WO2016152369A1 - 離型フィルム - Google Patents

離型フィルム Download PDF

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Publication number
WO2016152369A1
WO2016152369A1 PCT/JP2016/055619 JP2016055619W WO2016152369A1 WO 2016152369 A1 WO2016152369 A1 WO 2016152369A1 JP 2016055619 W JP2016055619 W JP 2016055619W WO 2016152369 A1 WO2016152369 A1 WO 2016152369A1
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WIPO (PCT)
Prior art keywords
release
film
release film
group
layer
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PCT/JP2016/055619
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English (en)
French (fr)
Japanese (ja)
Inventor
太朗 鈴木
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三菱樹脂株式会社
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Priority claimed from JP2015059601A external-priority patent/JP6488805B2/ja
Priority claimed from JP2015067803A external-priority patent/JP6488819B2/ja
Priority claimed from JP2015067804A external-priority patent/JP2016187871A/ja
Priority claimed from JP2015067802A external-priority patent/JP2016188265A/ja
Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Priority to CN201680014093.0A priority Critical patent/CN107428135B/zh
Priority to KR1020177020503A priority patent/KR101998239B1/ko
Publication of WO2016152369A1 publication Critical patent/WO2016152369A1/ja

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • 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
    • 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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • 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
    • C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating

Definitions

  • the present invention is particularly suitable for applications where light peeling is required for protecting various pressure-sensitive adhesives, and the amount of oligomer precipitation is extremely small.
  • the adhesive layer is attached via a pressure-sensitive adhesive layer.
  • LCD liquid crystal display
  • PDP plasma display panel
  • organic electroluminescence The present invention relates to a release film suitable for various display component production applications, such as production of various display components (hereinafter abbreviated as organic EL), and the like.
  • a release film based on a polyester film is used for manufacturing a capacitive touch panel, etc., for various purposes to be bonded via an adhesive layer, LCD polarizing plate, retardation plate manufacturing, PDP component It is used for various optical applications such as for manufacturing, for manufacturing organic EL components, for manufacturing various display components.
  • various display components particularly LCD polarizing plates
  • the release film and the thin polarizing plate have a high peeling force and cannot be peeled off successfully. If the release film cannot be peeled off successfully from the thin polarizing plate, the yield decreases, which is a problem.
  • 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 substrate-less double-sided pressure-sensitive adhesive sheet As a method of using the substrate-less double-sided pressure-sensitive adhesive sheet, first, the light release film is peeled off, and one surface of the exposed pressure-sensitive adhesive layer is adhered to the object surface of the other side to be bonded, and after the adhesion, the heavy release film is further peeled off, 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.
  • the present invention has been made in view of the above circumstances, and the solution is that the releasability from the pressure-sensitive adhesive is good, the amount of oligomer precipitation is extremely small, the migration is small, for example, the capacitance method For manufacturing various display components such as for manufacturing touch panel, LCD components such as polarizing plates and retardation plates used in liquid crystal displays (LCDs), plasma display panel components, and organic electroluminescence components
  • another object of the present invention is to provide a release film suitable for various adhesive layer protecting applications.
  • the gist of the present invention is that a polyester film has a silicone-based release layer formed from a coating solution containing a reactive silicone resin having a functional group, an unreactive silicone resin, and a platinum-based catalyst. It exists in the release film characterized by this.
  • the present invention it is possible to provide a release polyester film having good release properties with an adhesive, very little oligomer precipitation, and low migration, and its industrial value is high.
  • 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.
  • 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.
  • the particles include magnesium, kaolin, aluminum oxide, and titanium oxide.
  • 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 content of particles in the polyester is usually 0.001 to 5% by weight, preferably 0.005 to 3% by weight.
  • the particle content is less than 0.001% 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 release film of the present invention has an oligomer amount (OL) of 2.0 mg / m 2 or less on the release layer surface after heating at 180 ° C. for 10 minutes.
  • the amount of oligomer after heating is determined by washing the surface of the release film at 180 ° C. for 10 minutes with 4 ml of DMF (dimethylformamide), and determining the amount of oligomer in the DMF by liquid chromatography.
  • the value can be measured as the film surface oligomer amount (mg / m 2 ) divided by the film area contacted with DMF.
  • a method of reducing the amount of oligomer in the polyester by solid phase polymerization of the polyester there are a method of providing a coating layer for preventing oligomer precipitation, and the like.
  • it is effective to provide the coating layer with a function of preventing oligomer precipitation.
  • Various methods can be used to prevent oligomer precipitation. For example, there is a method of containing an organic compound containing aluminum in the coating layer, but the method is not limited thereto.
  • a production example of the polyester film in the present invention will be specifically described, but it is not limited to the following production examples. That is, a method of using the polyester raw material described above and cooling and solidifying a molten sheet extruded from a die with a cooling roll to obtain an unstretched sheet is preferable. 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. Next, 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.
  • the method for forming the coating layer on the surface of the polyester film is not particularly limited, but a method of coating the coating solution 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 coating layer in the process of heat-treating the film.
  • a method for forming the coating layer a method in which some of the above-described coating methods are used 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. Use the reverse roll coater, gravure coater, rod coater, air doctor coater, etc. shown in “Coating Method” by Yuji Harasaki, Tsuji Shoten, published in 1979, as a method of applying the coating solution to the surface of the polyester film. Can do.
  • the coating layer constituting the release film of the present invention contains an organosilicon compound in order to improve the oligomer precipitation preventing property and to improve the coating film adhesion between the release layer and the polyester film over time. It is preferable to use an organosilicon compound represented by the following general formula (1).
  • X is an organic group having at least one selected from an epoxy group, a mercapto group, a (meth) acryloyl group, an alkenyl group, a haloalkyl group and an amino group
  • R1 is a monovalent hydrocarbon group, and has a carbon number 1 to 10
  • Y is a hydrolyzable group
  • d is an integer of 1 or 2
  • e is an integer of 2 or 3
  • f is an integer of 0 or 1
  • d + e + f 4.
  • the organosilicon compound represented by the general formula (1) has two hydrolyzable groups Y (D unit source) or three (T unit) capable of forming a siloxane bond by hydrolysis / condensation reaction. Source) can be used.
  • the monovalent hydrocarbon group R 1 has 1 to 10 carbon atoms, and is particularly preferably a methyl group, an ethyl group, or a propyl group.
  • hydrolyzable group Y conventionally known ones can be used, and the following can be exemplified.
  • These hydrolyzable groups may be used alone or in combination.
  • the application of a methoxy group or an ethoxy group is particularly preferable because it can impart good storage stability to the coating material and has suitable hydrolyzability.
  • organosilicon compound contained in the coating layer examples include vinyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, 5-hexenyltri Methoxysilane, p-styryltrimethoxysilane, trifluoropropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane, 2- (3,4-epoxy
  • an organic compound containing aluminum is added to the coating layer. It is preferable to contain.
  • organic compound having an aluminum element examples include aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum-di-n-butoxide-monoethylacetoacetate, aluminum di- Examples include iso-propoxide monomethyl acetoacetate, aluminum tris (ethyl acetoacetate) and the like.
