がそれぞれ上記範囲となるように行うのが好ましい。
本発明の離型フィルムを構成する塗布層について説明する。
前記塗布層は、導電性化合物(A)とバインダーポリマー(B)とを含有することを必須要件とするものである。
本発明の離型フィルムを構成する塗布層は、帯電防止性、オリゴマー析出防止性を良好とするとするために、導電性化合物(A)が含有されていることが重要である。かかる導電性化合物(A)としては、チオフェンまたはチオフェン誘導体を単独または共重合して得られる重合体が好ましく、特に、チオフェンまたはチオフェン誘導体からなる化合物に、他の陰イオン化合物によりドーピングされたものもしくは、化合物中に陰イオン基を持ち自己ドープされたものが、優れた導電性を示し好適である。かかる化合物(A)としては、たとえば下記の化1もしくは化2の化合物を、ポリ陰イオンの存在下で重合して得られるものを例示できる。
(R1,R2はそれぞれ独立に、水素元素、炭素数1~12の脂肪族炭化水素基、脂環族炭化水素基、もしくは芳香族炭化水素基をあらわし、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、シクロヘキシレン基、ベンゼン基などである。)
なお、かかる重合体の製造方法としては、例えば特開平7-90060号公報に示される方法が採用できる。
重合時に使用するポリ陰イオンとしては、例えばポリ(メタ)アクリル酸、ポリマレイン酸、ポリスチレンスルホン酸などが例示される。またこれらの酸は、一部または全てが中和されていてもよい。
特に好ましい様態としては、ポリチオフェンとして上記化2でn=2の化合物、ポリ陰イオンとしてポリスチレンスルホン酸を用いたものが挙げられる。
本発明における塗布層を構成するバインダーポリマー(B)とは、高分子化合物安全性評価フロースキーム(昭和60年11月、化学物質審議会主催)に準じて、ゲルパーミエーションクロマトグラフィー(GPC)測定による数平均分子量(Mn)が1000以上の高分子化合物で、かつ造膜性を有するものと定義する。
本発明において使用するポリエステル樹脂とは、ジカルボン酸成分とグリコール成分とを構成成分とする線状ポリエステルと定義する。ジカルボン酸成分としては、テレフタル酸、イソフタル酸、フタル酸、2,6ーナフタレンジカルボン酸、4,4-ジフェニルジカルボン酸、1,4ーシクロヘキサンジカルボン酸、アジピン酸、セバシン酸、フェニルインダンジカルボン酸、ダイマー酸等を例示することができる。これらの成分は二種以上を用いることができる。さらに、これらの成分とともにマレイン酸、フマル酸、イタコン酸等のような不飽和多塩基酸やp-ヒドロキシ安息香酸、p-(β-ヒドロキシエトキシ)安息香酸等のようなヒドロキシカルボン酸を少割合用いることができる。不飽和多塩基酸成分やヒドロキシカルボン酸成分の割合は高々10モル%、好ましくは5モル%以下である。
アクリル樹脂としては、アクリル系、メタアクリル系のモノマーに代表されるような、炭素-炭素二重結合を持つ重合性モノマーからなる重合体である。これらは、単独重合体あるいは共重合体いずれでも差し支えない。また、それら重合体と他のポリマー(例えばポリエステル、ポリウレタン等)との共重合体も含まれる。例えば、ブロック共重合体、グラフト共重合体である。さらにポリエステル溶液、またはポリエステル分散液中で炭素-炭素二重結合を持つ重合性モノマーを重合して得られたポリマー(場合によってはポリマーの混合物)も含まれる。同様にポリウレタン溶液、ポリウレタン分散液中で炭素-炭素二重結合を持つ重合性モノマーを重合して得られたポリマー(場合によってはポリマーの混合物)も含まれる。同様にして他のポリマー溶液、または分散液中で炭素-炭素二重結合を持つ重合性モノマーを重合して得られたポリマー(場合によってはポリマー混合物)も含まれる。
本発明におけるポリウレタン樹脂とはウレタン結合を分子内に有する高分子化合物のことを指す。その中でも、インラインコーティングへの適性を考慮した場合、水分散性または水溶性のウレタン樹脂が好ましい。水分散性または水溶性を付与させるためには、水酸基、カルボキシル基、スルホン酸基、スルホニル基、リン酸基、エーテル基等の親水性基をウレタン樹脂に導入することが可能である。前記親水性基のなかでも、塗膜物性及び密着性向上の観点から、カルボン酸基またはスルホン酸基が好適に使用される。
シリコーン系離型層は、以下の離型剤組成物を使用して形成されてなるものである。本実施形態における離型剤組成物は、付加反応型シリコーン樹脂として、1分子中に少なくとも1個のアルケニル基を有する第1のポリジメチルシロキサンと、1分子中に少なくとも1個のヒドロシリル基を有する第2のポリジメチルシロキサンとを含有する。
