WO2014080715A1 - 基材レス両面粘着シート - Google Patents

基材レス両面粘着シート Download PDF

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Publication number
WO2014080715A1
WO2014080715A1 PCT/JP2013/078494 JP2013078494W WO2014080715A1 WO 2014080715 A1 WO2014080715 A1 WO 2014080715A1 JP 2013078494 W JP2013078494 W JP 2013078494W WO 2014080715 A1 WO2014080715 A1 WO 2014080715A1
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WIPO (PCT)
Prior art keywords
release
film
release film
sensitive adhesive
layer
Prior art date
Application number
PCT/JP2013/078494
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English (en)
French (fr)
Japanese (ja)
Inventor
智久 齋藤
公裕 井崎
Original Assignee
三菱樹脂株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from JP2012255750A external-priority patent/JP6046462B2/ja
Priority claimed from JP2012255751A external-priority patent/JP6046463B2/ja
Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Priority to CN201380058232.6A priority Critical patent/CN104781359B/zh
Priority to KR1020157012223A priority patent/KR101821257B1/ko
Publication of WO2014080715A1 publication Critical patent/WO2014080715A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens
    • 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
    • C09J2469/00—Presence of polycarbonate
    • C09J2469/006—Presence of polycarbonate 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 relates to a substrate-less double-sided pressure-sensitive adhesive sheet, and is excellent in antistatic properties, mold release properties, oligomer sealing properties, and easy testability, and has good release properties without causing release charge at the time of release film release. Peelable. Further, after the application of the adhesive, after the release film is bonded, the fluctuation of peeling from the adhesive layer is small, and the migration and precipitation of the oligomer to the adhesive layer is as small as possible.
  • the present invention provides a substrate-less double-sided pressure-sensitive adhesive sheet suitable for various uses to be bonded via an adhesive layer, such as for producing a liquid crystal polarizing plate and for producing a capacitive touch panel.
  • a base-less double-sided pressure-sensitive adhesive sheet is known as one of pressure-sensitive adhesive sheets.
  • 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.
  • Capacitive touch panels tend to have a thicker printing step than the resistive film method, and therefore 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 pressure-sensitive adhesive layer is provided on the second release film (heavy release side)
  • it may be bonded to the counterpart member and an inspection with optical evaluation may be performed.
  • the inspection visual field may become dark depending on the angle.
  • the present invention has been made in view of the above circumstances, and the problem to be solved is a substrate-less double-sided pressure-sensitive adhesive sheet in which release films are laminated on both sides of a pressure-sensitive adhesive layer, for example, a capacitance type
  • a substrate-less double-sided pressure-sensitive adhesive sheet that is suitably used as a touch panel member, has antistatic properties, mold release properties, oligomer sealing properties, and good testability, and has a mold sealing performance in the release film itself. Is.
  • the present invention comprises two related inventions, and the gist of each invention is as follows.
  • the gist of the first invention is that release films are laminated on both sides of the pressure-sensitive adhesive layer, and the release force of one release film (first release film) is the other release film (second release film).
  • the variation of the orientation angle in the plane of the biaxially stretched polyester film is 6 degrees / 500 mm or less.
  • the amount of oligomer extracted with dimethylformamide from the surface of the release layer of the release film is 0.5 mg / m 2 or less.
  • the gist of the second invention resides in the base material-less double-sided pressure-sensitive adhesive sheet according to the first aspect, wherein the film haze of the first release film is 6% or more. .
  • the first invention is suitable as a substrate-less double-sided pressure-sensitive adhesive sheet used for a capacitive touch panel, for example, because it has an antistatic property, good releasability and oligomer sealing performance, and its industrial value is high.
  • the second aspect of the invention further has good inspection ease and discrimination.
  • the polyester film constituting the first and second release films may have a single layer structure or a laminated structure.
  • the polyester film exceeds the gist of the present invention in addition to the two-layer or three-layer structure. As long as there is not, it may be a multilayer of four layers or more, and is not particularly limited.
  • 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.
  • the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid
  • examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol.
  • Representative polyester includes polyethylene terephthalate (PET) and the like.
  • 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 in which a part of a metal compound such as a catalyst is precipitated and finely dispersed during the polyester production process.
  • 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 for producing the polyester constituting each layer, but the polycondensation reaction may proceed preferably 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, but is usually 25 to 250 ⁇ m, preferably It is in the range of 38 to 188 ⁇ m, more preferably 50 to 125 ⁇ m.