  • the amount of the aluminum compound contained in the coating layer is usually 0.001 to 70% by weight, preferably 5 to 35% by weight, and more preferably 5 to 15% by weight.
  • the amount of the aluminum compound is 0.001% by weight or less, the curing reaction of the coating layer does not proceed rapidly, and the coating film adhesion on the release surface after forming the release layer on the coating layer is deteriorated.
  • the amount of the aluminum compound is 70% by weight or more, the aluminum compound remaining in the coating layer does not participate in the curing reaction of the coating layer and prevents the release layer from being cured, and the coating film adheres to the release surface. Sexuality may worsen.
  • the coating layer can also contain an organic compound having a metal element other than the aluminum element.
  • an organic tin compound is preferable.
  • organotin compounds include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dioleate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin, dibutyltin benzylmalate, dioctyl Examples thereof include tin diacetate and dioctyltin dilaurate.
  • inorganic particles may be contained for the purpose of improving the adhesion and slipperiness of the coating layer, and specific examples include silica, alumina, kaolin, calcium carbonate, titanium oxide, barium salt and the like.
  • an antifoaming agent a coating property improver, a thickener, an organic lubricant, organic polymer particles, an antioxidant, a UV absorber foaming agent, a dye, and the like may be contained as necessary.
  • only one type of organic solvent may be used for the purpose of improving dispersibility, improving film forming property, etc., and two or more types may be used as appropriate.
  • the coating amount (after drying) of the coating layer provided on the polyester film constituting the release film in the present invention is usually 0.005 to 1 g / m 2 , preferably 0.005 to 0.5 g / m 2 . is there.
  • the coating amount (after drying) is less than 0.005 g / m 2 , the uniformity of coating thickness may be insufficient, and the amount of oligomer deposited from the coating layer surface may increase after heat treatment. .
  • problems such as a decrease in slipperiness may occur.
  • the curing conditions for forming the coating layer on the polyester film are not particularly limited.
  • the coating layer is provided by off-line coating, usually at 60 to 200 ° C. for 3 to 40 seconds
  • the heat treatment is preferably performed at 80 to 180 ° C. for 3 to 40 seconds as a guide.
  • the type of release layer curable silicone resin to be formed on the outermost layer of one of the polyester films obtained in the present invention is any of addition type, condensation type, ultraviolet curable type, electron beam curable type, solventless type, etc.
  • the reaction type can also be used.
  • silicone resins having an alkenyl group and an alkyl group as functional groups used in the present invention include the following.
  • a curable silicone resin containing an alkenyl group is a diorganopolysiloxane having a trimethylsiloxy group-blocked dimethylsiloxane / methylhexenylsiloxane copolymer (96 mol% dimethylsiloxane unit, 4 mol% methylhexenylsiloxane unit).
  • Dimethylvinylsiloxy group-blocked dimethylsiloxane / methylhexenylsiloxane copolymer (97 mol% dimethylsiloxane unit, 3 mol% methylhexenylsiloxane unit), dimethylsiloxane / methylhexenyl blocked with dimethylhexenylsiloxy group blocked at both ends of the molecular chain Siloxane copolymers (95 mol% of dimethylsiloxane units and 5 mol% of methylhexenylsiloxane units) can be mentioned.
  • Genpolysiloxanes include trimethylsiloxy group-capped methylhydrogen polysiloxane with both molecular chains, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer with both molecular chains, and dimethylhydrogensiloxy group-capped methylhydro with molecular chains.
  • an organopolysiloxane represented by the following general formula (I) is preferable.
  • the chemical structure is shown by the general formula (I), it may be a linear structure or a branched structure.
  • the introduction part of each functional group may be optional.
  • a and b each represent a positive integer.
  • an organopolysiloxane represented by the following general formula (II) is preferable.
  • the chemical structure is shown by the general formula (II), but it may be a linear structure or a branched structure.
  • the introduction part of each functional group may be optional.
  • c and d each represent a positive integer.
  • the silicone resin having a hydrosilyl group used in the present invention is preferably an organopolysiloxane represented by the following general formula (III).
  • the chemical structure is shown by the general formula (III), but it may be a linear structure or a branched structure.
  • the introduction part of each functional group may be optional.
  • e and f each represent a positive integer.
  • silicone resin having a hexenyl group and the silicone resin having a vinyl polymer group are divided into the formulas (I) and (II), a hexenyl group and a vinyl polymer group may be contained in one organopolysiloxane.
  • the phenyl group is not necessarily contained in the hexenyl group and vinyl group-containing silicone resin, and one organopolysiloxane may contain the phenyl group.
  • the ratio of hexenyl group, vinyl group, phenyl group, and hydrosilyl group contained in the silicone resin used in the present invention is as follows.
  • the hydrosilyl group is 100
  • the hexenyl group is 35 to 65
  • the vinyl group is 5 to 35
  • the phenyl group is 1
  • it is ⁇ 20.
  • the hexenyl group is 45 to 55
  • the vinyl group is 15 to 25
  • the phenyl group is 2 to 10.
  • the silicone curing reaction becomes insufficient, the peel force at 30000 mm / min becomes high, and when the release film is peeled off from the adhesive at a high speed, there may be a problem that it does not peel off cleanly. is there.
  • the hexenyl group exceeds 65, the number of cross-linking points increases in the silicone curing, the peeling force at 300 mm / min becomes high, and there may be a problem that the release film cannot be peeled cleanly from the adhesive.
  • the vinyl group is less than 15, the silicone curing reaction becomes insufficient, the peel force at 30000 mm / min becomes high, and when the release film is peeled off from the adhesive at a high speed, there may be a problem that the film cannot be peeled cleanly. is there.
  • the vinyl group exceeds 35, the number of cross-linking points increases in the silicone curing, the peeling force at 300 mm / min becomes high, and there may be a problem that the release film cannot be peeled cleanly from the adhesive.
  • the silicone film becomes soft, the peeling force at 30000 mm / min becomes high, and when the release film is peeled off from the adhesive at a high speed, there may be a problem that the silicone film does not peel off beautifully.
  • the silicone film becomes too hard, the peeling force at 300 mm / min becomes high, and there may be a problem that the release film does not peel off from the adhesive.
  • the number of dimethylsilyl groups (a in general formula (I), c in general formula (II), and f in general formula (III)) contained in the silicone resin used in the present invention is preferably 2000 or more and 5000 or less. More preferably, 3000 or more and 4000 or less are preferable. If it is less than 2000, the molecular weight is small, and problems such as transfer of unreacted silicone to the adhesive layer may occur. If it exceeds 5000, the molecular weight is too large, the curing reaction does not proceed smoothly, and the desired release characteristics may not be obtained.
  • an unreactive silicone resin having a mass average molecular weight of 50,000 to 100,000.
  • the unreactive silicone resin is preferably an organopolysiloxane represented by the following general formula (IV).
  • g represents a positive integer.
  • the unreactive silicone resin contained in the silicone resin used in the present invention is in the range of 1 to 10% by weight, preferably 1 to 5% by weight.
  • the content of the unreactive silicone resin is lower than 1%, light peeling does not occur, and when it exceeds 5% by weight, the curability is remarkably lowered and the adhesion is also deteriorated.