離型剤組成物での第1のポリジメチルシロキサンの含有量は、40~90重量%が好ましく、50~80重量%がより好ましい。
離型剤組成物での第2のポリジメチルシロキサンの含有量は、10~60重量%が好ましく、20~50重量%がより好ましい。
R3SiO(R2SiO)mSiR3……(I)
(式中、Rは脂肪族不飽和結合を有しない同一または異種の一価炭化水素基、mは正の整数を表す。)
また、シリコーン系離型層を形成する方法として、必要に応じ、前述の塗布方法の幾つかを併用した方法も採用し得る。具体的には、未延伸シート表面に第一層を塗布して乾燥し、その後、一軸方向に延伸後、第二層を塗布して乾燥する方法等が挙げられる。ポリエステルフィルムの表面に塗布液を塗布する方法としては、原崎勇次著、槙書店、1979年発行、「コーティング方式」に示されるリバースロールコーター、グラビアコーター、ロッドコーター、エアドクターコーター、ほかにもバーコーター、ドクターブレードコーター等を使用することができる。
本発明において、粘着テープ(tesa社製「tesa7475」)による30m/分での剥離力は250g/25mm以下が好ましく、200g/25mm以下がより好ましい。前記剥離力が250g/25mm以下とすることで、粘着剤層保護用途に離型フィルムを用いる際、離型フィルムが粘着剤から綺麗に剥がれやすくなり、生産性の観点からも有効である。
一方、前記剥離力の下限は特に限定はされないが、10g/25mm以上がより好ましく、25g/25mm以上がさらに好ましい。
本発明の離型フィルムは、粘着剤層と貼り合せに好適である。
粘着剤層に用いられる粘着剤組成物は特に限定はしないが、具体的にはシリコーン系粘着剤、アクリル系粘着剤、ウレタン系粘着剤、エポキシ粘着剤などが挙げられる。中でも粘着特性の調整範囲が広く、汎用的に用いられている観点からアクリル系粘着剤が好ましく、アクリル溶剤系粘着剤であることがより好ましい。
遠心沈降式粒度分布測定装置(株式会社島津製作所社製SA-CP3型)を使用して測定した等価球形分布における積算(重量基準)50%の値を平均粒径とした。
試料フィルムのシリコーン系離型層の表面に粘着テープ(tesa社製「tesa7475」)の片面を貼り付けた後、室温にて1時間放置後の剥離力を測定する。剥離力は、引張試験機(インテスコ社製「インテスコモデル2001型」)を使用し、引張速度300mm/分条件下、180°剥離を行った。評価結果は表2A、表3Bに示す。
試料フィルムをA4大に切り取り、フィルムの測定面に粘着テープ(日東電工社製「No.31B」)をゴムローラーを用いて貼り合わせた後、1時間経過後に、粘着テープを剥がし、その粘着テープを、表面を洗浄したステンレス板にゴムローラーを用いて貼り合わせる。上部チャックに粘着テープ、下部チャックにステンレス板を固定し、300mm/minの速度で、180°方向に引き剥がし、接着力(I)を測定する。
試料と貼り合わせない粘着テープ(日東電工社製「No.31B」)を用い、上述と同じ手順で接着力(II)を測定する。残留接着率は次式により求める。評価結果は表2A、表3Bに示す。
残留接着率(%)={接着力(I)/接着力(II)}×100
下記(4-1)の方法に基づき、試料フィルムの離型層表面における表面固有抵抗を測定した。(4-1)の方法では、1×108Ωより高い表面固有抵抗は測定できないため、(4-1)で測定出来なかったサンプルについては(4-2)の方法を用いた。評価結果は表3Bに示す。
《測定方法》
(4-1)三菱化学社製低抵抗率計:ロレスタGPMCP-T600を使用し、23℃、50%RHの測定雰囲気でサンプルを30分間調湿後、表面固有抵抗値を測定した。
(4-2)日本ヒューレット・パッカード社製高抵抗測定器:HP4339Bおよび測定電極:HP16008Bを使用し、23℃,50%RHの測定雰囲気でサンプルを30分間調湿後、表面固有抵抗値を測定した。
《評価基準》
◎:R(Ω)が1×108以下(実用可能で、特に良好)
○:R(Ω)が1×109以下(実用可能)
△:R(Ω)が1×1010以下(実用上問題になる場合がある)
×:R(Ω)が1×1010を超える(実用困難)
試料フィルムを恒温恒湿槽中、60℃、80%RH雰囲気下、4週間放置した後に試料フィルムを取り出した。その後、試料フィルムの離型面を触手により5回擦り、離型層の脱落程度を以下の評価基準によって評価を行った。
《評価基準》
○:塗膜の脱落が見られない(実用可能で、特に良好)
△:塗膜が白くなるが脱落はしていない(実用可能な)
×:塗膜の脱落が確認された(実用困難)