  • the manufacture example of the polyester film in this invention is demonstrated concretely, it is not limited to the following manufacture examples at all.
  • 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.
  • 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.
  • conventionally known stretching methods such as a screw method, a pantograph method, and a linear drive method can be employed.
  • a so-called coating stretching method for treating the film surface during the above-described polyester film stretching step can be performed.
  • coating stretching method in-line coating
  • coating can be performed simultaneously with stretching and the thickness of the coating layer can be reduced according to the stretching ratio, producing a film suitable as a polyester film. it can.
  • the coating layer constituting the release film in the present invention will be described.
  • the coating layer constituting the release film in the present invention has good antistatic properties and oligomer precipitation prevention properties, and is also hydrolyzable in order to improve the adhesion between the release layer and the polyester film over time. It is an essential requirement to contain a silicon compound.
  • a compound represented by the general formula Si (OR 1 ) x (R 2 ) 4-x is preferably used for the purpose of the present invention.
  • x is preferably an integer of 2 to 4.
  • R 1 may be either an alkyl group or an acyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like, an alkyl group having 1 to 5 carbon atoms, and an acyl group.
  • R2 is an organic group having 1 to 10 carbon atoms, for example, an unsubstituted or substituted hydrocarbon group.
  • the unsubstituted hydrocarbon group includes methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, tert- Examples thereof include alkyl groups such as octyl group and n-decyl group, aryl groups such as phenyl group, alkenyl groups such as vinyl group and allyl group.
  • substituted hydrocarbon group examples include ⁇ -glycidoxypropyl group, ⁇ -mercaptopropyl group, 3,4-epoxycyclohexylethyl group, ⁇ -methacryloyloxypropyl group, and the like. These hydrolyzable silicon compounds may be used alone or in combination of two or more.
  • a material constituting the coating layer in the present invention it is preferable to use a metal element-containing organic compound in order to further improve the oligomer sealing property.
  • At least one metal element-containing organic compound selected from aluminum, titanium, and zirconium may be contained in the coating layer.
  • 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 and the like.
  • organic compound having titanium element examples include titanium orthoesters such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate; titanium acetylacetonate, Examples thereof include titanium chelates such as titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium triethanolamate, and titanium ethylacetoacetate.
  • titanium orthoesters such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate
  • titanium acetylacetonate examples thereof include titanium chelates such as titanium tetraacetylacetonate, polytitanium acetylace
  • organic compound having a zirconium element examples include, for example, zirconium acetate, zirconium normal propylate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate and the like.
  • a metal element-containing organic compound selected from aluminum and zirconium is preferable, and an organic compound having a chelate structure is more preferable from the viewpoint of particularly good oligomer precipitation preventing performance. It is also described in detail in the “Crosslinking agent handbook” (Yamashita Shinzo, Kaneko Tosuke editor Taiseisha Co., Ltd., 1990 edition).
  • the hydrolyzable silicon compound (A) and the metal element-containing organic compound (B) in order to improve the oligomer sealing property.
  • the release layer constituting the first release film and the second release film in the present invention refers to a layer having releasability, and specifically, the peeling force between the acrylic pressure-sensitive adhesive tape and the release layer.
  • the present invention can be completed by setting (F) within a certain range.
  • the peeling force of the first release film 31 corresponding to the light peeling side with respect to the adhesive layer 11 is preferably 5 to 40 mN / cm.
  • the peeling force of the first release film is less than 5 mN / cm, the release film may be easily peeled in a scene that does not need to be peeled.
  • the peeling force of the first release film exceeds 40 mN / cm, a peeling phenomenon called “floating” occurs between the second release film and the adhesive layer in the step of peeling the first release film. There is.
  • the peeling force of the second release film 32 corresponding to the heavy peeling side is preferably 45 to 100 mN / cm, more preferably 50 to 80 mN / cm.
  • the peeling force of the second release film is less than 45 mN / cm, when the first release film is peeled off, there may be a problem that a part of the second release film is peeled off.
  • the peeling force of a 2nd mold release film exceeds 100 mN / cm, malfunctions, such as the component derived from an adhesion layer remaining in a 2nd mold release film, may arise.
  • the base-material-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 peeling force of the second release film 32 is usually 2.0 times or more, preferably 3.0 times or more of the peeling force of the first release film 31.