  • 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 contained in the silicone resin used in the present invention is in the range of 1 to 10% by weight, preferably 1 to 5% by weight.
  • the content of the silicone oil component is lower than 1%, the speed dependency becomes high.
  • the content exceeds 5% by weight the transferability is high, and the adhesive peels off when the adhesive is processed. Etc. will occur.
  • the residual adhesion rate with the 31B tape is preferably 80% or more, and more preferably 85% or more. If the residual adhesive rate is lower than 80%, the transferability is high, and the adhesive may be transferred to roll dirt or the pressure-sensitive adhesive surface during processing of the pressure-sensitive adhesive, resulting in a decrease in pressure-sensitive adhesive peeling force.
  • the peeling force with a 31B tape at 300 mm / min is preferably 10 to 20 mN / cm.
  • the peeling force at 300 mm / min exceeds 20 mN / cm, there may be a problem that the release film does not peel off from the adhesive.
  • the peeling force at 30000 mm / min with the 31B tape is preferably less than 80 mN / cm. If the peeling force at 30000 mm / min exceeds 80 mN / cm, there may be a problem that when the release film is peeled off from the adhesive at a high speed, it cannot be peeled cleanly.
  • any of the curing reaction types such as an addition type, a condensation type, an ultraviolet curable type, an electron beam curable type, and a solventless type can be used.
  • Specific examples include KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-856, X-62-2422, X-62-2461, X, manufactured by Shin-Etsu Chemical Co., Ltd.
  • a conventionally known coating method such as reverse roll coating, gravure coating, bar coating, doctor blade coating, or the like can be used.
  • the coating amount of the release layer in the present invention is usually in the range of 0.01 to 1 g / m 2 .
  • a coating layer such as an adhesive layer, an antistatic layer and an oligomer precipitation preventing layer may be provided on the surface where the release layer is not provided, and the polyester film may be subjected to corona treatment, plasma treatment, etc. A surface treatment may be applied.
  • a platinum-based catalyst that promotes an addition-type reaction is used in order to make the 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 release layer is usually 0.3 to 3.0% by weight, preferably 0.5 to 2.0% by weight.
  • the platinum-based catalyst content in the release layer is lower than 0.3% by weight, there may be problems such as deterioration of the surface condition due to insufficient peeling force and insufficient curing reaction in the coating layer.
  • the platinum-based catalyst content in the release layer exceeds 3.0% by weight, the cost is increased, and the process becomes defective due to increased reactivity and generation of gel foreign matter. Sometimes.
  • 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 peeling force refers to a double-sided pressure-sensitive adhesive tape (“No. 31B” manufactured by Nitto Denko) attached to the release layer surface and left at room temperature for 1 hour, and then the substrate film and the peeling angle of 180 °.
  • the method for adjusting the specific peeling force in the present invention can be achieved by selecting the composition in the release layer, but other means can also be adopted, mainly the type of release agent for the silicone release layer. Is preferably changed according to the desired peeling force, and furthermore, since the peeling force largely depends on the application amount of the release agent to be used, a method of adjusting the application amount of the release agent is more preferable.
  • the low speed peel force in the 300 mm / min speed region is usually in the range of 10 to 20 mN / cm.
  • the peeling force is less than 10 mN / cm, there may be a problem that the peeling force becomes too light and easily peels even in a scene where it is not necessary to peel off. If the peel force exceeds 20 mN / cm, the difference in peel force between the release film with the greater peel force will be small, causing problems in the peel process, and the selection range for the release film with the greater peel force will be narrow. Sometimes it becomes.
  • the high-speed peeling force in the 60000 mm / min speed region taking into consideration workability is usually 90 mN / cm or less.
  • the peeling force is greater than 90 mN / cm, the difference in peeling force with the release film having the heavier peeling force becomes small, and peeling may not be performed well in the peeling process, or the adhesive may be peeled off.
  • the amount of polyester oligomer (OL) extracted from the release layer surface with dimethylformamide is usually 2.0 mg / m 2 or less, preferably 1 0.0 mg / m 2 or less.
  • the OL exceeds 2.0 mg / m 2 , for example, when the liquid crystal component is manufactured, the adhesive layer is used for protecting the adhesive layer, the transparency of the adhesive is lowered, the adhesive strength of the adhesive layer is reduced, or optical evaluation is performed. There may be problems such as causing trouble in the accompanying inspection process.
  • the value measured by the FP (Fundamental Parameter Method) method using a fluorescent X-ray measuring device as the amount of aluminum element contained in the coating layer is 0 so that OL satisfies the above range. .2 kcps or more, more preferably 0.5 kcps or more, and particularly preferably 0.8 kcps or more.
  • the amount of aluminum element is less than 0.2 kcps, the desired oligomer sealing performance may not be obtained.
  • oligomer is defined as a cyclic trimer among low molecular weight polyesters that crystallize and precipitate on the film surface after heat treatment.
  • the polyester film constituting the two types of release films in the present invention (hereinafter, the one having a smaller peel force may be referred to as a first release film and the one having a greater release desire may be referred to as a second release film) is a single layer. It may be a configuration or a laminated configuration. For example, it may be a multi-layer of 4 layers or more as long as it does not exceed the gist of the present invention other than a 2-layer or 3-layer configuration, and is particularly limited. It is not a thing.
  • the polyester used for the polyester film may be a homopolyester or a copolyester.
  • a homopolyester those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred.
  • aromatic dicarboxylic acid examples include terephthalic acid and 2,6-naphthalenedicarboxylic acid
  • aliphatic glycol examples include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol.
  • PET polyethylene terephthalate
  • examples of the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid (eg, P-oxybenzoic acid).
  • examples of the glycol component include one or more types such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol and the like.
  • the polyester referred to in the present invention refers to a polyester that is usually 60 mol% or more, preferably 80 mol% or more of polyethylene terephthalate or the like which is an ethylene terephthalate unit.
  • 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.
  • the particles include magnesium, kaolin, aluminum oxide, and titanium oxide.
  • the heat-resistant organic particles described in JP-B-59-5216, JP-A-59-217755 and the like may be used.
  • examples of other heat-resistant organic particles 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 0.01 to 1 ⁇ m.
  • the average particle diameter is less than 0.01 ⁇ m, the particles are likely to aggregate and dispersibility may be insufficient.
  • the average particle diameter exceeds 3 ⁇ m, the surface roughness of the film becomes too rough and There may be a problem when a release layer is applied in the process.
  • the particle content in the polyester layer is usually in the range of 0.001 to 5% by weight, preferably 0.005 to 3% by weight.
  • the particle content is less than 0.001% 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.
  • 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 of producing the polyester constituting each layer, but preferably a polycondensation reaction may be carried out after the esterification stage or after the transesterification reaction.
  • 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 constituting the first release film and the second release film of the present invention is not particularly limited as long as it can be formed as a film.
  • the first release film it is usually in the range of 25 to 75 ⁇ m, preferably 38 to 75 ⁇ m.
  • the second release film it is usually in the range of 25 to 250 ⁇ m, preferably 38 to 188 ⁇ m, more preferably 50 to 125 ⁇ m.
