WO2016175232A1 - Carrier film for transparent electroconductive film, and laminate - Google Patents

Carrier film for transparent electroconductive film, and laminate Download PDF

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Publication number
WO2016175232A1
WO2016175232A1 PCT/JP2016/063160 JP2016063160W WO2016175232A1 WO 2016175232 A1 WO2016175232 A1 WO 2016175232A1 JP 2016063160 W JP2016063160 W JP 2016063160W WO 2016175232 A1 WO2016175232 A1 WO 2016175232A1
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WIPO (PCT)
Prior art keywords
transparent conductive
film
conductive film
carrier film
layer
Prior art date
Application number
PCT/JP2016/063160
Other languages
French (fr)
Japanese (ja)
Inventor
真理 松本
数馬 三井
天野　立巳
Original Assignee
日東電工株式会社
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Priority claimed from JP2016086010A external-priority patent/JP6835477B2/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020177024521A priority Critical patent/KR102332014B1/en
Priority to CN201680021326.XA priority patent/CN107429132B/en
Publication of WO2016175232A1 publication Critical patent/WO2016175232A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives

Definitions

  • the present invention relates to a carrier film for a transparent conductive film having a support and an adhesive layer. Moreover, this invention relates to the laminated body which has the said carrier film for transparent conductive films, and a transparent conductive film.
  • ITO thin films In / Sn composite oxide
  • metal thin films such as silver and copper
  • silver nanowire thin films are used as materials for transparent electrodes.
  • the thickness of the thin film substrate including the nanowire thin film tends to become thinner year by year.
  • an anti-reflection (AR) layer is provided as a functional layer on the thin film substrate including the ITO thin film to improve visibility, or a hard coat (HC) layer is provided to prevent scratches.
  • a hard coat (HC) layer is provided to prevent scratches.
  • an anti-blocking (AB) layer is provided to prevent blocking, or an oligomer prevention (OB) layer is provided to prevent white turbidity during heating.
  • a surface protective film or the like is attached to an optical member such as an ITO thin film for the purpose of preventing scratches and dirt in a processing step and a conveyance step.
  • an adhesive film for surface protection used for an optical member for example, from an adhesive that uses two types of (meth) acrylic polymers having different glass transition temperatures at a specific blending ratio and adjusts the degree of crosslinking with a crosslinking agent.
  • a surface protective sheet having a pressure-sensitive adhesive layer formed on a support see Patent Document 1), an acrylic copolymer formed from a monomer component containing specific amounts of 2-ethylhexyl acrylate and hydroxyethyl methacrylate, and a specific amount of A pressure-sensitive adhesive film (see Patent Document 2) in which a pressure-sensitive adhesive layer obtained from a pressure-sensitive adhesive solution containing a polyfunctional isocyanate crosslinking agent is provided on one side of a plastic film is known.
  • a carrier film for a transparent conductive film an adhesive containing a (meth) acrylic polymer having a glass transition temperature of ⁇ 50 ° C. or lower, an isocyanate-based crosslinking agent, and a catalyst centered on iron on at least one surface of a support.
  • a carrier film for transparent conductive film having a pressure-sensitive adhesive layer formed from an adhesive composition is known (see Patent Document 3).
  • Patent Documents 1 and 2 do not fully study the use of transparent conductive films. Therefore, when the surface protection sheet of Patent Documents 1 and 2 is used as a carrier film for a transparent conductive film, the difference in adhesive strength between the low-speed peeling and the high-speed peeling is not sufficiently reduced, and the film is broken during the peeling. In some cases, the transparent conductive film, which is an adherend, cracks.
  • Patent Document 3 although the zipping at the time of peeling from the transparent conductive film can be eliminated, the difference in adhesive force between the low speed peeling and the high speed peeling is not sufficiently small, from the viewpoint of workability, There was room for further study.
  • “Zipping” that occurs when the transparent conductive film is peeled off from the carrier film is a phenomenon in which the transparent conductive film does not peel smoothly when peeled off from the carrier film, and repeats peeling or stopping while making a crisp sound. Means.
  • the carrier film has a high adhesive strength with respect to the transparent conductive film as the adherend, if the zipping occurs, the transparent conductive film may be cracked or leave traces, which is not preferable.
  • the adhesive strength when peeled at a high speed tends to be higher than the adhesive strength when peeled at a low speed.
  • the carrier film is peeled off manually, and generally, an operator often peels off at a high speed, so that the carrier film is hardly peeled off and the workability may be inferior.
  • the film may be broken or broken during peeling. In general, such manual peeling is often performed at a constant peeling speed so that peeling is initially performed at a low speed and then gradually performed at a high speed.
  • a carrier film for a transparent conductive film having a constant adhesive force at any peeling speed has been desired.
  • the present invention can suppress the occurrence of zipping, has excellent adhesion and re-peelability to a transparent conductive film, and has a small difference in adhesive force between high-speed peeling and low-speed peeling and has excellent workability. It aims at providing the carrier film for films. Furthermore, this invention aims at providing the laminated body containing the said carrier film for transparent conductive films, and a transparent conductive film.
  • the present inventors have intensively studied to achieve the above object, and as a result, have found that the above object can be achieved by using the following carrier film for transparent conductive film, and have completed the present invention.
  • the present invention is a carrier film for a transparent conductive film having an adhesive layer on at least one side of a support,
  • the adhesive strength Q when peeled at a tensile speed of 10 m / min is 0.7 N / 50 mm or less, and the absolute value of the difference between the adhesive strength P and the adhesive strength Q is 0.2 N / 50 mm. It is related with the carrier film for transparent conductive films characterized by the following.
  • the pressure-sensitive adhesive layer polymerizes a monomer component containing an alkyl (meth) acrylate, a hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C., and a hydroxyl group-containing monomer having a glass transition temperature of the homopolymer of 50 ° C. or more. It is preferable that it is formed from the adhesive composition containing the (meth) acrylic-type polymer obtained.
  • the amount of the hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C. of the homopolymer is 10 to 17% by weight based on the total amount of the monomer components,
  • the amount of the hydroxyl group-containing monomer having a glass transition temperature of 50 ° C. or higher of the homopolymer is preferably 2 to 8% by weight based on the total amount of the monomer components.
  • the monomer component preferably further contains a carboxyl group-containing monomer, and the amount of the carboxyl group-containing monomer is preferably 0.005 to 0.10% by weight based on the total amount of the monomer component.
  • the pressure-sensitive adhesive composition further contains a crosslinking agent, and the amount of the crosslinking agent exceeds 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.
  • the cross-linking agent is preferably an aliphatic polyisocyanate-based cross-linking agent, and the aliphatic polyisocyanate-based cross-linking agent more preferably contains hexamethylene diisocyanate.
  • a carrier film for a transparent conductive film having an adhesive layer on at least one side of a support is obtained by polymerizing a monomer component containing a hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C. of the homopolymer and a hydroxyl group-containing monomer having a glass transition temperature of the homopolymer of 50 ° C. or more.
  • the carrier film for transparent conductive films characterized by being formed from the adhesive composition containing a base polymer may be sufficient.
  • the present invention is a laminate having a transparent conductive film laminated on the transparent conductive film carrier film and the transparent conductive film carrier film,
  • the present invention relates to a laminate, wherein the adhesive surface of the adhesive layer of the carrier film for transparent conductive film is bonded to at least one surface of the transparent conductive film.
  • the transparent conductive film has a transparent conductive layer and a transparent substrate
  • the adhesive surface of the adhesive layer of the said carrier film for transparent conductive films is affixed on the surface on the opposite side to the surface which contacts the said transparent conductive layer of the said transparent base material is mentioned.
  • the transparent conductive film has a transparent conductive layer and a transparent substrate, and further has a functional layer on the surface of the transparent substrate opposite to the surface in contact with the transparent conductive layer. And The thing by which the adhesive surface of the adhesive layer of the said carrier film for transparent conductive films is affixed on the surface on the opposite side to the surface which contacts the said transparent base material of the said functional layer is mentioned.
  • the carrier film for transparent conductive film of the present invention can suppress the occurrence of zipping, has excellent adhesion and re-peelability to the transparent conductive film, and has a small difference in adhesive force between high-speed peeling and low-speed peeling. Excellent. Furthermore, this invention can provide the laminated body containing the said carrier film for transparent conductive films, and a transparent conductive film.
  • the transparent conductive film as an adherend is not wrinkled or scratched, and the shape of the transparent conductive film is maintained. Can do.
  • the carrier film 3 for transparent conductive film of the present invention has a pressure-sensitive adhesive layer 1 on at least one surface of a support 2, and the surface of the pressure-sensitive adhesive layer 1 that contacts the support 2. It has an adhesive surface A on the opposite side.
  • the adhesive surface A is formed on the surface of the transparent substrate 5 (transparent substrate) constituting the transparent conductive film. 5 where the transparent conductive layer 4 does not exist), and when the transparent conductive film as the adherend is the transparent conductive film 8 with a functional layer as shown in FIG. It is a surface that contacts the functional layer 7.
  • the laminated body 9 of this invention mentioned later contains the carrier film 3 for transparent conductive films, and the transparent conductive film 6 (or transparent conductive film 8 with a functional layer) as shown in FIG.