  • the peeling force of the second release film 32 is less than 2.0 times the peeling force of the first release film 31, the second release film 32 adheres when the first release film 31 on the light release side is peeled off. In some cases, a phenomenon that the phenomenon of floating from the agent layer 11 occurs, the adhesive layer component remains in the second release film 32, or a problem such as zipping occurs.
  • the release layer constituting the first release film in the present invention can be provided on the polyester film by the above-described coating stretching method (in-line coating).
  • the coating stretching method is not limited to the following, but for example, in sequential biaxial stretching, the first stage of stretching may be completed and the coating treatment may be performed before the second stage of stretching. it can.
  • the film can be applied simultaneously with stretching, and the thickness of the release layer can be reduced according to the stretching ratio. Can be manufactured.
  • 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.
  • 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 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 provided by off-line coating, usually at 120 to 200 ° C. for 3 to 40 seconds
  • the heat treatment is preferably performed at 100 to 180 ° C. for 3 to 40 seconds as a guide.
  • a conventionally well-known apparatus and energy source can be used as an energy source for hardening by active energy ray irradiation.
  • the coating amount (after drying) of the release layer is usually 0.005 to 1 g / m 2 , preferably 0.005 to 0.5 g / m 2 , and more preferably 0.01 to 0.5 g from the viewpoint of coating properties.
  • the range is 0.2 g / m 2 .
  • 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 second release film in the present invention needs to have a variation in orientation angle within the film of 6 degrees / 500 mm or less. If the variation in the orientation angle exceeds 6 degrees / 500 mm, it is not suitable for this application.
  • conventionally known coating methods such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating and the like can be used as a method for providing a release layer on the polyester film.
  • coating method there is an example described in “Coating Method”, published by Yoji Harasaki, published in 1979.
  • 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.
  • 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 surface specific resistance (R) value of the release surface is 1 ⁇ 10 12 from the viewpoint of foreign matter adhesion to the pressure-sensitive adhesive layer surface or prevention of peeling electrification. ( ⁇ ) or less is preferable.
  • the R value is preferably 1 ⁇ 10 11 ( ⁇ ) or less, more preferably 1 ⁇ 10 10 ( ⁇ ) or less.
  • the amount of oligomer (OL) extracted from the surface of the release layer after heat treatment is preferably 0.5 mg / m 2 or less.
  • the OL exceeds 0.5 mg / m 2
  • oligomers precipitate over time, causing trouble during inspection in the inspection process involving optical evaluation. It may become like this.
  • the pressure-sensitive adhesive layer in the present invention means a layer composed of an adhesive material, 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 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. preferable.
  • the monomer component forming the acrylic polymer that is the base polymer in the pressure-sensitive adhesive layer of the present invention further contains a polar group-containing monomer, a polyfunctional monomer, and other copolymerizable monomers. It may be contained as a polymerization 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 based on the total weight (100% by weight) of the pressure-sensitive adhesive layer. Preferably it is 80 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 (maleic anhydride, etc.) 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-hydroxy Amide group-containing monomers such as ethylacrylamide; Amino group
  • Sulfonic acid group-containing monomer 2-hydroxyethyla Phosphoric acid group-containing monomers such as Leroy Le phosphate; cyclohexyl maleimide, imide group-containing monomers such as isopropyl maleimide; 2-methacryloyloxy such acryloyloxyethyl isocyanate group-containing monomers such as 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.
  • solvents include 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; cyclohexane and methylcyclohexane Organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • 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 is not particularly limited as long as it does not impair the gist of the present invention. For example, the amount of the photopolymerization initiator is 0. 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 cross-linking agent for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble, if necessary) Phenol resins, etc.
  • a tackifier for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble, if necessary
  • Phenol resins, etc. rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble, if necessary
  • anti-aging agents fillers, colorants (pigments and dyes, etc.), UV absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, etc.
  • An additive can be used in the range which does not impair the characteristic of this invention.
  • 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 crosslinking agent can control the gel fraction of the pressure-sensitive adhesive layer by crosslinking the base polymer of the pressure-sensitive 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 pressure-sensitive adhesive layer 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 By replacing the air gap between the display surfaces of the image display unit) with a transparent adhesive sheet having a refractive index close to that of the optical member as compared with air, the light transmission is improved, and the brightness of the image display device
  • the pressure-sensitive adhesive layer itself is preferably designed flexibly.
  • the storage elastic modulus (G ′) in dynamic viscoelasticity is preferably 1.0 ⁇ 10 5 Pa or less, and more preferably 5.0 ⁇ 10 4 Pa or less.