  • 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 is preferable.
  • a method in which 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 is preferable.
  • an electrostatic application adhesion method and / or a liquid application adhesion method are 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 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times.
  • the stretching temperature orthogonal to the first-stage stretching direction is usually 70 to 170 ° C., and the draw ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times.
  • 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.
  • the simultaneous biaxial stretching method can be adopted for the production of the polyester film in the present invention.
  • the simultaneous biaxial stretching method is a method in which the unstretched sheet is usually stretched and oriented simultaneously in the machine direction and the width direction in a state where the temperature is controlled at 70 to 120 ° C, preferably 80 to 110 ° C.
  • the area magnification is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times.
  • 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 which comprises the release film in this invention contains a conductive compound (A) in order to improve antistatic properties and oligomer precipitation preventing properties.
  • a 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.
  • the compound (A) include those obtained by polymerizing a compound of the following formula (1) or (2) in the presence of a polyanion.
  • 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, for example, Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclohexylene group, and a benzene group.
  • n is an integer of 1 to 4.
  • polythiophene or polythiophene derivatives include compounds in which a functional group is bonded to positions 3 and 4 of the thiophene ring.
  • a compound in which an oxygen atom is bonded to the 3rd and 4th carbon atoms is preferable.
  • a compound having a structure in which a carbon atom or a hydrogen atom is directly bonded to the carbon atom it may not be easy to make the coating liquid aqueous.
  • polyanion used at the time of polymerization examples include poly (meth) acrylic acid, polymaleic acid, polystyrene sulfonic acid and the like. These acids may be partially or completely neutralized.
  • JP-A-7-90060 As a method for producing such a polymer, for example, a method disclosed in JP-A-7-90060 can be employed.
  • the coating layer constituting the release film in the present invention is required to contain the above conductive compound and binder polymer.
  • 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 (sponsored by the Chemical Substance Council in November 1985). It is defined as a polymer compound having a number average molecular weight (Mn) of 1000 or more and having a film-forming property.
  • GPC gel permeation chromatography
  • the binder polymer (B) constituting the coating layer in the present invention may be either a thermosetting resin or a thermoplastic resin as long as it is compatible with, or mixed 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; Aramid resin; Polyimide silicone; Polyurethane
  • the blending ratio of the conductive compound (A) in the coating layer is 10 to 90% by weight, preferably 20 to 80% by weight. If it is less than 10% by weight, the antistatic property and the oligomer precipitation preventing property may be insufficient. On the other hand, if it exceeds 80% by weight, the antistatic property is already in a saturated state, and even if the amount is increased further, it may be difficult to obtain a remarkable effect.
  • binder polymers (B) may be dissolved in an organic solvent, or may be formed 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, itaconic acid and the like, and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- ( ⁇ -hydroxyethoxy) benzoic acid, etc.
  • 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 usually 40 ° C. or higher, preferably 60 ° C. or higher. When 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 an acrylic or methacrylic monomer. 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 usually 40 ° C. or higher, 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 group such as a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfonyl group, a phosphoric acid group, or an ether group into the urethane resin.
  • a hydrophilic groups a carboxylic acid group or a sulfonic acid group is preferably used from the viewpoint of improving physical properties of the coating film and adhesion.
  • 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-bisaminomethylcyclohexane, etc. And alicyclic diamines.
  • the blending ratio of the binder polymer (B) in the coating layer is in the range of 10 to 90%, more preferably in the range of 20 to 80%.
  • the said range is less than 10%, the adhesiveness with respect to a mold release layer may fall.
  • it exceeds 80% the adhesion performance becomes saturated, and even if the amount is increased further, a remarkable effect may not be obtained.
  • 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 selected from the group of glycerin (C1), polyglycerin (C2), glycerin or an alkylene oxide adduct (C3) to polyglycerin as the component (C). It is preferred to contain more than one compound or derivative thereof. Those having an average number of glycerin units in the molecule in the range of 2 to 20 are preferred. Incidentally, when glycerin is used, the transparency of the coating layer may be slightly inferior.
  • the alkylene oxide adduct to glycerin or polyglycerin has a structure in which alkylene oxide or a derivative thereof is added and polymerized 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 glycerin or polyglycerin skeleton is not particularly limited, but when the glycerin or polyglycerin moiety is 1 in terms of molecular weight ratio
  • the alkylene oxide moiety is preferably 20 or less, more preferably 10 or less.
  • 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 alkylene oxide adduct (C3) to glycerol or polyglycerol.
  • polyglycerin (C2) those having n of 2 to 20 in the compound of the above formula (3) are particularly preferred.
  • the number is particularly preferably in the range of 300 to 2000 in terms of the weight average molecular weight as the final compound (C3).
  • the blending ratio of component (C) in the coating layer is in the range of 10 to 90%, more preferably in the range of 20 to 80%. When the said range is less than 10%, applicability
  • the weight of the coating agent component (A) which occupies in a coating layer is 0.5 mg / m ⁇ 2 > or more normally, Preferably it is 1 mg / m ⁇ 2 > or more.
  • the amount of the coating agent component (A) is less than 0.5 mg / m 2 , the antistatic property tends to be insufficient.
  • the ratio of the coating agent component (A) in the coating layer constituting the release film is not limited, but the upper limit is preferably 90%, more preferably 80%, and most preferably 60%. It is. When the ratio of the coating agent component (A) exceeds 90% by weight, the transparency of the coating film may be insufficient, or the antistatic performance may be insufficient. On the other hand, the lower limit is preferably 1%, more preferably 2%. When the weight ratio of the coating agent component (A) is less than 1%, the antistatic performance may be insufficient.
  • the ratio of the coating agent component (A) and the coating agent component (B) is preferably in the range of 90/10 to 1/99 by weight. More preferably, it is in the range of 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.
  • a surfactant can be contained in order to improve the coating property to the polyester film.
  • this surfactant it is more preferable to use a surfactant containing (poly) alkylene oxide, (poly) glycerin, or a derivative thereof in the structure, since it does not inhibit the antistatic property of the resulting coating layer.
  • 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. Moreover, as these additives, it is more preferable to use those containing (poly) alkylene oxide, (poly) glycerin, or derivatives thereof in the structure without inhibiting the antistatic property of the resulting coating layer.
  • 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 and exceeds 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 release layer constituting the first release film and the second release film in the present invention refers to a layer having releasability. Specifically, the peeling force between the adhesive layer and the release layer is constant. By setting the range, the present invention can be completed.
  • the low-speed peeling force at 0.3 m / min of the first release film 31 needs to be 10 to 20 mN / cm.
  • the peeling force of the first release film is less than 10 mN / cm, the release film is easily peeled in a scene that does not need to be peeled.
  • the peeling force of a 1st release film exceeds 20 mN / cm, it becomes difficult to peel smoothly in the process of peeling a 1st release film.
  • the high-speed peeling force of 60 m / min to 90 mN / cm or less.
  • it is 85 mN / cm or less.
  • the high-speed peeling force exceeds 90 mN / cm, it becomes difficult to peel smoothly.