離型フィルムに下記組成のアクリル系粘着剤組成物を塗工後、100℃、5分間加熱処理して、乾燥後の厚みが200μmの粘着剤を得た。その後、離型フィルムと粘着剤貼り合わせ品を室温で1週間保管した後、離型フィルムを剥がし、粘着剤より離型フィルムを剥がした時の状況より、以下の評価基準によって離型特性を評価した。評価結果は表2A、表3Bに示す。
《アクリル系粘着剤組成物》
主剤:AT352(サイデン化学社製) 100重量部
硬化剤:AL(サイデン化学社製) 0.25重量部
添加剤:X-301-375SK(サイデン化学社製) 0.25重量部
添加剤:X-301-352S(サイデン化学社製) 0.4重量部
トルエン: 40重量部
《評価基準》
○:離型フィルムがきれいに剥がれ、粘着剤がシリコーン系離型層に付着する現象が見られない。
△:離型フィルムは剥がれるが、速い速度で剥離した場合に粘着剤がシリコーン系離型層に付着する。
×:離型フィルムに粘着剤が付着する、上手く剥がれない。
テレフタル酸ジメチル100重量部とエチレングリコール60重量部とを出発原料とし、触媒として酢酸マグネシウム・四水塩0.09重量部を反応器にとり、反応開始温度を150℃とし、メタノールの留去とともに徐々に反応温度を上昇させ、3時間後に230℃とした。4時間後実質的にエステル交換反応を終了させた。この反応混合物にエチルアシッドフォスフェート0.04重量部を添加した後、平均粒径1.6μmのエチレングリコールに分散させたシリカ粒子を0.06重量部、三酸化アンチモン0.04重量部を加えて、4時間重縮合反応を行った。すなわち、温度を230℃から徐々に昇温し280℃とした。一方、圧力は常圧より徐々に減じ、最終的には0.3mmHgとした。反応開始後、4時間を経た時点で反応を停止し、窒素加圧下ポリマーを吐出させた。得られたポリエステルの極限粘度は0.53dl/gであった。
以下の実施例1A~4A及び比較例1A~6Aは第1発明の説明用であり、以下の実施例1B~4B及び比較例1B~6Bは第2発明の説明用である。
先に述べたポリエステル(1)を原料として、ベント付き押出機に供給し、290℃で溶融押出した後、静電印加密着法を用いて表面温度を40℃に設定した冷却ロール上で冷却固化して厚さ約550μmの無定形フィルムを得た。
このフィルムを85℃で縦方向に3.7倍延伸し、100℃で横方向に3.9倍延伸し、210℃で熱処理して、厚さ38μmの二軸延伸ポリエステルフィルムを得た。
第1のポリジメチルシロキサンとして、ポリジメチルシロキサンの構造中にビニル基を少なくとも2個有するビニル変性シリコーン樹脂(重量平均分子量:2000)と、第2のポリジメチルシロキサンとして、ポリジメチルシロキサンの構造中にヒドロシリル基を少なくとも2個有するポリメチルハイドロジェンシロキサン(重量平均分子量:200)を第1のポリジメチルシロキサン/第2のポリジメチルシロキサン=77/22となるように混ぜ合わせ、固形分3重量%となるようにトルエン/MEK/ヘキサン=1/1/18の配合比の溶剤で希釈したのち、白金系触媒(東レ・ダウコーニング社製 SRX-212)2重量部を加えて、離型剤組成物を得た。
上記の白金系触媒の重量部は第1のポリジメチルシロキサンと第2のポリジメチルシロキサンの合計部数を100とした時の値である。
シリコーン系離型層について、表1Aに示す離型剤組成物に変更以外は実施例1Aと同様にして製造し、離型フィルムを得た。離型フィルムの評価結果を表2Aに示す。
<離型剤組成物の原料>
a1:ポリジメチルシロキサンの構造中にビニル基を少なくとも2個有するビニル変性シリコーン樹脂(重量平均分子量:2000)
a2:ポリジメチルシロキサンの構造中にビニル基を少なくとも2個有するビニル変性シリコーン樹脂(重量平均分子量:20000)
a3:ポリジメチルシロキサンの構造中にビニル基を少なくとも2個有するビニル変性シリコーン樹脂(重量平均分子量:1000)
a4:ポリジメチルシロキサンの構造中にビニル基を少なくとも2個有するビニル変性シリコーン樹脂(重量平均分子量:60000)
a5:ポリジメチルシロキサンの構造中にビニル基を少なくとも2個有するビニル変性シリコーン樹脂(重量平均分子量:300)
b1:ポリジメチルシロキサンの構造中にヒドロシリル基を少なくとも2個有するポリメチルハイドロジェンシロキサン(重量平均分子量:200)
b2:ポリジメチルシロキサンの構造中にヒドロシリル基を少なくとも1個有するポリメチルハイドロジェンシロキサン(重量平均分子量:5000)
b3:ポリジメチルシロキサンの構造中にヒドロシリル基を少なくとも1個有するポリメチルハイドロジェンシロキサン(重量平均分子量:30000)