  • the thickness of the pressure-sensitive adhesive layer constituting the substrate-less double-sided pressure-sensitive adhesive sheet in the present invention is in the range of 25 ⁇ m to 200 ⁇ m, preferably 50 ⁇ m to 150 ⁇ m.
  • the pressure-sensitive adhesive layer has a thickness of 25 ⁇ m or less, 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 pressure-sensitive adhesive layer exceeds 200 ⁇ m, the pressure-sensitive adhesive layer thickness becomes excessively thicker than the gap generated between the optical members, and the excess pressure-sensitive adhesive layer components protrude from between the optical members. May occur.
  • the present invention is different from the first invention only in that the film haze of the first release film is 6% or more as a constituent requirement from the viewpoint of facilitating identification from the outside.
  • the film haze of the first release film is preferably 10% or more. When the film haze is less than 6%, the release film may be mistaken when the release film is peeled from the substrate-less double-sided pressure-sensitive adhesive sheet.
  • the measuring method used in the present invention is as follows.
  • film haze measurement of the first release film In accordance with JIS-K6714, film haze (turbidity) was measured with a ball turbidimeter NDH-20D manufactured by Nippon Denshoku Industries Co., Ltd.
  • the change in the orientation angle every 500 mm is calculated by proportional calculation. In this way, the variation in the orientation angle every 500 mm in the width direction was determined, and the average value was taken as the orientation angle variation in the width direction of the film.
  • Release force (F1 / F2) measurement of release film After applying one side of double-sided adhesive tape (“No. 502” manufactured by Nitto Denko) to the surface of the release layer of the sample film, cut it to a size of 50 mm ⁇ 300 mm and measure the peel force after standing at room temperature for 1 hour To do.
  • a tensile tester (“Intesco model 2001 type” manufactured by Intesco Co., Ltd.) was used, and 180 ° peeling was performed under a tensile speed of 300 mm / min.
  • oligomer amount (OL) extracted from release layer surface of release film An unheat-treated release film is heated in air at 180 ° C. for 10 minutes in advance. 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 an oligomer (cyclic trimer) collected in advance and dissolving it in accurately measured DMF.
  • the concentration of the standard sample is preferably in the range of 0.001 to 0.01 mg / ml.
  • Zipping property evaluation (practical property substitution evaluation): The following pressure-sensitive adhesive composition was applied to the second release film, heat-treated at 100 ° C. for 5 minutes, and then a pressure-sensitive adhesive layer having a thickness (after drying) of 50 ⁇ m was obtained. Next, in the base material-less double-sided pressure-sensitive adhesive sheet in which the first release film is bonded to the surface of the pressure-sensitive adhesive layer, the peeling state is observed when the first release film is peeled off, and the occurrence of zipping is determined according to the following criteria. It was.
  • ⁇ Acrylic adhesive composition > (Monomer composition) 2-ethylhexyl acrylate 70% by weight 2-methoxyethyl acrylate 29% by weight 4-hydroxybutyl acrylate 1% by weight 0.1 part of Nippon Polyurethane Coronate L was added to 100 parts by weight of the monomer composition to obtain an acrylic pressure-sensitive adhesive layer forming composition.
  • Coronate L was added to 100 parts by weight of the monomer composition to obtain an acrylic pressure-sensitive adhesive layer forming composition.
  • A It peels very smoothly, there is no peeling stripe, and no peeling noise is generated.
  • B Minor peeling streaks are observed, peeling noise is slightly generated, or slight zipping occurs (a level that may cause a problem in practical use).
  • C Peeling streaks are observed and peeling sound is generated. Zipping occurs (a level that is problematic in practice).
  • Peelability evaluation of first and second release films (practical property substitution evaluation): In the item (7), sensory evaluation was performed according to the following criteria for the situation of the interface between the second release layer and the pressure-sensitive adhesive layer when the first release film was peeled off. (Criteria) A: No abnormality is observed at the interface between the second release layer and the pressure-sensitive adhesive layer (a level that causes no problem in practical use). B: Slight floating is observed at the interface between the second release layer and the pressure-sensitive adhesive layer (a level that may cause a practical problem). C: Clear floating is observed at the interface between the second release layer and the pressure-sensitive adhesive layer (practically problematic level).
  • Oligomer sealing evaluation (practical property substitution evaluation): From the oligomer amount obtained in the item (8), the determination was made according to the following determination criteria. (Criteria) A: The amount of oligomer is 0.5 mg / m 2 or less. B: The amount of oligomer exceeds 0.5 mg / m 2 .