  • the inventor cut in advance into a small piece sheet shape close to the size of the electronic component. After that, it is common for an operator to peel off by hand. In the peeling operation step, the cut pieces are used to give a chance to peel off the first release film and then peeled 180 degrees in the diagonal direction of the pieces.
  • the release film is peeled 180 degrees from the normal adhesive tape, in the peeling direction, the release film is peeled in the diagonal direction, so that the peeling area gradually increases as the peeling progresses.
  • the present inventor paid attention to this peeling method and regarded the phenomenon in which the peeling area increases at a constant peeling speed as a peeling method with a faster peeling propagation speed as a phenomenon of peeling a larger area within the same time.
  • As in the present invention when using a flexible adhesive layer in consideration of step absorbability, it has been found that it is effective to suppress the high-speed peeling force at a constant peeling force level to 60 m / min. The invention has been completed.
  • the peeling force at 0.3 m / min of the second release film is preferably 20 to 100 mN / cm, more preferably 40 to 80 mN / cm.
  • the peeling force of the second release film is less than 20 mN / cm, when the first release film is peeled from the substrate-less double-sided pressure-sensitive adhesive sheet, there may be a problem that a part of the second release film is peeled off. is there.
  • the peeling force of a 2nd mold release film exceeds 100 mN / cm, malfunctions, such as a component derived from an adhesive layer remaining in a 2nd mold release film, may arise.
  • the substrate-less double-sided pressure-sensitive adhesive sheet of the present invention provides a difference in peel force between the first release film and the second release film in addition to the above-described peel force adjustment.
  • the peel force of the second release film is usually 2.0 times or more, preferably 3.0 times or more of the peel force of the first release film.
  • the peel force of the second release film is less than 2.0 times the peel force of the first release film, the second release film floats from the pressure-sensitive adhesive layer when the first release film on the light release side is peeled off. The phenomenon may occur, or the adhesive layer component may remain on the second release film, or a defect such as zipping may occur.
  • the release layer constituting the release film in the present invention preferably contains a curable silicone resin in order to improve the release property. It may be a type mainly composed of a curable silicone resin, or a modified silicone type by graft polymerization with an organic resin such as a urethane resin, an epoxy resin or an alkyd resin may be used as long as the gist of the present invention is not impaired. Also good.
  • the release film having a smaller peel force comprises a reactive silicone resin having an alkenyl group and an alkyl group as functional groups on a polyester film, an unreactive silicone resin having a mass average molecular weight of 400,000 or more, a platinum-based catalyst, It is necessary to have a release layer containing.
  • a curable silicone resin containing an alkenyl group is a diorganopolysiloxane having a trimethylsiloxy group-blocked dimethylsiloxane / methylhexenylsiloxane copolymer (96 mol% dimethylsiloxane unit, 4 mol% methylhexenylsiloxane unit).
  • Dimethylvinylsiloxy group-blocked dimethylsiloxane / methylhexenylsiloxane copolymer (97 mol% dimethylsiloxane unit, 3 mol% methylhexenylsiloxane unit), dimethylsiloxane / methyl-blocked dimethylhexenylsiloxy group blocked at both ends of the molecular chain Hexenylsiloxane copolymer (95 mol% of dimethylsiloxane units, 5 mol% of methylhexenylsiloxane units).
  • the curable silicone resin containing an alkyl group is a trimethylsiloxy group-blocked methylhydrogenpolysiloxane having both molecular chains and trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane as both organohydrogenpolysiloxanes.
  • examples thereof include a polymer, a dimethylhydrogensiloxy group-capped methylhydrogen polysiloxane having both molecular chains, and a dimethylsiloxane / methylhydrogensiloxane copolymer having both molecular chains having both ends dimethylhydrogensiloxy group-capped.
  • 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 above formula, R represents the same or different monovalent hydrocarbon group having no aliphatic unsaturated bond, and m represents a positive integer.)
  • the unreactive silicone resin contained in the silicone resin used in the present invention is in the range of 1 to 10% by weight, preferably 1 to 5% by weight.
  • the content of the unreactive silicone resin is lower than 1%, the speed dependency is increased, and when it exceeds 5% by weight, the curability is remarkably lowered and the adhesion may be deteriorated.
  • silicone oil may be added to reduce the peeling force in the high speed range.
  • 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 contained in the silicone resin used in the present invention is usually in the range of 1 to 10% by weight, preferably 1 to 5% by weight.
  • the content of the silicone oil component is lower than 1%, the speed dependency becomes high.
  • the content exceeds 5% by weight the transferability is high, and the adhesive peels off when the adhesive is processed. May occur.
  • the residual adhesion rate by 31B tape is preferably 85% or more, and more preferably 90% or more. If the residual adhesive rate is lower than 80%, the transferability is high, and the adhesive may be transferred to roll dirt or the pressure-sensitive adhesive surface during processing of the pressure-sensitive adhesive, resulting in a decrease in pressure-sensitive adhesive peeling force.
  • any of the curing reaction types such as an addition type, a condensation type, an ultraviolet curable type, an electron beam curable type, and a solventless type can be used.
  • Specific examples include KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-856, X-62-2422, X-62-2461, X, manufactured by Shin-Etsu Chemical Co., Ltd.
  • a release control agent may be used in combination in order to adjust the release property of the release layer.
  • the curing conditions for forming the release layer on the polyester film are not particularly limited.
  • the release layer is usually 120 to 200 ° C. for 3 to 40 seconds, preferably Is preferably heat-treated at 100 to 180 ° C. for 3 to 40 seconds as a guide.
  • a conventionally well-known apparatus and an energy source can be used as an energy source for hardening by active energy ray irradiation.
  • the coating amount of the release layer (after drying) is usually 0.005 to 1 g / m 2 , preferably 0.005 to 0.5 g / m 2 , more preferably 0.01 to 0 from the viewpoint of coating properties. .2 g / m 2 range.
  • the coating amount (after drying) is less than 0.005 g / m 2 , the coating property may be less stable and it may be difficult to obtain a uniform coating film.
  • the coating is thicker than 1 g / m 2 , the coating layer adhesion and curability of the release layer itself may be lowered.
  • the base material-less double-sided pressure-sensitive adhesive sheet in the present invention it is necessary to bond release films on both sides of the pressure-sensitive adhesive layer.
  • the thickness ratio of each release film the handleability is taken into consideration, and the thickness of the second release film is preferably 2 times or more, preferably 3 times or more the thickness of the first release film. For example, by reducing the film thickness of the first release film, there is an advantage that it is possible to prevent floating that occurs at the adhesive interface with the second release film when the first release film is peeled off.
  • the adhesive layer is applied on the release surface of the second release film, in order to eliminate the influence of foreign matter and unevenness in the process, the influence of unevenness and foreign matter is more It is preferable to further increase the film thickness of the second release film that is easily received.
  • the thickness of the second release film is less than twice the thickness of the first release film, there is no difference in stiffness of the film substrate, and the first release film is peeled from the substrate-less double-sided pressure-sensitive adhesive sheet. At this time, there may be a problem that a part of the second release film is peeled off.
  • an adhesive layer an antistatic layer, an oligomer precipitation-preventing layer, etc., as long as the gist of the present invention is not impaired on the film surface on which no release layer is provided.