  • the carrier film for transparent conductive film of the present invention is heated at 140 ° C. for 90 minutes in a state where the pressure-sensitive adhesive layer of the carrier film is bonded to an adherend, and then the carrier film is pulled from the adherend at a tensile rate of 0.
  • the adhesive strength P when peeled at 3 m / min and the adhesive strength Q when peeled at a tensile speed of 10 m / min are both 0.7 N / 50 mm or less, and the adhesive strength P and the adhesive strength Q
  • the absolute value of the difference is 0.2 N / 50 mm or less.
  • the adhesive strength P is 0.7 N / 50 mm or less, preferably 0.6 N / 50 mm or less, and more preferably 0.5 N / 50 mm or less.
  • the lower limit value of the adhesive strength P is not particularly limited, but is preferably 0.1 N / 50 mm or more from the viewpoint of the adhesive strength with respect to the transparent conductive film as the adherend.
  • the adhesive force when peeled at a tensile speed of 0.3 m / min is in the above range, so that zipping does not occur even when the carrier film for transparent conductive film is peeled off from the transparent conductive film at a low speed, This is preferable because of excellent balance between adhesion and removability.
  • the adhesive strength Q is 0.7 N / 50 mm or less, preferably 0.6 N / 50 mm or less, and more preferably 0.5 N / 50 mm or less.
  • the lower limit value of the adhesive strength Q is not particularly limited, but is preferably 0.1 N / 50 mm or more from the viewpoint of the adhesive strength with respect to the transparent conductive film as the adherend.
  • the absolute value of the difference between the adhesive strength P and the adhesive strength Q is 0.2 N / 50 mm or less, preferably 0.15 N / 50 mm or less, more preferably 0.1 N / 50 mm or less, 0 .05 N / 50 mm or less is particularly preferable.
  • the lower limit of the absolute value of the difference between the adhesive force P and the adhesive force Q is not particularly limited, and the smaller the smaller the better, the more ideally there is no difference (0 N / 50 mm). . If the absolute value of the difference between the adhesive strength P and the adhesive strength Q exceeds 0.2 N / 50 mm, the film may be broken during the peeling or transparent when the carrier film for transparent conductive film is peeled off from the transparent conductive film.
  • a crack may enter the conductive layer.
  • the absolute value of the difference between the adhesive force P and the adhesive force Q is within the above range, so that the peeling is performed like a manual peeling operation (usually peeling at low speed at the beginning and gradually approaching high speed peeling). Even in the case where the speed is not constant, the film is not broken during the peeling or the transparent conductive layer is cracked, and therefore, the releasability of the carrier film for transparent conductive film is excellent, which is preferable.
  • the “adhered body” at the time of measuring the adhesive force is a transparent conductive film, and when the transparent conductive film does not have a functional layer, the adherend surface is a transparent substrate constituting the transparent conductive film. When the transparent conductive film has a functional layer, the adherend surface is the surface of the functional layer.
  • the carrier film for transparent conductive film of the present invention is not particularly limited as long as it has an adhesive layer on at least one surface of the support and has the above-mentioned adhesive force, and the adhesive composition is not particularly limited. The composition will be described.
  • the pressure-sensitive adhesive layer in the present invention is not particularly limited, and may be acrylic, synthetic rubber-based, rubber-based, silicone-based, etc. From the viewpoint of properties and the like, an acrylic pressure-sensitive adhesive having a (meth) acrylic polymer as a base polymer is preferable.
  • the (meth) acrylic polymer used as the base polymer of the acrylic pressure-sensitive adhesive is obtained by polymerizing a monomer component containing an alkyl (meth) acrylate, and the glass transition temperature of the alkyl (meth) acrylate and homopolymer is 50.
  • alkyl (meth) acrylate for example, those having an alkyl group having 2 to 14 carbon atoms can be used.
  • main monomer component of the alkyl (meth) acrylate an alkyl group having 4 to 14 carbon atoms can be used. Certain alkyl (meth) acrylates are preferred, alkyl (meth) acrylates having 6 to 14 carbon atoms are more preferred, and alkyl (meth) acrylates having 6 to 9 carbon atoms are particularly preferred.
  • the main monomer is 50% by weight or more, more preferably 60% by weight or more, and still more preferably 80% by weight or more based on the total amount of “alkyl (meth) acrylate” contained in the monomer component. Particularly preferably 100% by weight.
  • alkyl (meth) acrylate having an alkyl group having 2 to 14 carbon atoms examples include ethyl (meth) acrylate, n-butyl (meth) acrylate (BA), t-butyl (meth) acrylate, isobutyl (meth) ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (2EHA), n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n -Decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth)
  • Te n-butyl (meth) acrylate (BA) and 2-ethylhexyl (meth) acrylate (2EHA) are preferable, and 2-ethylhexyl (meth) acrylate (2EHA) is particularly preferable.
  • the alkyl (meth) acrylate having an alkyl group having 6 to 14 carbon atoms is preferably used, and the alkyl having an alkyl group having 6 to 14 carbon atoms (
  • the (meth) acrylate is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 80% by weight or more, and particularly preferably 90% by weight or more based on the total amount of the alkyl (meth) acrylate.
  • the content of the alkyl (meth) acrylate is preferably 65% by weight in the monomer component, more preferably 75% by weight or more, and further preferably 80% by weight or more.
  • the homopolymer has a glass transition temperature of less than 50 ° C. and has an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. And those having a functional group and having a hydroxyl group.
  • 2-hydroxyethyl acrylate (homopolymer Tg: ⁇ 15 ° C.), 2-hydroxypropyl methacrylate (homopolymer Tg: 26 ° C.), 2-hydroxypropyl acrylate (homopolymer Tg: ⁇ 7 ° C.) ), 4-hydroxybutyl acrylate (homopolymer Tg: ⁇ 32 ° C.), etc., hydroxyalkyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate (homopolymer Tg: 17 ° C.), 1,4-cyclohexane (Meth) acrylate having a cyclic structure such as dimethanol monoacrylate (homopolymer Tg: 18 ° C.), polyethylene glycol monoacrylate (number of moles of ethylene glycol: 10, homopolymer Tg: ⁇ 64 ° C.), polypropylene glycol mono Accel Relay (Meth) acrylates having an alkylene oxide structure such as propylene
  • the glass transition temperature of the homopolymer of the hydroxyl group-containing monomer may be less than 50 ° C., for example, preferably 30 ° C. or less, more preferably ⁇ 40 to 30 ° C., and ⁇ 40 to 0 More preferably, the temperature is C.
  • the content of the hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C. of the homopolymer is preferably 10 to 17% by weight, more preferably 10 to 15% by weight, based on the total amount of the monomer components. More preferably, it is ⁇ 14% by weight.
  • the content ratio of the hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C. of the homopolymer is less than 10% by weight, the number of reaction points is small, so that the crosslinking density is lowered and the adhesive strength tends to be increased. In that case, since the removability with respect to a transparent conductive film will fall, it is unpreferable.
  • hydroxyl group-containing monomer having a glass transition temperature of 50 ° C. or higher of the homopolymer a polymer having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group having a glass transition temperature of the homopolymer of 50 ° C. or higher. And those having a functional group and having a hydroxyl group.
  • 2-hydroxyethyl methacrylate (homopolymer Tg: 55 ° C.), N-methylolacrylamide (homopolymer Tg: 110 ° C.), N- (2-hydroxyethyl) acrylamide (homopolymer Tg: 98) ° C) and the like, and these can be used alone or in combination of two or more.
  • 2-hydroxyethyl methacrylate (homopolymer Tg: 55 ° C.) is preferable from the viewpoint that zipping can be suppressed.
  • the glass transition temperature of the homopolymer of the hydroxyl group-containing monomer may be 50 ° C. or more, but is preferably 50 to 150 ° C., more preferably 50 to 100 ° C., and more preferably 50 to 90 ° C. More preferably.
  • the content of the hydroxyl group-containing monomer having a glass transition temperature of 50 ° C. or higher in the homopolymer is preferably 2 to 8% by weight, more preferably 3 to 6% by weight, based on the total amount of the monomer components.
  • the content ratio of the hydroxyl group-containing monomer having a glass transition temperature of 50 ° C. or higher of the homopolymer is less than 2% by weight, the adhesive force at high-speed peeling tends to be difficult to decrease. There is a tendency that the adhesive strength of the resin tends to decrease too much, which is not preferable.
  • the monomer component may contain other polymerizable monomer other than the alkyl (meth) acrylate and the hydroxyl group-containing monomer.
  • the polymerizable monomer for adjusting the glass transition point and peelability of a (meth) acrylic-type polymer etc. can be used in the range which does not impair the effect of this invention.
  • Other polymerizable monomers may be used alone or in combination, but the blending amount of the other polymerizable monomer is preferably 10% by weight or less, preferably 5% by weight or less based on the total amount of the monomer components. Is more preferable.
  • Examples of the polymerizable monomer include carboxyl group-containing monomers.
  • the carboxyl group-containing monomer can be used from the viewpoint that the crosslinking reaction can be carried out more efficiently and the adhesive force at high speed peeling can be lowered.
  • Examples of the carboxyl group-containing monomer include those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and containing a carboxyl group. (Meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like.