  • Discrimination evaluation (practical property substitution evaluation) The substrate-less double-sided pressure-sensitive adhesive sheet was visually observed, and the side on which the release film having a light peeling force was bonded was determined according to the following criteria.
  • polyester used in the examples and comparative examples was prepared as follows.
  • Production Example 1 Polyethylene terephthalate A1 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol and 0.09 part of magnesium acetate tetrahydrate are placed in a reactor, the temperature is raised by heating, methanol is distilled off, transesterification is performed, and 4 hours are required from the start of the reaction. The temperature was raised to 230 ° C. to substantially complete the transesterification reaction. Next, after adding 0.04 part of ethylene glycol slurry ethyl acid phosphate and 0.03 part of antimony trioxide, the temperature reached 280 ° C. and the pressure reached 15 mmHg in 100 minutes. It was 0.3 mmHg. After 4 hours, the system was returned to atmospheric pressure to obtain polyethylene terephthalate A1 having an intrinsic viscosity of 0.61.
  • Production Example 2 (Polyethylene terephthalate A2) In Production Example 1, production was carried out in the same manner as in Production Example 1 except that 0.6 part of silica particles having an average particle diameter of 2.5 ⁇ m was added to obtain polyethylene terephthalate A2 having an intrinsic viscosity of 0.62.
  • This film was stretched 3.5 times in the longitudinal direction at 90 ° C., stretched 4.1 times in the transverse direction at 130 ° C., heat treated at 230 ° C., and then subjected to a relaxation treatment of 4.3% in the width direction.
  • a polyester film F1a having a thickness of 50 ⁇ m (thickness ratio 2.5 ⁇ m / 45 ⁇ m / 2.5 ⁇ m) was obtained.
  • This film was stretched 3.5 times in the longitudinal direction at 90 ° C., stretched 4.1 times in the transverse direction at 130 ° C., heat treated at 230 ° C., and then subjected to a relaxation treatment of 4.3% in the width direction.
  • a polyester film having a thickness of 50 ⁇ m (thickness ratio 2.5 ⁇ m / 45 ⁇ m / 2.5 ⁇ m) was obtained.
  • heat treatment is performed at 120 ° C. for 30 seconds.
  • a polyester film F2a having a thickness of 50 ⁇ m provided with a coating layer was obtained.
  • AC1 Colcoat N-103X (manufactured by Colcoat)
  • AC2 Aluminum tris (acetylacetonate)
  • AC3 Zirconium tetraacetylacetonate
  • AC4 Titanium tetraacetylacetonate (mixing conditions)
  • Production Example 5 (Polyester film F3a) A polyester film F3a was obtained in the same manner as in Production Example 4 except that the composition of the coating layer in Production Example 4 was different.
  • Production Example 6 (Polyester film F4a) Manufactured in the same manner as in Manufacture Example 4 except that the composition of the coating layer was different in Manufacture Example 4, and a polyester film F4a was obtained.
  • Production Example 7 (Polyester film F5a) A polyester film F5a was obtained in the same manner as in Production Example 4 except that the composition of the coating layer in Production Example 4 was different.
  • Production Example 8 (Polyester film F6a)
  • the raw materials blended with polyethylene terephthalate A1 and A2 at a ratio of 80% and 20%, respectively, are used as the surface layer raw material, and the raw material of polyethylene terephthalate A1 100% is supplied to the two vented extruders as the intermediate layer raw material.
  • an amorphous film having a thickness of about 740 ⁇ m was obtained by cooling and solidifying on a cooling roll whose surface temperature was set to 40 ° C. using an electrostatic application adhesion method.
  • the film was stretched 2.8 times in the machine direction at 90 ° C., 5.4 times in the transverse direction at 120 ° C., heat treated at 200 ° C., and then subjected to a relaxation treatment of 4.3% in the width direction.
  • a polyester film having a thickness of 50 ⁇ m (thickness ratio 2.5 ⁇ m / 45 ⁇ m / 2.5 ⁇ m) was obtained.
  • heat treatment is performed at 120 ° C. for 30 seconds.
  • a 50 ⁇ m-thick polyester film F6a provided with a coating layer was obtained.