  • a coating layer may be provided.
  • a platinum-based catalyst that promotes an addition-type reaction is used in order to make the release layer of the release film having a trans-peeling force clean and strong.
  • 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 release layer is usually 0.3 to 3.0% by weight, preferably 0.5 to 2.0% by weight.
  • the platinum-based catalyst content in the release layer is lower than 0.3% by weight, there may be problems such as deterioration of the surface condition due to insufficient peeling force and insufficient curing reaction in the coating layer.
  • the platinum-based catalyst content in the release layer exceeds 3.0% by weight, the cost is increased, and the process becomes defective due to increased reactivity and generation of gel foreign matter. Sometimes.
  • 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.
  • polyester film constituting the first release film and the second release film may be subjected to surface treatment such as corona treatment or plasma treatment in advance.
  • a release layer when manufacturing a release film, after apply
  • the adhesive layer in the present invention means a layer composed of a material having adhesiveness, and conventionally known materials can be used as long as the gist of the present invention is not impaired.
  • an acrylic adhesive is used as one specific example, the case where an acrylic adhesive is used will be described below.
  • the acrylic pressure-sensitive adhesive means a pressure-sensitive adhesive layer containing, as a base polymer, an acrylic polymer formed using an acrylic monomer as an essential monomer component.
  • the acrylic polymer has (meth) acrylic acid alkyl ester and / or (meth) acrylic acid alkoxyalkyl ester having a linear or branched alkyl group as an essential monomer component (more preferably as a main monomer component). ) It is preferably an acrylic polymer to be formed.
  • the acrylic polymer is preferably an acrylic polymer formed using (meth) acrylic acid alkyl ester and acrylic acid alkoxyalkyl ester having a linear or branched alkyl group as essential monomer components.
  • the pressure-sensitive adhesive layer of the present invention is preferably an acrylic pressure-sensitive adhesive layer formed using (meth) acrylic acid alkyl ester and acrylic acid alkoxyalkyl ester having a linear or branched alkyl group as essential monomer components.
  • the monomer component forming the acrylic polymer that is the base polymer in the adhesive layer of the present invention is further copolymerized with a polar group-containing monomer, a polyfunctional monomer, and other copolymerizable monomers. It may be contained as a monomer component.
  • said "(meth) acryl” represents “acryl” and / or "methacryl", and others are the same.
  • the content of the acrylic polymer as the base polymer in the pressure-sensitive adhesive layer of the present invention is preferably 60% by weight or more, more preferably based on the total weight (100% by weight) of the pressure-sensitive adhesive layer. 80% by weight or more.
  • a (meth) acrylic acid alkyl ester having a linear or branched alkyl group (hereinafter sometimes simply referred to as “(meth) acrylic acid alkyl ester”) is used. It can be used suitably.
  • (meth) acrylic acid alkyl ester examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth ) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate , Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic acid I
  • the (meth) acrylic acid alkyl ester may be used alone or in combination of two or more. Among them, (meth) acrylic acid alkyl esters having 2 to 14 carbon atoms in the alkyl group are preferable, and (meth) acrylic acid alkyl esters having 2 to 10 carbon atoms in the alkyl group are more preferable.
  • Examples of the polar group-containing monomer include, for example, (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and other carboxyl group-containing monomers or anhydrides thereof (such as maleic anhydride) Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, Hydroxyl group (hydroxyl group) -containing monomers such as vinyl alcohol and allyl alcohol; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N -Butoxymethyl (meth) acrylamide, N-hydro Amide group-containing monomers such as ethyl acrylamide; Amino
  • Sulfonic acid group-containing monomer of 2-hydroxyethyl Chestnut phosphoric acid group-containing monomers such as acryloyl phosphate; cyclohexyl maleimide, imide group-containing monomers such as isopropyl maleimide; 2-methacryloyloxy such acryloyl isocyanate group-containing monomers such as methacryloyloxyethyl isocyanate.
  • the polar group-containing monomers can be used alone or in combination of two or more.
  • polyfunctional monomer examples include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methanetri (meth) Examples include acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate.
  • the said polyfunctional monomer can also be used individually or in combination of 2 or more types.
  • the content of the polyfunctional monomer is preferably 0.5% by weight or less with respect to 100% by weight of the monomer component forming the acrylic polymer.
  • the content exceeds 0.5% by weight for example, the cohesive force of the pressure-sensitive adhesive layer becomes too high, and the stress relaxation property may be lowered.
  • copolymerizable monomers (other copolymerizable monomers) other than the polar group-containing monomer and multifunctional monomer examples include cyclopentyl (meth) acrylate and cyclohexyl (meth) acrylate.
  • the acrylic polymer can be prepared by polymerizing the above monomer components by a conventionally known or conventional polymerization method.
  • the polymerization method of the acrylic polymer include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by active energy ray irradiation (active energy ray polymerization method).
  • the solution polymerization method and the active energy ray polymerization method are preferable in terms of transparency, water resistance, production cost and the like.
  • Examples of the active energy rays irradiated in the above active energy ray polymerization (photopolymerization) include ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, neutron rays, electron rays, and ultraviolet rays, among others. Ultraviolet rays are suitable for the use of the present invention. Further, the irradiation energy, irradiation time, irradiation method, and the like of the active energy ray are not particularly limited as long as they do not impair the gist of the present invention.
  • esters such as ethyl acetate and n-butyl acetate
  • aromatic hydrocarbons such as toluene and benzene
  • aliphatic hydrocarbons such as n-hexane and n-heptane
  • alicyclic rings such as cyclohexane and methylcyclohexane.
  • Organic hydrocarbons such as formula hydrocarbons; ketones such as methyl ethyl ketone and methyl isobutyl ketone are exemplified.
  • a solvent can be used individually or in combination of 2 or more types.
  • a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) can be used depending on the type of polymerization reaction.
  • a polymerization initiator can also be used individually or in combination of 2 or more types.
  • the photopolymerization initiator is not particularly limited, but is a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an ⁇ -ketol photopolymerization initiator, an aromatic sulfonyl chloride photopolymerization initiator, Photoactive oxime photopolymerization initiators, benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, thioxanthone photopolymerization initiators, and the like can be used.
  • the amount of the photopolymerization initiator used is not particularly limited as long as it does not impair the gist of the present invention.
  • the amount of the photopolymerization initiator is 0.1% relative to 100 parts by weight of the total amount of monomer components forming the acrylic polymer. A range of 01 to 0.2 parts by weight is preferred.
  • benzoin ether photopolymerization initiator examples include, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one And anisole methyl ether.
  • acetophenone photopolymerization initiator examples include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl). Examples include dichloroacetophenone.
  • Examples of the ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one, and the like.
  • Specific examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
  • Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.
  • Examples of the benzoin photopolymerization initiator include benzoin.
  • Examples of the benzyl photopolymerization initiator include benzyl.
  • benzophenone photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
  • ketal photopolymerization initiator examples include benzyldimethyl ketal.
  • thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
  • thermal polymerization initiator examples include azo polymerization initiators [for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis. (2-methylpropionic acid) dimethyl, 4,4′-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [ 2- (5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2′-azobis (N, N′-di) Methyleneisobutylamidine) dihydrochloride], peroxide polymerization initiators (eg, dibenzoyl peroxide, tert-butylpermaleate, etc.), red Box-type polymerization initiators and the like.
  • a crosslinking agent for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin) Etc.
  • a tackifier for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin
  • anti-aging agents fillers, colorants (pigments, dyes, etc.)
  • UV absorbers antioxidants
  • chain transfer agents plasticizers
  • softeners surfactants
  • various general solvents can also be used.
  • the type of the solvent is not particularly limited, and those exemplified as the solvent used in the above solution polymerization can be used.
  • the cross-linking agent can control the gel fraction of the adhesive layer by crosslinking the base polymer of the adhesive layer.
  • crosslinking agents isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents Agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, amine crosslinking agents, and the like, and isocyanate crosslinking agents and epoxy crosslinking agents can be preferably used.
  • a crosslinking agent can also be used individually or in combination of 2 or more types.
  • the base material-less double-sided pressure-sensitive adhesive sheet of the present invention when an acrylic pressure-sensitive adhesive composition is used at the time of forming the pressure-sensitive adhesive layer, for example, an optical member (for example, a surface protective layer, a touch panel, and an image display unit)
  • an optical member for example, a surface protective layer, a touch panel, and an image display unit
  • the light transmission is improved and the brightness and contrast of the image display device are reduced.
  • the thickness of the pressure-sensitive adhesive layer (after drying) constituting the substrate-less double-sided pressure-sensitive adhesive sheet in the present invention is usually in the range of 25 to 200 ⁇ m, preferably 50 to 100 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer is less than 25 ⁇ m, for example, the gap generated between the optical members becomes too large, and it may be difficult to fill the corners with the pressure-sensitive adhesive layer.
  • the thickness of the adhesive layer exceeds 200 ⁇ m, the adhesive layer thickness becomes too thicker than the gap generated between the optical members, and the excess adhesive layer component protrudes from between the optical members. There is.
  • Residual adhesion rate (%) Adhesive strength (1) ⁇ Adhesive strength (2) ⁇ 100
  • Amount of polyester oligomer (OL) extracted from the surface of the release layer of the release film In advance, an unheat-treated release film is heated in air at 180 ° C. for 10 minutes. After that, the heat-treated film is brought into close contact with the inner surface of a box having a top and width of 10 cm and a height of 3 cm, and the box shape is obtained. When the coating layer is provided, the coating layer surface is set to the inside. Next, 4 ml of DMF (dimethylformamide) is placed in the box prepared by the above method and left for 3 minutes, and then DMF is recovered.
  • DMF dimethylformamide
  • the recovered DMF was supplied to liquid chromatography (manufactured by Shimadzu Corporation: LC-7A) to determine the amount of oligomer in DMF, and this value was divided by the area of the film in contact with DMF to determine the amount of oligomer on the film surface (mg / M 2 ).
  • the amount of oligomer in DMF was determined from the peak area ratio between the standard sample peak area and the measured sample peak area (absolute calibration curve method).
  • the standard sample was prepared by accurately weighing the oligomer (cyclic trimer) collected in advance and dissolving it in DMF accurately measured.
  • the concentration of the standard sample is preferably in the range of 0.001 to 0.01 mg / ml.
  • Element amount from the release surface side of the release film The following table is prepared by the FP (Fundamental Parameter Method) method using a fluorescent X-ray measurement apparatus (model “XRF-1500” manufactured by Shimadzu Corporation) from the surface provided with the release layer of the sample sample in advance. The element amount was measured under the measurement conditions shown in 1.
  • Tg Glass transition temperature of polyester resin: Using a DSC-II type measuring device manufactured by Perkin Elmer, the sample was heated at a rate of temperature increase of 10 ° C./min under a sample weight of 10 mg and a nitrogen stream, and the baseline start temperature of the baseline was defined as Tg.
  • Release force of release film (II): An adhesive tape (“No. 31B” manufactured by Nitto Denko) is attached to the surface of the release layer of the sample film, then cut to a size of 50 mm ⁇ 300 mm, and the peel force after standing at room temperature for 1 hour is measured. The peel force was measured using a high-speed peel tester (Tester Sangyo Co., Ltd., high-speed peel tester “TE-702 type”). In the manner of peeling the 31B adhesive tape, 180 ° peeling was performed under each measurement condition of peeling speed of 0.3 m / min and 60 m / min.
  • Coating film adhesion of release film (practical property substitution evaluation): The sample film was left in a constant temperature and humidity chamber at 60 ° C. and 80% RH for 4 weeks, and then the sample film was taken out. Thereafter, the release surface of the sample film was rubbed with a tentacle five times, and the degree of release of the release layer was determined according to the following criteria. ⁇ Criteria> A: Coating film is not removed (practical level) B: The coating film turns white but does not fall off (practical level) C: The drop of the coating was confirmed (practical level)
  • the polyester used in the examples and comparative examples was prepared as follows. ⁇ Manufacture of polyester> ⁇ Polyester (1) Using 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol as starting materials, 0.09 parts by weight of magnesium acetate tetrahydrate as a catalyst is placed in the reactor, the reaction start temperature is set to 150 ° C., and the methanol is distilled off gradually. The reaction temperature was raised to 230 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially terminated.
  • Example 1-1 Manufacture of polyester film>
  • the polyester (1) as a raw material is supplied to an extruder with a vent, melt-extruded at 290 ° C., and then cooled and solidified on a cooling roll having a surface temperature set to 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., 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.
  • a release agent composed of release agent composition-A shown below was applied to the obtained polyester film by a reverse gravure coating method so that the coating amount (after drying) was 0.12 g / m 2 , and a dryer temperature of 150 A roll-shaped release polyester film was obtained under the conditions of ° C and a line speed of 30 m / min.
  • Examples 1-2 to 1-5 and Comparative Examples 1-1 to 1-7 A release film was obtained in the same manner as in Example 1 except that the release agent composition in Example 1-1 was changed to the coating composition shown in Table 2 below. The obtained results are summarized in Table 3 below.
  • Example 2-1 A biaxially stretched polyester film having a thickness of 38 ⁇ m was obtained in the same manner as Example 1-1. Next, the following coating agent was applied by a reverse gravure coating method so that the coating amount (after drying) was 0.05 g / m 2, and then heat-treated at 120 ° C. for 30 seconds. Examples of compounds constituting the coating layer are as follows.
  • Example compounds -Organic compound having an aluminum element: (A1) Aluminum tris (ethyl acetoacetate) ⁇ Organic compound containing tin element: (A2) Dioctyldiacetoxytin / organosilicon compound: (B1) 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane
  • ⁇ Coating composition> Organic compound having aluminum element (A1): 33% by weight
  • the coating agent was diluted with a toluene / MEK mixed solvent (mixing ratio was 1: 4) to 4 wt%.
  • a release agent having a release agent composition shown below is applied on the coating layer by a reverse gravure coating method so that the coating amount (after drying) is 0.12 g / m 2 , the dryer temperature is 150 ° C., the line A roll-shaped release polyester film was obtained under the condition of a speed of 30 m / min.