  • acrylic acid is preferred from the viewpoints of polymerizability, cohesiveness, cost, and versatility.
  • the content of the carboxyl group-containing monomer is preferably 0.005 to 0.10% by weight, more preferably 0.005 to 0.05% by weight, based on the total amount of the monomer components. It is preferable that the content of the carboxyl group-containing monomer is in the above-mentioned range since there is an effect of reducing the adhesive strength at high speed peeling.
  • Examples of the other polymerizable monomers include components for improving cohesion and heat resistance such as sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, and acid anhydrides.
  • a monomer component having a functional group that functions as a crosslinking point such as a group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, N-acryloylmorpholine, or a vinyl ether monomer, can be used as appropriate.
  • These monomer components may be used alone or in admixture of two or more.
  • Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride.
  • sulfonic acid group-containing monomer examples include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) ) Acrylyloxynaphthalene sulfonic acid and the like.
  • Examples of the phosphoric acid group-containing monomer include 2-hydroxyethylacryloyl phosphate, 2- (phosphonooxy) ethyl methacrylate, 3-chloro-2- (phosphonooxy) propyl methacrylate, and the like.
  • Examples of the cyano group-containing monomer include acrylonitrile.
  • vinyl ester monomer examples include vinyl acetate, vinyl propionate, vinyl laurate, and the like.
  • aromatic vinyl monomer examples include styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene, and the like.
  • amide group-containing monomer examples include acrylamide and diethyl acrylamide.
  • amino group-containing monomer examples include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like.
  • epoxy group-containing monomer examples include glycidyl (meth) acrylate and allyl glycidyl ether.
  • vinyl ether monomer examples include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.
  • the (meth) acrylic polymer used in the present invention is obtained by polymerizing the monomer components, and the polymerization method is not particularly limited, and is solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization. Polymerization can be performed by a known method such as turbid polymerization, and solution polymerization is more preferable from the viewpoint of workability and the like.
  • the obtained polymer may be any of homopolymer, random copolymer, block copolymer and the like.
  • the (meth) acrylic polymer used in the present invention preferably has a weight average molecular weight of 300,000 to 5,000,000, more preferably 400,000 to 2,000,000, particularly preferably 500,000 to 1,000,000.
  • the weight average molecular weight is less than 300,000, the adhesive strength at the time of peeling increases due to the improvement of wettability to the transparent conductive film that is the adherend (with functional layer). This may cause damage to the adherend, and the adhesive force tends to be generated due to the reduced cohesive force of the pressure-sensitive adhesive layer.
  • a weight average molecular weight means what was obtained by measuring by GPC (gel permeation chromatography).
  • the glass transition temperature (Tg) of the (meth) acrylic polymer is preferably 0 ° C. or lower (usually ⁇ 100 ° C. or higher, and preferably ⁇ 70 ° C. or higher) for easy balance of adhesive performance. -10 ° C or lower is more preferable, -20 ° C or lower is further preferable, and -30 ° C or lower is particularly preferable.
  • the glass transition temperature is higher than 0 ° C., the polymer is difficult to flow, and the transparent conductive film as the adherend is not sufficiently wetted with the transparent base material, and the gap between the adherend and the adhesive layer of the carrier film Tend to cause blisters to occur.
  • the glass transition temperature (Tg) of a (meth) acrylic-type polymer can be adjusted in the said range by changing the monomer component and composition ratio to be used suitably.
  • a crosslinking agent to the pressure-sensitive adhesive composition used in the present invention.
  • a crosslinking agent an isocyanate compound, an epoxy compound, a melamine resin, an aziridine derivative, a metal chelate compound, or the like is used.
  • an isocyanate compound is particularly preferably used mainly from the viewpoint of obtaining an appropriate cohesive force. These compounds may be used alone or in combination of two or more.
  • Examples of the isocyanate compound include compounds having at least two isocyanate groups.
  • aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and the like are generally used.
  • aliphatic polyisocyanates can be preferably used from the viewpoint of zipping suppression and adhesive strength, but alicyclic polyisocyanates and aromatic polyisocyanates are not used from the viewpoint of zipping suppression and adhesive strength. preferable.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl.
  • trimethylene diisocyanate tetramethylene diisocyanate
  • hexamethylene diisocyanate pentamethylene diisocyanate
  • 1,2-propylene diisocyanate 1,3-butylene diisocyanate
  • dodecamethylene diisocyanate 2,4,4-trimethyl.
  • Hexamethylene diisocyanate and the like can be mentioned, and among these, aliphatic polyisocyanates containing hexamethylene diisocyanate are preferable from the viewpoints of suppression of zipping and adhesive strength.
  • isocyanate crosslinking agents examples include trade names “Coronate HL” and “Coronate HX” (manufactured by Nippon Polyurethane Industry Co., Ltd.); trade names “Takenate D-160N” and “Takenate D-165N”. "Takenate D-170HN”, “Takenate D-178N” (above, manufactured by Mitsui Chemicals, Inc.) and the like. These compounds may be used alone or in combination of two or more.
  • the amount of the isocyanate-based crosslinking agent is preferably more than 20 parts by weight, more preferably more than 20 parts by weight and not more than 30 parts by weight based on 100 parts by weight of the (meth) acrylic polymer.
  • the amount is more preferably 21 to 25 parts by weight, and particularly preferably 22 to 24 parts by weight.
  • an appropriate adhesive strength can be expressed by high-speed peeling and low-speed peeling, and the difference in adhesive strength between high-speed peeling and low-speed peeling can be reduced.
  • the isocyanate crosslinking agent is added in an amount of 0.89 to 1.22 in terms of an OH / NCO equivalent ratio with respect to the hydroxyl group of the (meth) acrylic polymer. It is more preferable to add in an amount of .95 to 1.14.
  • isocyanate-based crosslinking agents may be used alone or in combination of two or more, and a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound may be used in combination.
  • Examples of the epoxy compound include N, N, N ′, N′-tetraglycidyl-m-xylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like. These compounds may be used alone or in combination of two or more.
  • Examples of the melamine resin include hexamethylol melamine.
  • an aziridine derivative for example, a trade name HDU (manufactured by Mutual Yakuko Co., Ltd.), a brand name TAZM (manufactured by Mutual Yakuko Co., Ltd.), a brand name TAZO (manufactured by Mutual Yakuko Co., Ltd.), etc. Is mentioned. These compounds may be used alone or in combination of two or more.
  • metal chelate compound examples include aluminum, titanium, nickel, zirconium and the like as the metal component, and acetylene, methyl acetoacetate, ethyl acetoacetate, ethyl lactate, acetylacetone and the like as the chelate component. These compounds may be used alone or in combination.
  • the amount used is not particularly limited as long as the effects of the present invention are not impaired, but the total amount of the isocyanate crosslinking agent is 100 parts by weight of the (meth) acrylic polymer. It is preferable to use in an amount exceeding 20 parts by weight and the ratio of the isocyanate-based crosslinking agent in the total amount of the crosslinking agent is in the range of 50% by weight or more, further 70% by weight or more, and further 90% by weight or more.
  • the pressure-sensitive adhesive composition of the present invention may contain a polyfunctional monomer having two or more radiation-reactive unsaturated bonds in addition to the (meth) acrylic polymer.
  • the polyfunctional monomer can be used as a monomer component when preparing the (meth) acrylic polymer.
  • the (meth) acrylic polymer is crosslinked by irradiating radiation or the like.
  • a polyfunctional monomer having two or more radiation-reactive unsaturated bonds in one molecule for example, it can be crosslinked (cured) by irradiation with radiation such as a vinyl group, an acryloyl group, a methacryloyl group, or a vinylbenzyl group.
  • a polyfunctional monomer having two or more kinds of radiation reactivity of one kind or two kinds or more can be mentioned.
  • the polyfunctional monomer generally, those having 10 or less radiation-reactive unsaturated bonds are preferably used. These compounds may be used alone or in combination of two or more.
  • polyfunctional monomer examples include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6 hexane.
  • examples include diol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, and N, N′-methylenebisacrylamide.
  • the blending amount of the polyfunctional monomer is preferably 30 parts by weight or less with respect to 100 parts by weight (solid content) of the (meth) acrylic polymer.
  • Examples of the radiation include ultraviolet rays, laser rays, ⁇ rays, ⁇ rays, ⁇ rays, X rays, electron rays, and the like, and ultraviolet rays are preferably used from the viewpoints of controllability, good handleability, and cost. More preferably, ultraviolet rays having a wavelength of 200 to 400 nm are used. Ultraviolet rays can be irradiated using an appropriate light source such as a high-pressure mercury lamp, a microwave excitation lamp, or a chemical lamp. In addition, when using an ultraviolet-ray as a radiation, a photoinitiator is mix
  • the photopolymerization initiator may be any substance that generates radicals or cations by irradiating ultraviolet rays having an appropriate wavelength that can trigger the polymerization reaction according to the type of the radiation-reactive component.
  • radical photopolymerization initiators for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, methyl o-benzoylbenzoate-p-benzoin ethyl ether, benzoin isopropyl ether, ⁇ -methylbenzoin, benzyl dimethyl ketal, trichloro Acetophenones such as acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-isopropyl-2-methylpropiophenone, etc.
  • benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, methyl o-benzoylbenzoate-p-benzoin ethyl ether, benzoin isopropyl ether, ⁇ -methylbenzoin, benzyl dimethyl
  • Propiophenones benzophenone, methylbenzophenone, p-chlorobenzophenone, benzophenones such as p-dimethylaminobenzophenone, 2-chlorothioxanthone, 2-ethyl Thioxanthones such as oxanthone and 2-isopropylthioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl)- Examples include acylphosphine oxides such as (ethoxy) -phenylphosphine oxide, benzyl, dibenzosuberone, ⁇ -acyloxime ester, and the like. These compounds may be used alone or in combination of two or more.
  • Examples of the cationic photopolymerization initiator include onium salts such as aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes, nitro Examples thereof include benzyl ester, sulfonic acid derivative, phosphoric acid ester, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, and N-hydroxyimide sulfonate. These compounds may be used alone or in combination of two or more.
  • the photopolymerization initiator is usually added in an amount of 0.1 to 10 parts by weight and preferably 0.2 to 7 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.
  • a photoinitiated polymerization aid such as amines in combination.
  • the photoinitiator aid include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and the like. These compounds may be used alone or in combination of two or more.
  • the polymerization initiation assistant is preferably added in an amount of 0.05 to 10 parts by weight, more preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer.
  • a catalyst can be added to the pressure-sensitive adhesive composition used in the present invention.
  • the type of the catalyst is not particularly limited, and a catalyst known in this field such as a tin catalyst can be used, but it is preferable to use a tin catalyst. Moreover, in this invention, it is preferable not to contain the catalyst which uses iron as an active center.
  • tin catalyst examples include dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin diolate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin, dibutyltin benzyl Malate, dioctyltin diacetate, etc. can be mentioned, These can be used individually or in mixture of 2 or more types. Among these, dioctyltin dilaurate is preferable.
  • the amount of the catalyst added is not particularly limited, but for example, it is preferably about 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the acrylic polymer.
  • the pressure-sensitive adhesive composition used in the present invention may contain other known additives, such as powders such as colorants and pigments, surfactants, plasticizers, and tackifiers.
  • powders such as colorants and pigments, surfactants, plasticizers, and tackifiers.
  • powders such as colorants and pigments, surfactants, plasticizers, and tackifiers.
  • leveling agent such as antioxidant, corrosion inhibitor, light stabilizer, UV absorber, polymerization inhibitor, silane coupling agent, inorganic or organic filler, metal powder, particulate
  • blend suitably according to the use which uses a foil-like thing.
  • the solid content of the pressure-sensitive adhesive composition is not particularly limited, and is preferably 20% by weight or more, and more preferably 30% by weight or more.
  • the pressure-sensitive adhesive layer used in the present invention is formed from the pressure-sensitive adhesive composition as described above.
  • the carrier film for transparent conductive films (with a functional layer) of this invention forms such an adhesive layer on a support body (a base material, a base material layer).
  • the crosslinking of the (meth) acrylic polymer is generally performed after the application of the pressure-sensitive adhesive composition, but the pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition after crosslinking may be transferred to a support or the like. Is possible.
  • a method for forming the pressure-sensitive adhesive layer on the support is not particularly limited.
  • the pressure-sensitive adhesive composition is applied to the support (for example, as a solid content). 20% by weight or more, and more preferably 30% by weight or more), and the pressure-sensitive adhesive layer is formed on the support by drying and removing the polymerization solvent and the like. Thereafter, curing may be performed for the purpose of adjusting the component transfer of the pressure-sensitive adhesive layer, adjusting the crosslinking reaction, and the like.
  • the pressure-sensitive adhesive composition when the pressure-sensitive adhesive composition is applied on a support to produce a carrier film for a transparent conductive film, the pressure-sensitive adhesive composition is a kind other than the polymerization solvent so that it can be uniformly applied on the support.
  • the above solvent may be newly added.
  • a known method used for manufacturing a pressure-sensitive adhesive tape or the like is used as a method for applying the pressure-sensitive adhesive composition. Specifically, for example, roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating and the like can be mentioned.
  • the drying conditions for drying the pressure-sensitive adhesive composition applied to the support can be appropriately determined depending on the composition, concentration, type of solvent in the composition, etc., and are not particularly limited. However, it can be dried at 80 to 200 ° C. for about 10 seconds to 30 minutes.
  • the pressure-sensitive adhesive layer is applied by light irradiation after coating on one side or both sides of the support (base material, base material layer).
  • the pressure-sensitive adhesive layer is obtained by photopolymerization by irradiating an ultraviolet ray having an illuminance of 1 to 200 mW / cm 2 at a wavelength of 300 to 400 nm with a light amount of about 400 to 4000 mJ / cm 2 .
  • the thickness of the pressure-sensitive adhesive layer of the carrier film for transparent conductive film of the present invention is preferably 5 to 50 ⁇ m, more preferably 10 to 30 ⁇ m. Within the above range, the balance between adhesion and removability is excellent and a preferred embodiment is obtained.
  • the pressure-sensitive adhesive layer is formed on at least one surface of a support (base material layer) used in the present invention by coating or the like to form a film, sheet, tape or the like.
  • the support (base material) (2 in FIG. 1) constituting the carrier film for transparent conductive film of the present invention is not particularly limited.
  • a paper-based support such as paper; Non-woven fabrics, nets and other fiber-based supports (the raw materials are not particularly limited, for example, Manila hemp, rayon, polyester, pulp fibers, etc. can be selected as appropriate); metal-based supports such as metal foils and metal plates Body; Plastic support such as plastic film or sheet; Rubber support such as rubber sheet; Foam such as foam sheet or laminate thereof (for example, lamination of plastic support and other support)
  • a suitable thin leaf body such as a body or a laminate of plastic films (or sheets) can be used.
  • ⁇ -olefin such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) is used as a monomer component.
  • Olefin resins Polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); polycarbonate resins; polyvinyl chloride (PVC); vinyl acetate resins; polyphenylene sulfide (PPS) Amide resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); polyimide resins; polyolefin resins having a cyclic or norbornene structure; polyether ether ketone (PEEK) It is. These materials can be used alone or in combination of two or more. Among these, the polyester-based resin has toughness, workability, transparency, and the like, and therefore, by using it as a carrier film for a transparent conductive film, workability and testability are improved. This is a more preferable embodiment.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PBT polybutylene terephthalate
  • PVC
  • the polyester resin is not particularly limited as long as it can be formed into a sheet shape or a film shape, and examples thereof include polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate. . These polyester resins may be used alone (homopolymer), or two or more kinds may be mixed and polymerized (copolymers, etc.).
  • PET polyethylene terephthalate
  • polyethylene terephthalate since it is used as a carrier film for a transparent conductive film, polyethylene terephthalate is preferably used as a support. By using polyethylene terephthalate, it becomes a carrier film for a transparent conductive film excellent in toughness, workability, and transparency, and workability is improved, which is a preferred embodiment.
  • the thickness of the support is generally 25 to 300 ⁇ m, preferably 75 to 200 ⁇ m, more preferably 80 to 140 ⁇ m, and particularly preferably 90 to 130 ⁇ m.
  • the transparent conductive film carrier film is attached to a transparent conductive film (with a functional layer) and used to maintain the shape of the transparent conductive film that is flexible and flexible. This is useful because it can prevent the occurrence of defects such as wrinkles and scratches in the processing step and the conveying step.
  • the support may include a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, release with a silica powder, antifouling treatment, acid treatment, alkali treatment, primer, if necessary.
  • Anti-adhesive treatment such as treatment, corona treatment, plasma treatment, ultraviolet treatment, coating type, kneading type, vapor deposition type, etc. can also be performed.
  • the surface of the support may be subjected to corona treatment or the like. Moreover, you may perform a back surface process to a support body.
  • the carrier film for a transparent conductive film (with a functional layer) of the present invention is a silicone-based, fluorine-based, long-chain alkyl-based, or fatty acid amide-based release agent on the pressure-sensitive adhesive surface for the purpose of protecting the pressure-sensitive adhesive surface as necessary. It is possible to bond a separator treated with an agent.
  • the substrate constituting the separator there are paper and plastic film, but a plastic film is preferably used from the viewpoint of excellent surface smoothness.
  • the film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer.
  • a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
  • the support for the separator may be subjected to anti-static treatment such as alkali treatment, primer treatment, corona treatment, plasma treatment, ultraviolet treatment, coating type, kneading type, vapor deposition type, etc., if necessary. It can also be processed. In particular, when an antistatic treatment is performed, it is preferable to provide an antistatic treatment layer between the support and the release agent.
  • anti-static treatment such as alkali treatment, primer treatment, corona treatment, plasma treatment, ultraviolet treatment, coating type, kneading type, vapor deposition type, etc.
  • Transparent conductive film 6 can mention the film which has the transparent conductive layer 4 and the transparent base material 5, as shown in FIG.
  • the transparent substrate 5 examples include a resin film and a substrate made of glass or the like (for example, a sheet-like, film-like, or plate-like substrate (member)). In particular, a resin film can be mentioned. .