  • AC1 Colcoat N-103X (manufactured by Colcoat)
  • AC2 Aluminum tris (acetylacetonate)
  • AC3 Zirconium tetraacetylacetonate
  • AC4 Titanium tetraacetylacetonate (mixing conditions)
  • Production Example 9 (Polyester film F7a) Manufactured in the same manner as in Manufacture Example 4 except that no coating layer was provided in Manufacture Example 4 to obtain a polyester film F7a.
  • Example 1 ⁇ Manufacture of first release film>
  • the following release layer composition-A was applied to the polyester film F1a by a reverse gravure coating method so that the coating amount (after drying) was 0.1 g / m 2, and then heat treated at 120 ° C. for 30 seconds.
  • Example number in Table 4 means the Example number in Table 5 mentioned later (hereinafter the same).
  • ⁇ Acrylic pressure-sensitive adhesive layer forming composition > (Monomer composition) 2-ethylhexyl acrylate 70% by weight 2-methoxyethyl acrylate 29% by weight 4-hydroxybutyl acrylate 1% by weight 0.1 part of Nippon Polyurethane Coronate L was added to 100 parts by weight of the monomer composition to obtain an acrylic pressure-sensitive adhesive layer forming composition. Next, using a 2 kg rubber roller, the release layer and the pressure-sensitive adhesive layer of the first release film were bonded together to obtain a substrate-less double-sided pressure-sensitive adhesive sheet. Table 5 shows the properties of the obtained substrate-less double-sided pressure-sensitive adhesive sheet.
  • Example 2 In Example 1, the coating agent composition, the release agent composition, and the polyester film base material thickness were produced in the same manner as in Example 1 except that the thicknesses were changed as shown in Tables 2 and 3 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. Tables 2 to 5 show the properties of the release films and the baseless double-sided PSA sheets obtained in the above examples and comparative examples.
  • polyester used in the examples and comparative examples was prepared as follows.
  • Polyethylene terephthalate A1 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol and 0.09 part of magnesium acetate tetrahydrate are placed in a reactor, the temperature is raised by heating, methanol is distilled off, transesterification is performed, and 4 hours are required from the start of the reaction. The temperature was raised to 230 ° C. to substantially complete the transesterification reaction.
  • the temperature reached 280 ° C. and the pressure reached 15 mmHg in 100 minutes. It was 0.3 mmHg. After 4 hours, the system was returned to atmospheric pressure to obtain polyethylene terephthalate A1 having an intrinsic viscosity of 0.61.
  • Production Example 11 Polyethylene terephthalate A2 In Production Example 10, production was carried out in the same manner as in Production Example 1 except that 0.6 part of silica particles having an average particle diameter of 2.5 ⁇ m was added to obtain polyethylene terephthalate A2 having an intrinsic viscosity of 0.62.
  • Production Example 12 (polyethylene terephthalate A3) In Production Example 1, production was carried out in the same manner as in Production Example 10 except that 1.0 part of synthetic calcium carbonate particles having an average particle diameter of 0.8 ⁇ m was added to obtain polyethylene terephthalate A3 having an intrinsic viscosity of 0.62.
  • Production Example 13 (Polyester film F1b) Two raw materials were blended with polyethylene terephthalate A1 and A3 in proportions of 92% and 8%, respectively, and raw materials blended with polyethylene terephthalate A1 and A3 in proportions of 80% and 20%, respectively. After being melted and extruded at 290 ° C., it was cooled and solidified on a cooling roll set at a surface temperature of 40 ° C. using an electrostatic application adhesion method. An amorphous film having a thickness of about 1300 ⁇ m was obtained.
  • This film was stretched 3.5 times in the longitudinal direction at 90 ° C., stretched 4.1 times in the transverse direction at 130 ° C., heat treated at 230 ° C., and then subjected to a relaxation treatment of 4.3% in the width direction.
  • a polyester film F1b having a thickness of 50 ⁇ m (thickness ratio 2.5 ⁇ m / 45 ⁇ m / 2.5 ⁇ m) was obtained.
  • Production Example 14 (Polyester film F2b) Two raw materials were blended with polyethylene terephthalate A1 and A3 in proportions of 92% and 8%, respectively, and raw materials blended with polyethylene terephthalate A1 and A3 in proportions of 80% and 20%, respectively. After being melt-extruded at 290 ° C. and cooled and solidified on a cooling roll set at a surface temperature of 40 ° C. using an electrostatic application adhesion method, an amorphous film having a thickness of about 740 ⁇ m was obtained. Obtained.