  • Example 2-1 the coating agent composition was changed to the coating agent composition shown in Table 4 below, and the releasing agent composition was changed to the release agent composition shown in Table 5 below, in the same manner as in Example 2-1. A release film was obtained. The properties of the release films obtained in the above examples and comparative examples are shown in Table 6 below.
  • Example 3-1 Manufacture of polyester film
  • Polyester film-1 50 ⁇ m
  • the polyester (1) as a raw material is supplied to an extruder with a vent, melt-extruded at 290 ° C., and then cooled and solidified on a cooling roll having a surface temperature set to 40 ° C. using an electrostatic application adhesion method.
  • An amorphous film having a thickness of about 600 ⁇ m was obtained.
  • This film was stretched 3.3 times in the machine direction at 85 ° C., stretched 3.6 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 50 ⁇ m.
  • Polyester film-2 (100 ⁇ m)
  • the polyester (1) as a raw material is supplied to an extruder with a vent, melt-extruded at 290 ° C., and then cooled and solidified on a cooling roll having a surface temperature set to 40 ° C. using an electrostatic application adhesion method.
  • An amorphous film having a thickness of about 1200 ⁇ m was obtained.
  • This film was stretched 3.3 times in the machine direction at 85 ° C., stretched 3.6 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 100 ⁇ m.
  • a release agent comprising the following release agent composition A was applied to polyester film-1 by a reverse gravure coating method so that the coating amount (after drying) was 0.1 g / m 2, and heat-treated at 150 ° C. for 30 seconds. A first release film was obtained later.
  • ⁇ Release agent compound> a1: Curing type silicone resin (LTC310: manufactured by Toray Dow Corning) a2: curable silicone resin (LTC303E: manufactured by Toray Dow Corning, transition component content 15%) a3: curable silicone resin (KS-847H: manufactured by Shin-Etsu Chemical Co., Ltd.) a4: curable silicone resin (SD-7292: manufactured by Toray Dow Corning) b1: Unreactive silicone resin having a mass average molecular weight of 400,000 or more c1: Addition type platinum catalyst (SRX212: manufactured by Toray Dow Corning) c2: Addition type platinum catalyst (PL-50T: manufactured by Shin-Etsu Chemical Co., Ltd.)
  • a release agent comprising the following release agent composition B was applied to polyester film-2 by a reverse gravure coating method so that the coating amount (after drying) was 0.1 g / m 2 and heat-treated at 150 ° C. for 30 seconds. Later, a second release film was obtained.
  • the first release film was bonded to the exposed adhesive layer surface to obtain a substrate-less double-sided adhesive sheet.
  • Example 3-1 In Example 3-1, except that the release agent composition and the polyester film substrate thickness were changed as shown in Tables 7 and 8 below, the production was performed in the same manner as in Example 3-1, and the first release film, A two release film was obtained. Then, it bonded together through the adhesive layer using both, and obtained the base material-less double-sided adhesive sheet. Table 8 shows the characteristics of the release films obtained in the above Examples and Comparative Examples.
  • Example 4-1 Manufacture of polyester film
  • the polyester (1) as a raw material is supplied to an extruder with a vent, melt-extruded at 290 ° C., and then cooled and solidified on a cooling roll having a surface temperature set to 40 ° C. using an electrostatic application adhesion method.
  • An amorphous film having a thickness of about 600 ⁇ m was obtained.
  • the film was stretched 3.3 times in the longitudinal direction at 85 ° C., and a coating layer composed of the following coating agent composition was applied so that the coating thickness (after drying) was 0.03 g / m 2 , and then 100 ° C.
  • the film was stretched 3.6 times in the transverse direction and heat treated at 210 ° C. to obtain a biaxially stretched polyester film having a thickness of 50 ⁇ m.
  • Polyester film-2 (100 ⁇ m)
  • the polyester (1) as a raw material is supplied to an extruder with a vent, melt-extruded at 290 ° C., and then cooled and solidified on a cooling roll having a surface temperature set to 40 ° C. using an electrostatic application adhesion method.
  • An amorphous film having a thickness of about 1200 ⁇ m was obtained.
  • the film was stretched 3.3 times in the longitudinal direction at 85 ° C., and a coating layer composed of the following coating agent composition was applied so that the coating thickness (after drying) was 0.03 g / m 2 , and then 100 ° C.
  • the film was stretched 3.6 times in the transverse direction and heat-treated at 210 ° C. to obtain a biaxially stretched polyester film having a thickness of 100 ⁇ m.
  • a / B / C 40/40/20 (% by weight)
  • a release agent comprising the following release agent composition A was applied to polyester film-1 by a reverse gravure coating method so that the coating amount (after drying) was 0.1 g / m 2, and heat-treated at 150 ° C. for 30 seconds. A first release film was obtained later.
  • ⁇ Release agent compound> a1: Curing type silicone resin (LTC310: manufactured by Toray Dow Corning) a2: curable silicone resin (LTC303E: manufactured by Toray Dow Corning, transition component content 15%) a3: curable silicone resin (KS-847H: manufactured by Shin-Etsu Chemical Co., Ltd.) a4: curable silicone resin (SD-7292: manufactured by Toray Dow Corning) b1: Unreactive silicone resin having a mass average molecular weight of 400,000 or more c1: Addition type platinum catalyst (SRX212: manufactured by Toray Dow Corning) c2: Addition type platinum catalyst (PL-50T: manufactured by Shin-Etsu Chemical Co., Ltd.)
  • a release agent comprising the following release agent composition B was applied to polyester film-2 by a reverse gravure coating method so that the coating amount (after drying) was 0.1 g / m 2 and heat-treated at 150 ° C. for 30 seconds. Later, a second release film was obtained.
  • the first release film was bonded to the exposed adhesive layer surface to obtain a substrate-less double-sided adhesive sheet.
  • Example 4-1 a coating agent composition, a release agent composition, and a polyester film substrate thickness were prepared in the same manner as in Example 4-1, except that the thicknesses were changed as shown in Tables 9 and 10 below. A mold film and a second release film were obtained. Then, it bonded together through the adhesive layer using both, and obtained the base material-less double-sided adhesive sheet. The characteristics of the release films obtained in the above examples and comparative examples are shown in Tables 11 and 12 below.
  • the release film of the present invention has good releasability from the pressure-sensitive adhesive and less migration, for example, for polarizing plate and retardation plate used for liquid crystal display (LCD) for manufacturing capacitive touch panels.
  • LCD liquid crystal display
  • various display components such as for the production of LCD components such as, for the production of plasma display panel components, for the production of organic electroluminescence components, etc., it can be suitably used for various adhesive layer protection applications.

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KR101973155B1 (ko) * 2018-12-10 2019-04-26 (주)딥스원에듀 도트필름, 다층광학시트 및 스마트 전자칠판
KR102306997B1 (ko) 2019-11-11 2021-09-29 도레이첨단소재 주식회사 초경박리 이형필름
KR102227259B1 (ko) * 2019-12-12 2021-03-11 도레이첨단소재 주식회사 캐리어 필름용 점착제 조성물 및 이를 포함하는 캐리어 필름
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