  • the thickness of the transparent substrate 5 is not particularly limited, but is preferably about 10 to 200 ⁇ m, more preferably about 15 to 150 ⁇ m.
  • the material of the resin film is not particularly limited, and various plastic materials having transparency can be mentioned.
  • the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins.
  • polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.
  • the transparent base material 5 is subjected to an etching process such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, or undercoating treatment on the surface in advance, and the transparent conductive layer 4 provided thereon. You may make it improve the adhesiveness with respect to the said transparent base materials 5, such as. Further, before the transparent conductive layer 4 is provided, dust may be removed and cleaned by solvent cleaning, ultrasonic cleaning, or the like, if necessary.
  • an etching process such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, or undercoating treatment on the surface in advance, and the transparent conductive layer 4 provided thereon. You may make it improve the adhesiveness with respect to the said transparent base materials 5, such as. Further, before the transparent conductive layer 4 is provided, dust may be removed and cleaned by solvent cleaning, ultrasonic cleaning, or the like, if necessary.
  • the constituent material of the transparent conductive layer 4 is not particularly limited, and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten.
  • a metal oxide of at least one metal is used.
  • the metal oxide may further contain a metal atom shown in the above group, if necessary.
  • indium oxide (ITO) containing tin oxide, tin oxide containing antimony, or the like is preferably used, and ITO is particularly preferably used.
  • ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.
  • the thickness of the transparent conductive layer 4 is not particularly limited, but is preferably 10 to 300 nm, and more preferably 15 to 100 nm.
  • the method for forming the transparent conductive layer 4 is not particularly limited, and a conventionally known method can be employed. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified. In addition, an appropriate method can be adopted depending on the required film thickness.
  • an undercoat layer, an oligomer prevention layer, etc. can be provided between the transparent conductive layer 4 and the transparent base material 5 as necessary.
  • the transparent conductive film 6 having the transparent conductive layer 4 can be used as a substrate for optical devices (optical member).
  • the substrate for an optical device is not particularly limited as long as it is a substrate having optical characteristics.
  • a display device liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic Paper, etc.
  • base materials members constituting devices such as input devices (touch panels, etc.) or base materials (members) used in these devices.
  • These substrate materials for optical devices have become stiff due to the recent trend of thinning, and have been prone to bend and deform in shape during processing and transporting processes.
  • a shape can be hold
  • a functional layer 7 can be provided on the surface of the transparent conductive film 6 where the transparent conductive layer 5 is not provided.
  • Examples of the functional layer include an antiglare treatment (AG) layer, an antireflection (AR) layer, a hard coat (HC), and an antiblocking (AB) layer for the purpose of improving visibility.
  • AG antiglare treatment
  • AR antireflection
  • HC hard coat
  • AB antiblocking
  • the constituent material of the antiglare treatment layer is not particularly limited, and for example, an ionizing radiation curable resin, a thermosetting resin, a thermoplastic resin, or the like can be used.
  • the thickness of the antiglare treatment layer is preferably from 0.1 to 30 ⁇ m.
  • titanium oxide, zirconium oxide, silicon oxide, magnesium fluoride, or the like is used.
  • the antireflection layer can be provided with a plurality of layers.
  • the material for forming the hard coat (HC) layer for example, a cured film made of a curable resin such as a melamine resin, a urethane resin, an alkyd resin, an acrylic resin, or a silicone resin is preferably used.
  • the thickness of the hard coat layer is preferably from 0.1 to 30 ⁇ m. The thickness is preferably 0.1 ⁇ m or more for imparting hardness.
  • the antiglare treatment layer, the antireflection layer, and the antiblocking layer can be provided on the hard coat layer. Further, a hard coat layer having an antiglare function, an antireflection function, an antiblocking function, and an oligomer prevention function can be used.
  • a curable resin layer containing fine particles, a curable resin composition using a coating composition containing two or more components that are phase-separated, or a combination thereof are used.
  • those having irregularities formed on the surface are preferably used.
  • the component of the curable resin layer include a thermosetting resin, an ultraviolet curable resin, and an electron beam curable resin.
  • a coating composition containing 2 or more types of components which phase-separate the composition as described in the international publication 2005/073763 pamphlet can be used suitably, for example.
  • the thickness of the anti-blocking layer is preferably 0.1 to 30 ⁇ m.
  • the thickness of the transparent conductive film with a functional layer is preferably 210 ⁇ m or less, and more preferably 150 ⁇ m or less.
  • this invention is the laminated body 9 which has the transparent conductive film 6 laminated
  • the carrier film for transparent conductive film 3 is a carrier film for transparent conductive film described in the present specification,
  • the transparent conductive film 6 has a transparent conductive layer 4 and a transparent substrate 5,
  • the adhesive surface of the adhesive layer 1 of the carrier film 3 for transparent conductive film is bonded to the surface of the transparent substrate 5 opposite to the surface that contacts the transparent conductive layer 4.
  • the laminated body 9 for example, FIG. 2).
  • the present invention is a laminate having a transparent conductive film carrier film 3 and a transparent conductive film 6 laminated on the transparent conductive film carrier film 3,
  • the carrier film for transparent conductive film 3 is a carrier film for transparent conductive film described in the present specification
  • the transparent conductive film 3 has a transparent conductive layer 4 and a transparent substrate 5, and further has a functional layer 7 on the surface of the transparent substrate opposite to the surface in contact with the transparent conductive layer,
  • a laminate in which the adhesive surface of the adhesive layer 1 of the carrier film 3 for transparent conductive film is bonded to the surface of the functional layer 7 opposite to the surface in contact with the transparent substrate 5.
  • Examples of the carrier film for transparent conductive film used in the laminate of the present invention and the transparent conductive film (with a functional layer) include those described above.
  • Production Examples 2 to 12 In Production Example 1, as shown in Table 1, the acrylic polymers (A2) to (A) were prepared in the same manner as in Production Example 1 except that the type of monomer used for the preparation of the acrylic polymer and the use ratio thereof were changed. Solutions of (A8) and (A11) to (A14) were prepared.
  • Tg glass transition temperature
  • Example 1 Adjustment of adhesive solution
  • the acrylic polymer (A1) solution (about 35% by weight) obtained in Production Example 1 was diluted to 29% by weight with ethyl acetate, and hexamethylene was added to 100 parts by weight (solid content) of the acrylic polymer in this solution.
  • the acrylic pressure-sensitive adhesive composition (1) is applied to one side of a polyethylene terephthalate (PET) substrate (thickness 125 ⁇ m, support) and heated at 150 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m. Formed.
  • PET polyethylene terephthalate
  • the surface of the pressure-sensitive adhesive layer was bonded with a silicone-treated surface of a PET release liner (thickness 25 ⁇ m) that had been subjected to silicone treatment on one side, and stored at 50 ° C. for 1 day to obtain a carrier film for transparent conductive film. Produced. In use, the release liner was removed before use.
  • Comparative Examples 1 to 6 As shown in Table 2, the type of acrylic polymer, the cross-linking agent constituting the pressure-sensitive adhesive composition, or the blending amount thereof was changed. Further, in Comparative Examples 3 and 4, an iron catalyst (acetylacetone first) was used instead of the tin catalyst. A carrier film for a transparent conductive film was produced in the same manner as in Example 1 except that diiron) was used.
  • a transparent conductive film (trade name: V150-OFJ, PET film having a width of 50 mm and a length of 100 mm, fixed to a SUS plate (SUS430BA), has a transparent conductive layer on one side and an anti-surface on the other side.
  • Nitto Denko film having a blocking layer formed from a coating composition composed of amorphous silica, acrylic monomer, photoinitiator and additives containing less than 5% by weight of 0.8 ⁇ m acrylic particles
  • the pressure-sensitive adhesive layer of the carrier film for transparent conductive film was bonded to the surface of the anti-blocking layer (manufactured by Co., Ltd.) (pressure bonding with a bonding machine: 0.25 MPa, pressure bonding speed 2.0 m / min). Next, after heating at 140 ° C.
  • a transparent conductive film (trade name: V150-OFJ, PET film having a width of 50 mm and a length of 100 mm, fixed to a SUS plate (SUS430BA), has a transparent conductive layer on one side and an anti-surface on the other side.
  • Nitto Denko film having a blocking layer formed from a coating composition composed of amorphous silica, acrylic monomer, photoinitiator and additives containing less than 5% by weight of 0.8 ⁇ m acrylic particles
  • the pressure-sensitive adhesive layer of the carrier film for transparent conductive film was bonded to the surface of the anti-blocking layer (manufactured by Co., Ltd.) (pressure bonding with a bonding machine: 0.25 MPa, pressure bonding speed 2.0 m / min). Next, after heating at 140 ° C.
  • the carrier film for transparent conductive film was peeled 80 mm from the transparent conductive film under the conditions, and the peel force (N / 50 mm) at this time was measured. Using the measurement data for the latter half 60 mm of the peeling force, the presence or absence of zipping was evaluated by the following formula.
  • A1 to A14 are (meth) acrylic polymers produced in Production Examples 1 to 12, respectively.
  • C / HX is an isocyanate crosslinking agent (isocyanurate of hexamethylene diisocyanate, trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.)