  • This film was stretched 3.5 times in the longitudinal direction at 90 ° C., stretched 4.1 times in the transverse direction at 130 ° C., heat treated at 230 ° C., and then subjected to a relaxation treatment of 4.3% in the width direction.
  • a polyester film having a thickness of 50 ⁇ m (thickness ratio 2.5 ⁇ m / 45 ⁇ m / 2.5 ⁇ m) was obtained.
  • heat treatment is performed at 120 ° C. for 30 seconds.
  • a 50 ⁇ m thick polyester film F2b provided with a coating layer was obtained.
  • AC1 Colcoat N-103X (manufactured by Colcoat)
  • AC2 Aluminum tris (acetylacetonate)
  • AC3 Zirconium tetraacetylacetonate
  • AC4 Titanium tetraacetylacetonate (mixing conditions)
  • Production Example 15 (Polyester film F3b) A polyester film F3b was obtained in the same manner as in Production Example 14 except that the composition of the coating layer in Production Example 14 was different.
  • Production Example 16 (Polyester film F4b) Manufactured in the same manner as in Manufacture Example 14 except that the composition of the coating layer was different in Manufacture Example 14, and a polyester film F4b was obtained.
  • Production Example 17 (Polyester film F5b) A polyester film F5b was obtained in the same manner as in Production Example 14 except that the composition of the coating layer in Production Example 14 was different.
  • Production Example 18 (Polyester film F6b) Two raw materials were blended with polyethylene terephthalate A1 and A3 in proportions of 92% and 8%, respectively, and raw materials blended with polyethylene terephthalate A1 and A3 in proportions of 80% and 20%, respectively. After being melt-extruded at 290 ° C. and cooled and solidified on a cooling roll set at a surface temperature of 40 ° C. using an electrostatic application adhesion method, an amorphous film having a thickness of about 740 ⁇ m was obtained. Obtained.
  • the film was stretched 2.8 times in the machine direction at 90 ° C., 5.4 times in the transverse direction at 120 ° C., heat treated at 200 ° C., and then subjected to a relaxation treatment of 4.3% in the width direction.
  • a polyester film having a thickness of 50 ⁇ m (thickness ratio 2.5 ⁇ m / 45 ⁇ m / 2.5 ⁇ m) was obtained.
  • heat treatment is performed at 120 ° C. for 30 seconds.
  • a polyester film F6b having a thickness of 50 ⁇ m provided with a coating layer was obtained.
  • AC1 Colcoat N-103X (manufactured by Colcoat)
  • AC2 Aluminum tris (acetylacetonate)
  • AC3 Zirconium tetraacetylacetonate
  • AC4 Titanium tetraacetylacetonate (mixing conditions)
  • Production Example 19 (Polyester film F7b) A polyester film F7b was obtained in the same manner as in Production Example 14 except that no coating layer was provided in Production Example 14.
  • Production Example 20 (Polyester film F8b)
  • the raw material composition of the surface layer and the intermediate layer was different as described below, and production was carried out in the same manner as in Production Example 14 except that no coating layer was provided to obtain a polyester film F8b.
  • Surface layer raw materials Raw materials obtained by blending polyethylene terephthalate A1 and A2 at a ratio of 80% and 20%, respectively.
  • Example 7 ⁇ Manufacture of first release film>
  • the following release layer composition-A was applied to the polyester film F1b offline by a reverse gravure coating method so that the coating amount (after drying) was 0.1 g / m 2 , followed by heat treatment at 120 ° C. for 30 seconds.
  • Example number in Table 8 means the Example number in Table 9 described later (hereinafter the same).
  • Polyester film F In 2b, the following release layer composition-D was applied on the coating layer offline by reverse gravure coating so that the coating amount was 0.1 g / m 2 (after drying), and then 120 ° C. for 30 seconds. Heat treated. Tables 6 to 8 show the characteristics of the obtained second release film.
  • ⁇ Acrylic pressure-sensitive adhesive layer forming composition > (Monomer composition) 2-ethylhexyl acrylate 70% by weight 2-methoxyethyl acrylate 29% by weight 4-hydroxybutyl acrylate 1% by weight 0.1 part of Nippon Polyurethane Coronate L was added to 100 parts by weight of the monomer composition to obtain an acrylic pressure-sensitive adhesive layer forming composition. Next, using a 2 kg rubber roller, the release layer and the pressure-sensitive adhesive layer of the first release film were bonded together to obtain a substrate-less double-sided pressure-sensitive adhesive sheet.