b4:ポリジメチルシロキサンの構造中にヒドロシリル基を少なくとも2個有するポリメチルハイドロジェンシロキサン(重量平均分子量:100)
c1:白金系触媒(東レ・ダウコーニング社製「SRX-212」)
実施例1Aで得た二軸延伸ポリエステルフィルムに離型剤組成物を塗布せず、シリコーン系離型層を設けなかったポリエステルフィルムを離型フィルムとして用いた。離型フィルムの評価結果を表2Aに示す。
先に述べたポリエステル(1)を原料として、ベント付き押出機に供給し、290℃で溶融押出した後、静電印加密着法を用いて表面温度を40℃に設定した冷却ロール上で冷却固化して厚さ約550μmの無定形フィルムを得た。
このフィルムを85℃で縦方向に3.7倍延伸し、下記塗布剤組成物から構成される塗布層を厚み(乾燥後)が0.03g/m2になるように塗布した後、100℃で横方向に3.9倍延伸し、210℃で熱処理して、厚さ38μmの二軸延伸ポリエステルフィルムを得た。
A:ポリエチレンジオキシチオフェンとポリスチレンスルホン酸からなる、
スタルク株式会社製 BaytronPAG
B:ポリウレタン樹脂
テレフタル酸を664重量部、イソフタル酸を631重量部、1,4-ブタンジオールを472重量部、ネオペンチルグリコールを447重量部からなるポリエステルポリオールを得た。次いで、得られたポリエステルポリオールに、アジピン酸を321重量部、ジメチロールプロピオン酸を268重量部加え、ペンダントカルボキシル基含有ポリエステルポリオールAを得た。更に、前記ポリエステルポリオールAを1880重量部に、ヘキサメチレンジイソシアネートを160重量部加えてポリウレタン塗布剤組成物を得た。
C:前記式(3)で、n=1であるグリセリン
配合重量比:A/B/C=40/40/20(重量%)
塗布層および離型層について、表1B、2Bに示す塗布剤組成物と離型剤組成物に変更以外は実施例1Bと同様にして製造し、離型フィルムを得た。
実施例1で得た二軸延伸ポリエステルフィルムに離型剤を塗布せず、離型層を設けなかったポリエステルフィルムを離型フィルムとして用いた。
Claims (3)
- ポリエステルフィルムの少なくとも片面に、重量平均分子量が500以上、30000以下であり、1分子中に少なくとも1個のアルケニル基を有する第1のポリジメチルシロキサンと、重量平均分子量が150以上、10000以下であり、1分子中に少なくとも1個のヒドロシリル基を有する第2のポリジメチルシロキサンと、白金系触媒とを含有する離型剤組成物からなるシリコーン系離型層を有することを特徴とする離型フィルム。
- ポリエステルフィルムの少なくとも片面に塗布層と離型層とが順次設けられた離型フィルムであり、当該塗布層が、導電性化合物(A)とバインダーポリマー(B)とを含有し、当該離型層が、重量平均分子量が500以上、30000以下であり、1分子中に少なくとも1個のアルケニル基を有する第1のポリジメチルシロキサンと、重量平均分子量が150以上、10000以下であり、1分子中に少なくとも1個のヒドロシリル基を有する第2のポリジメチルシロキサンと、白金系触媒とを含有する離型剤組成物からなるシリコーン系離型層であることを特徴とする離型フィルム。
- 剥離速度が300mm/分における、シリコーン系離型層表面と粘着テープとの剥離力が9g/25mm以下である請求項1又は2に記載の離型フィルム。
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WO2023190169A1 (ja) * | 2022-03-29 | 2023-10-05 | 東洋紡株式会社 | 離型フィルム |
WO2023234140A1 (ja) * | 2022-05-30 | 2023-12-07 | 東洋紡株式会社 | シリコーン離型ポリエステルフィルム、及びその製造方法 |
WO2024053483A1 (ja) * | 2022-09-06 | 2024-03-14 | 東洋紡株式会社 | 離型フィルム |
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CN108883615A (zh) | 2018-11-23 |
CN108883615B (zh) | 2020-11-10 |
JPWO2017200056A1 (ja) | 2019-03-14 |
KR20180124063A (ko) | 2018-11-20 |
JP7003915B2 (ja) | 2022-01-21 |
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