  • C / L is an isocyanate crosslinking agent (trimethylolpropane / tolylene diisocyanate trimer adduct, trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.)
  • the tin catalyst is dioctyltin dilaurate,
  • the iron catalyst refers to ferric acetylacetone.

Abstract

A purpose of the present invention is to provide a carrier film for transparent electroconductive films which can be inhibited from causing zipping, is excellent in terms of tight adhesion to transparent electroconductive films and removability therefrom, and has a small difference in adhesive force between a high-speed separation and a low-speed separation to attain excellent operation efficiency. Another purpose of the present invention is to provide a laminate comprising the carrier film for transparent electroconductive films and a transparent electroconductive film. The carrier film for transparent electroconductive films comprises a support and a pressure-sensitive adhesive layer formed on at least one surface of the support, and is characterized in that when the carrier film in such a state that the pressure-sensitive adhesive layer thereof has been applied to an adherend is heated at 140ºC for 90 minutes and is then separated from the adherend at a pulling speed of 0.3 m/min and at a pulling speed of 10 m/min to obtain adhesive force P and adhesive force Q, respectively, then the adhesive force P and the adhesive force Q are 0.7 N/50 mm or less each and the absolute value of the difference between the adhesive force P and the adhesive force Q is 0.2 N/50 mm or less.

Description

透明導電性フィルム用キャリアフィルム及び積層体Carrier film and laminate for transparent conductive film
　本発明は、支持体と粘着剤層を有する透明導電性フィルム用キャリアフィルムに関する。また、本発明は、当該透明導電性フィルム用キャリアフィルムと透明導電性フィルムを有する積層体に関する。 The present invention relates to a carrier film for a transparent conductive film having a support and an adhesive layer. Moreover, this invention relates to the laminated body which has the said carrier film for transparent conductive films, and a transparent conductive film.
　近年、タッチパネル、液晶ディスプレイパネル、有機ＥＬパネル、エレクトロクロミックパネル、電子ペーパー素子等において、プラスチックフィルム上に透明電極を設けてなるフィルム基板を用いた素子の需要が増加しつつある。 In recent years, in touch panels, liquid crystal display panels, organic EL panels, electrochromic panels, electronic paper elements, etc., the demand for elements using a film substrate in which a transparent electrode is provided on a plastic film is increasing.
　透明電極の材料として、現在、ＩＴＯ薄膜（Ｉｎ・Ｓｎ複合酸化物）、銀や銅などの金属薄膜、銀ナノワイヤー薄膜が用いられており、前記ＩＴＯ薄膜・銀や銅などの金属薄膜・銀ナノワイヤー薄膜を含む薄膜基材の厚さは、年々薄くなる傾向にある。 Currently, ITO thin films (In / Sn composite oxide), metal thin films such as silver and copper, and silver nanowire thin films are used as materials for transparent electrodes. The thickness of the thin film substrate including the nanowire thin film tends to become thinner year by year.
　また、前記ＩＴＯ薄膜を含む薄膜基材等に、機能層として、反射防止（ＡＲ）層を設けて、視認性の向上を図ったり、ハードコート（ＨＣ）層を設けて、傷の発生を防止したり、アンチブロッキング（ＡＢ）層を設けて、ブロッキングを防止したり、オリゴマー防止（ＯＢ）層を設けて、加熱時の白濁を防止したりすることも多い。 In addition, an anti-reflection (AR) layer is provided as a functional layer on the thin film substrate including the ITO thin film to improve visibility, or a hard coat (HC) layer is provided to prevent scratches. In some cases, an anti-blocking (AB) layer is provided to prevent blocking, or an oligomer prevention (OB) layer is provided to prevent white turbidity during heating.
　このような中で、ＩＴＯ薄膜等の光学部材に対して、加工工程や搬送工程等において、キズや汚れ等を防止する目的で、表面保護フィルム等が貼り合わされて使用されている。 In such circumstances, a surface protective film or the like is attached to an optical member such as an ITO thin film for the purpose of preventing scratches and dirt in a processing step and a conveyance step.
　光学部材に用いる表面保護用の粘着フィルムとしては、例えば、ガラス転移温度の異なる２種類の（メタ）アクリル系ポリマーを特定の配合比で用い、かつ架橋剤による架橋の程度を調整した粘着剤から形成される粘着剤層を支持体上に有する表面保護シート（特許文献１参照）や、２－エチルヘキシルアクリレートとヒドロキシエチルメタクリレートを特定量含むモノマー成分から形成されるアクリル共重合体と、特定量の多官能イソシアネート架橋剤を含む粘着剤溶液から得られる粘着剤層をプラスチックフィルムの片面に設けた粘着フィルム（特許文献２参照）等が知られている。 As an adhesive film for surface protection used for an optical member, for example, from an adhesive that uses two types of (meth) acrylic polymers having different glass transition temperatures at a specific blending ratio and adjusts the degree of crosslinking with a crosslinking agent. A surface protective sheet having a pressure-sensitive adhesive layer formed on a support (see Patent Document 1), an acrylic copolymer formed from a monomer component containing specific amounts of 2-ethylhexyl acrylate and hydroxyethyl methacrylate, and a specific amount of A pressure-sensitive adhesive film (see Patent Document 2) in which a pressure-sensitive adhesive layer obtained from a pressure-sensitive adhesive solution containing a polyfunctional isocyanate crosslinking agent is provided on one side of a plastic film is known.
　また、透明導電性フィルム用キャリアフィルムとして、支持体の少なくとも片面に、ガラス転移温度が－５０℃以下である（メタ）アクリル系ポリマー、イソシアネート系架橋剤、及び鉄を中心とする触媒を含む粘着剤組成物から形成された粘着剤層を有する透明導電性フィルム用キャリアフィルムが知られている（特許文献３参照）。 In addition, as a carrier film for a transparent conductive film, an adhesive containing a (meth) acrylic polymer having a glass transition temperature of −50 ° C. or lower, an isocyanate-based crosslinking agent, and a catalyst centered on iron on at least one surface of a support. A carrier film for transparent conductive film having a pressure-sensitive adhesive layer formed from an adhesive composition is known (see Patent Document 3).
特開２００５－１４６１５１号公報JP 2005-146151 A 特開２０１２－２１１６４号公報JP 2012-21164 A 特開２０１５－４８３９４号公報Japanese Patent Laid-Open No. 2015-48394
　特許文献１、２では、透明導電性フィルム用途については十分に検討がなされていない。従って、特許文献１、２の表面保護シートを、透明導電性フィルム用キャリアフィルムとして用いた場合、低速剥離と高速剥離で粘着力の差が十分に小さくならず、剥離の途中でフィルムが折れてしまったり、被着体である透明導電性フィルムにクラックが入ったりする場合があった。 Patent Documents 1 and 2 do not fully study the use of transparent conductive films. Therefore, when the surface protection sheet of Patent Documents 1 and 2 is used as a carrier film for a transparent conductive film, the difference in adhesive strength between the low-speed peeling and the high-speed peeling is not sufficiently reduced, and the film is broken during the peeling. In some cases, the transparent conductive film, which is an adherend, cracks.
　また、特許文献３では、透明導電フィルムから剥離する際のジッピングについては解消できるものではあるが、低速剥離と高速剥離で粘着力の差が十分に小さいものではなく、作業性の観点からは、さらなる検討の余地があった。 Further, in Patent Document 3, although the zipping at the time of peeling from the transparent conductive film can be eliminated, the difference in adhesive force between the low speed peeling and the high speed peeling is not sufficiently small, from the viewpoint of workability, There was room for further study.
　透明導電性フィルムをキャリアフィルムから剥離する際に起こる「ジッピング」とは、透明導電性フィルムをキャリアフィルムから剥離する場合に滑らかに剥離せず、パリパリと音を立てながら剥がれたり止まったりを繰り返す現象を意味する。被着体である透明導電性フィルムに対するキャリアフィルムの粘着力が高い場合に前記ジッピングが発生すると、透明導電性フィルムにクラックが生じたり、剥離痕が残ったりするため、好ましくない。 “Zipping” that occurs when the transparent conductive film is peeled off from the carrier film is a phenomenon in which the transparent conductive film does not peel smoothly when peeled off from the carrier film, and repeats peeling or stopping while making a crisp sound. Means. When the carrier film has a high adhesive strength with respect to the transparent conductive film as the adherend, if the zipping occurs, the transparent conductive film may be cracked or leave traces, which is not preferable.