  • Example 7 the coating agent composition, the release agent composition, and the polyester film substrate thickness were produced in the same manner as in Example 7 except that the thicknesses were changed as shown in Tables 6 and 7 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. Tables 6 to 9 show the characteristics of the release films and the baseless double-sided PSA sheets obtained in the above Examples and Comparative Examples.
  • the substrate-less double-sided pressure-sensitive adhesive sheet of the present invention has good antistatic properties, releasability, oligomer sealing properties, and good testability, for example, liquid crystal polarizing plate manufacturing, capacitive touch panel manufacturing members, etc. It is suitable as various optical members.
  • Substrate-less double-sided adhesive sheet 11 Adhesive layer 13: First release film substrate 14: First application layer 15: First release agent layer 23: Second release film substrate 24: Second application Layer 25: Second release agent layer 31: First release film (light release sheet) 32: Second release film (heavy release sheet)

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PCT/JP2013/078494 2012-11-22 2013-10-21 基材レス両面粘着シート WO2014080715A1 (ja)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107428135A (zh) * 2015-03-23 2017-12-01 三菱化学株式会社 脱模膜
CN113950409A (zh) * 2019-12-17 2022-01-18 东洋纺株式会社 层叠体

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017200973A (ja) * 2016-05-06 2017-11-09 リンテック株式会社 基材レス両面粘着シート
CN113462311A (zh) * 2016-09-15 2021-10-01 三菱化学株式会社 粘合片层叠体、赋形粘合片层叠体及其制造方法
CN110870087B (zh) 2017-07-10 2023-11-21 高丽大学校世宗产学协力团 伸缩性基板及其制作方法、基板结构体制作装置及方法
CN108456492B (zh) * 2017-12-29 2020-11-24 江西合力泰科技有限公司 一种整版式fpc双面胶及其使用方法
CN110144175A (zh) * 2018-02-13 2019-08-20 日东电工株式会社 粘合片以及粘合片层叠体
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008143047A (ja) * 2006-12-11 2008-06-26 Mitsubishi Plastics Ind Ltd 離型フィルム
JP2009235231A (ja) * 2008-03-27 2009-10-15 Toray Ind Inc 離型用ポリエステルフィルム
JP2009242562A (ja) * 2008-03-31 2009-10-22 Dic Corp キーシート用熱接着シート及びキーシート
JP2011104981A (ja) * 2009-11-19 2011-06-02 Toray Advanced Materials Korea Inc 離型フィルム用２軸延伸ポリエステルフィルム及びこれを用いた離型フィルム
JP2012003007A (ja) * 2010-06-16 2012-01-05 Toyobo Co Ltd 偏光板離型用二軸延伸ポリエチレンテレフタレートフィルム
JP2012207166A (ja) * 2011-03-30 2012-10-25 Mitsubishi Plastics Inc 基材レス両面粘着シート
JP2012214014A (ja) * 2011-03-30 2012-11-08 Mitsubishi Plastics Inc 離型フィルム

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4916131B2 (ja) * 2005-05-31 2012-04-11 三菱樹脂株式会社 離型フィルム

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008143047A (ja) * 2006-12-11 2008-06-26 Mitsubishi Plastics Ind Ltd 離型フィルム
JP2009235231A (ja) * 2008-03-27 2009-10-15 Toray Ind Inc 離型用ポリエステルフィルム
JP2009242562A (ja) * 2008-03-31 2009-10-22 Dic Corp キーシート用熱接着シート及びキーシート
JP2011104981A (ja) * 2009-11-19 2011-06-02 Toray Advanced Materials Korea Inc 離型フィルム用２軸延伸ポリエステルフィルム及びこれを用いた離型フィルム
JP2012003007A (ja) * 2010-06-16 2012-01-05 Toyobo Co Ltd 偏光板離型用二軸延伸ポリエチレンテレフタレートフィルム
JP2012207166A (ja) * 2011-03-30 2012-10-25 Mitsubishi Plastics Inc 基材レス両面粘着シート
JP2012214014A (ja) * 2011-03-30 2012-11-08 Mitsubishi Plastics Inc 離型フィルム

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107428135A (zh) * 2015-03-23 2017-12-01 三菱化学株式会社 脱模膜
CN107428135B (zh) * 2015-03-23 2019-12-24 三菱化学株式会社 脱模膜
CN113950409A (zh) * 2019-12-17 2022-01-18 东洋纺株式会社 层叠体

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