　また、透明導電性フィルムからキャリアフィルムを剥離する際、高速で剥離した場合の粘着力が、低速で剥離した場合の粘着力よりが高くなる傾向がある。キャリアフィルムの剥離は手作業で行われる場合が多く、一般的に、作業者は高速で剥離することが多いため、キャリアフィルムが剥がれにくく、作業性に劣る場合があった。さらに、剥離途中でフィルムが破断したり、折れてしまったりする場合があった。また、通常、このような手作業での剥離は、始めは低速で剥がして徐々に高速で剥離するように、剥離速度が一定でない場合が多い。そのような場合に、低速剥離と高速剥離で粘着力の差が大きいと、剥離の途中でフィルムが折れてしまったり、被着体である透明導電性フィルムにクラックが入ったりする危険性があり、どのような剥離速度でも一定の粘着力である透明導電性フィルム用キャリアフィルムが切望されていた。 Also, when the carrier film is peeled from the transparent conductive film, the adhesive strength when peeled at a high speed tends to be higher than the adhesive strength when peeled at a low speed. In many cases, the carrier film is peeled off manually, and generally, an operator often peels off at a high speed, so that the carrier film is hardly peeled off and the workability may be inferior. Furthermore, the film may be broken or broken during peeling. In general, such manual peeling is often performed at a constant peeling speed so that peeling is initially performed at a low speed and then gradually performed at a high speed. In such a case, if there is a large difference in adhesive strength between low-speed peeling and high-speed peeling, there is a risk that the film may break during the peeling or the transparent conductive film that is the adherend may crack. A carrier film for a transparent conductive film having a constant adhesive force at any peeling speed has been desired.
　本発明は、ジッピングの発生を抑制することができ、透明導電性フィルムに対する密着性と再剥離性に優れ、かつ、高速剥離と低速剥離で粘着力の差が小さくて作業性に優れる透明導電性フィルム用キャリアフィルムを提供することを目的とする。さらに、本発明は、前記透明導電性フィルム用キャリアフィルム及び透明導電性フィルムを含む積層体を提供することを目的とする。 The present invention can suppress the occurrence of zipping, has excellent adhesion and re-peelability to a transparent conductive film, and has a small difference in adhesive force between high-speed peeling and low-speed peeling and has excellent workability. It aims at providing the carrier film for films. Furthermore, this invention aims at providing the laminated body containing the said carrier film for transparent conductive films, and a transparent conductive film.
　本発明者らは、上記目的を達成すべく、鋭意検討したところ、下記の透明導電性フィルム用キャリアフィルムを用いることにより、上記目的が達成できることを見出し、本発明を完成するに至った。 The present inventors have intensively studied to achieve the above object, and as a result, have found that the above object can be achieved by using the following carrier film for transparent conductive film, and have completed the present invention.
　すなわち、本発明は、支持体の少なくとも片面に粘着剤層を有する透明導電性フィルム用キャリアフィルムであって、
　前記キャリアフィルムの前記粘着剤層を被着体に貼り合せた状態で１４０℃、９０分間加熱した後、前記キャリアフィルムを被着体から引張速度０．３ｍ／分で剥離した時の粘着力Ｐ、及び、引張速度１０ｍ／分で剥離した時の粘着力Ｑが、いずれも０．７Ｎ／５０ｍｍ以下であり、かつ
　前記粘着力Ｐと粘着力Ｑの差の絶対値が、０．２Ｎ／５０ｍｍ以下であることを特徴とする透明導電性フィルム用キャリアフィルムに関する。 That is, the present invention is a carrier film for a transparent conductive film having an adhesive layer on at least one side of a support,
The adhesive strength P when the carrier film was peeled off from the adherend at a tensile rate of 0.3 m / min after heating at 140 ° C. for 90 minutes with the pressure-sensitive adhesive layer of the carrier film bonded to the adherend. The adhesive strength Q when peeled at a tensile speed of 10 m / min is 0.7 N / 50 mm or less, and the absolute value of the difference between the adhesive strength P and the adhesive strength Q is 0.2 N / 50 mm. It is related with the carrier film for transparent conductive films characterized by the following.
　前記粘着剤層が、アルキル（メタ）アクリレート、ホモポリマーのガラス転移温度が５０℃未満の水酸基含有モノマー、及びホモポリマーのガラス転移温度が５０℃以上の水酸基含有モノマーを含むモノマー成分を重合して得られる（メタ）アクリル系ポリマーを含む粘着剤組成物から形成されたものであることが好ましい。 The pressure-sensitive adhesive layer polymerizes a monomer component containing an alkyl (meth) acrylate, a hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C., and a hydroxyl group-containing monomer having a glass transition temperature of the homopolymer of 50 ° C. or more. It is preferable that it is formed from the adhesive composition containing the (meth) acrylic-type polymer obtained.
　前記ホモポリマーのガラス転移温度が５０℃未満の水酸基含有モノマーの配合量が、前記モノマー成分全量に対して１０～１７重量％であり、
　前記ホモポリマーのガラス転移温度が５０℃以上の水酸基含有モノマーの配合量が、前記モノマー成分全量に対して２～８重量％であることが好ましい。 The amount of the hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C. of the homopolymer is 10 to 17% by weight based on the total amount of the monomer components,
The amount of the hydroxyl group-containing monomer having a glass transition temperature of 50 ° C. or higher of the homopolymer is preferably 2 to 8% by weight based on the total amount of the monomer components.
　前記モノマー成分が、さらにカルボキシル基含有モノマーを含み、当該カルボキシル基含有モノマーの配合量が、前記モノマー成分全量に対して０．００５～０．１０重量％であることが好ましい。 The monomer component preferably further contains a carboxyl group-containing monomer, and the amount of the carboxyl group-containing monomer is preferably 0.005 to 0.10% by weight based on the total amount of the monomer component.
　前記粘着剤組成物が、さらに架橋剤を含み、当該架橋剤の配合量が、前記（メタ）アクリル系ポリマー１００重量部に対して２０重量部を超えることが好ましい。 It is preferable that the pressure-sensitive adhesive composition further contains a crosslinking agent, and the amount of the crosslinking agent exceeds 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.
　前記架橋剤が、脂肪族ポリイソシアネート系架橋剤であることが好ましく、前記脂肪族ポリイソシアネート系架橋剤が、ヘキサメチレンジイソシアネートを含有することがより好ましい。 The cross-linking agent is preferably an aliphatic polyisocyanate-based cross-linking agent, and the aliphatic polyisocyanate-based cross-linking agent more preferably contains hexamethylene diisocyanate.
　また、支持体の少なくとも片面に粘着剤層を有する透明導電性フィルム用キャリアフィルムであって、
　前記粘着剤層が、ホモポリマーのガラス転移温度が５０℃未満の水酸基含有モノマー、及びホモポリマーのガラス転移温度が５０℃以上の水酸基含有モノマーを含むモノマー成分を重合して得られる（メタ）アクリル系ポリマーを含む粘着剤組成物から形成されたものであることを特徴とする透明導電性フィルム用キャリアフィルムであってもよい。 Moreover, a carrier film for a transparent conductive film having an adhesive layer on at least one side of a support,
The pressure-sensitive adhesive layer is obtained by polymerizing a monomer component containing a hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C. of the homopolymer and a hydroxyl group-containing monomer having a glass transition temperature of the homopolymer of 50 ° C. or more. The carrier film for transparent conductive films characterized by being formed from the adhesive composition containing a base polymer may be sufficient.
　また、本発明は、前記透明導電性フィルム用キャリアフィルムと、前記透明導電性フィルム用キャリアフィルムに積層された透明導電性フィルムを有する積層体であって、
　前記透明導電性フィルムの少なくとも片方の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされていることを特徴とする積層体に関する。 The present invention is a laminate having a transparent conductive film laminated on the transparent conductive film carrier film and the transparent conductive film carrier film,
The present invention relates to a laminate, wherein the adhesive surface of the adhesive layer of the carrier film for transparent conductive film is bonded to at least one surface of the transparent conductive film.
　また、前記積層体としては、前記透明導電性フィルムが透明導電層及び透明基材を有し、
　前記透明基材の前記透明導電層と接触する面とは反対側の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされているものが挙げられる。 Moreover, as the laminate, the transparent conductive film has a transparent conductive layer and a transparent substrate,
The thing by which the adhesive surface of the adhesive layer of the said carrier film for transparent conductive films is affixed on the surface on the opposite side to the surface which contacts the said transparent conductive layer of the said transparent base material is mentioned.
　また、前記積層体としては、前記透明導電性フィルムが透明導電層及び透明基材を有し、さらに前記透明基材の前記透明導電層と接触する面とは反対側の表面に機能層を有しており、
　前記機能層の前記透明基材と接触する面とは反対側の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされているものが挙げられる。 As the laminate, the transparent conductive film has a transparent conductive layer and a transparent substrate, and further has a functional layer on the surface of the transparent substrate opposite to the surface in contact with the transparent conductive layer. And
The thing by which the adhesive surface of the adhesive layer of the said carrier film for transparent conductive films is affixed on the surface on the opposite side to the surface which contacts the said transparent base material of the said functional layer is mentioned.
　本発明の透明導電性フィルム用キャリアフィルムは、ジッピングの発生を抑制することができ、透明導電性フィルムに対する密着性と再剥離性に優れ、高速剥離と低速剥離で粘着力の差が小さく作業性に優れる。さらに、本発明は、前記透明導電性フィルム用キャリアフィルム及び透明導電性フィルムを含む積層体を提供することができる。 The carrier film for transparent conductive film of the present invention can suppress the occurrence of zipping, has excellent adhesion and re-peelability to the transparent conductive film, and has a small difference in adhesive force between high-speed peeling and low-speed peeling. Excellent. Furthermore, this invention can provide the laminated body containing the said carrier film for transparent conductive films, and a transparent conductive film.
　また、本発明の透明導電性フィルム用キャリアフィルムを用いることで、被着体である透明導電性フィルムにシワやキズ等を発生させることがなく、また、透明導電性フィルムの形状を維持することができる。 Moreover, by using the carrier film for transparent conductive film of the present invention, the transparent conductive film as an adherend is not wrinkled or scratched, and the shape of the transparent conductive film is maintained. Can do.
本発明の透明導電性フィルム用キャリアフィルムの一実施形態を示す模式図である。It is a schematic diagram which shows one Embodiment of the carrier film for transparent conductive films of this invention. 本発明の透明導電性フィルム用キャリアフィルムの粘着剤層面に、透明導電性フィルムを貼付した積層体の一実施形態を示す模式図である。It is a schematic diagram which shows one Embodiment of the laminated body which affixed the transparent conductive film on the adhesive layer surface of the carrier film for transparent conductive films of this invention. 本発明の透明導電性フィルム用キャリアフィルムの粘着剤層面に、機能層付透明導電性フィルムを貼付した積層体一実施形態を示す模式図である。It is a schematic diagram which shows one Embodiment of the laminated body which affixed the transparent conductive film with a functional layer on the adhesive layer surface of the carrier film for transparent conductive films of this invention.
１．透明導電性フィルム用キャリアフィルム
　以下、本発明の実施の形態について、図１～３を用いて詳細に説明する。ただし、本発明は、図１～３の実施形態に限定されるものではない。 1. Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. 1 to 3. However, the present invention is not limited to the embodiment shown in FIGS.
　図１に示すように、本発明の透明導電性フィルム用キャリアフィルム３は、支持体２の少なくとも片面に粘着剤層１を有し、前記粘着剤層１の前記支持体２と接触する面と反対側に粘着面Ａを有する。前記粘着面Ａは、図２に示すように、被着体である透明導電性フィルム６が機能層を有さない場合には、透明導電性フィルムを構成する透明基材５表面（透明基材５の透明導電層４が存在しない側）と接触する面であり、図３に示すように、被着体である透明導電性フィルムが機能層付き透明導電性フィルム８である場合には、前記機能層７と接触する面である。なお、後述する本発明の積層体９は、図２、３に示すように、透明導電性フィルム用キャリアフィルム３と透明導電性フィルム６（又は機能層付き透明導電性フィルム８）を含むものである。 As shown in FIG. 1, the carrier film 3 for transparent conductive film of the present invention has a pressure-sensitive adhesive layer 1 on at least one surface of a support 2, and the surface of the pressure-sensitive adhesive layer 1 that contacts the support 2. It has an adhesive surface A on the opposite side. As shown in FIG. 2, when the transparent conductive film 6 that is an adherend does not have a functional layer, the adhesive surface A is formed on the surface of the transparent substrate 5 (transparent substrate) constituting the transparent conductive film. 5 where the transparent conductive layer 4 does not exist), and when the transparent conductive film as the adherend is the transparent conductive film 8 with a functional layer as shown in FIG. It is a surface that contacts the functional layer 7. In addition, the laminated body 9 of this invention mentioned later contains the carrier film 3 for transparent conductive films, and the transparent conductive film 6 (or transparent conductive film 8 with a functional layer) as shown in FIG.
　本発明の透明導電性フィルム用キャリアフィルムは、前記キャリアフィルムの前記粘着剤層を被着体に貼り合せた状態で１４０℃、９０分間加熱した後、前記キャリアフィルムを被着体から引張速度０．３ｍ／分で剥離した時の粘着力Ｐ、及び、引張速度１０ｍ／分で剥離した時の粘着力Ｑが、いずれも０．７Ｎ／５０ｍｍ以下であり、かつ
　前記粘着力Ｐと粘着力Ｑの差の絶対値が、０．２Ｎ／５０ｍｍ以下であることを特徴とする。 The carrier film for transparent conductive film of the present invention is heated at 140 ° C. for 90 minutes in a state where the pressure-sensitive adhesive layer of the carrier film is bonded to an adherend, and then the carrier film is pulled from the adherend at a tensile rate of 0. The adhesive strength P when peeled at 3 m / min and the adhesive strength Q when peeled at a tensile speed of 10 m / min are both 0.7 N / 50 mm or less, and the adhesive strength P and the adhesive strength Q The absolute value of the difference is 0.2 N / 50 mm or less.
　前記粘着力Ｐは、０．７Ｎ／５０ｍｍ以下であり、０．６Ｎ／５０ｍｍ以下であることが好ましく、０．５Ｎ／５０ｍｍ以下であることがさらに好ましい。粘着力Ｐの下限値は特に限定されるものではないが、被着体である透明導電性フィルムに対する粘着力の観点から、０．１Ｎ／５０ｍｍ以上であることが好ましい。引張速度０．３ｍ／分で剥離した時の粘着力が前記範囲であることで、透明導電性フィルム用キャリアフィルムを透明導電性フィルムから低速度で剥離した際にもジッピングが発生することなく、密着性と再剥離性のバランスに優れるため好ましい。 The adhesive strength P is 0.7 N / 50 mm or less, preferably 0.6 N / 50 mm or less, and more preferably 0.5 N / 50 mm or less. The lower limit value of the adhesive strength P is not particularly limited, but is preferably 0.1 N / 50 mm or more from the viewpoint of the adhesive strength with respect to the transparent conductive film as the adherend. The adhesive force when peeled at a tensile speed of 0.3 m / min is in the above range, so that zipping does not occur even when the carrier film for transparent conductive film is peeled off from the transparent conductive film at a low speed, This is preferable because of excellent balance between adhesion and removability.
　前記粘着力Ｑは、０．７Ｎ／５０ｍｍ以下であり、０．６Ｎ／５０ｍｍ以下であることが好ましく、０．５Ｎ／５０ｍｍ以下であることがさらに好ましい。粘着力Ｑの下限値は特に限定されるものではないが、被着体である透明導電性フィルムに対する粘着力の観点から、０．１Ｎ／５０ｍｍ以上であることが好ましい。引張速度１０ｍ／分で剥離した時の粘着力が０．７Ｎ／５０ｍｍを超えると、作業性が悪くなり、また、透明導電性フィルム用キャリアフィルムを透明導電性フィルムから剥離する際に、フィルム破断や折れが発生する場合がある。一方、引張速度１０ｍ／分で剥離した時の粘着力が前記範囲にあることで、透明導電性フィルム用キャリアフィルムを透明導電性フィルムから高速で剥離した際にもジッピングが発生することなく、密着性と再剥離性のバランスに優れるため好ましい。 The adhesive strength Q is 0.7 N / 50 mm or less, preferably 0.6 N / 50 mm or less, and more preferably 0.5 N / 50 mm or less. The lower limit value of the adhesive strength Q is not particularly limited, but is preferably 0.1 N / 50 mm or more from the viewpoint of the adhesive strength with respect to the transparent conductive film as the adherend. When the adhesive strength when peeled at a tensile speed of 10 m / min exceeds 0.7 N / 50 mm, workability deteriorates, and when the carrier film for transparent conductive film is peeled from the transparent conductive film, the film breaks. Or breakage may occur. On the other hand, since the adhesive force when peeled at a tensile speed of 10 m / min is in the above range, even when the carrier film for transparent conductive film is peeled off from the transparent conductive film at a high speed, adhesion does not occur. This is preferable because of its excellent balance between releasability and removability.
　前記粘着力Ｐと粘着力Ｑの差の絶対値は、０．２Ｎ／５０ｍｍ以下であり、０．１５Ｎ／５０ｍｍ以下であることが好ましく、０．１Ｎ／５０ｍｍ以下であることがさらに好ましく、０．０５Ｎ／５０ｍｍ以下であることが特に好ましい。前記粘着力Ｐと粘着力Ｑの差の絶対値の下限値は、特に限定されるものではなく、小さければ小さいほど好ましいものであり、理想的には差がない（０Ｎ／５０ｍｍ）ことが好ましい。粘着力Ｐと粘着力Ｑの差の絶対値が０．２Ｎ／５０ｍｍを超えると、透明導電性フィルム用キャリアフィルムを透明導電性フィルムから剥離する際に、剥離の途中でフィルムが折れたり、透明導電層へクラックが入ったりする場合がある。一方、粘着力Ｐと粘着力Ｑの差の絶対値が前記範囲内であることで、手作業での剥離作業（通常、始めが低速で剥がして徐々に高速剥離に近づく）のように、剥離速度が一定ではないような場合であっても、剥離の途中でフィルムが折れたり、透明導電層にクラックが入ったりすることなく、透明導電性フィルム用キャリアフィルムの再剥離性に優れるため好ましい。 The absolute value of the difference between the adhesive strength P and the adhesive strength Q is 0.2 N / 50 mm or less, preferably 0.15 N / 50 mm or less, more preferably 0.1 N / 50 mm or less, 0 .05 N / 50 mm or less is particularly preferable. The lower limit of the absolute value of the difference between the adhesive force P and the adhesive force Q is not particularly limited, and the smaller the smaller the better, the more ideally there is no difference (0 N / 50 mm). . If the absolute value of the difference between the adhesive strength P and the adhesive strength Q exceeds 0.2 N / 50 mm, the film may be broken during the peeling or transparent when the carrier film for transparent conductive film is peeled off from the transparent conductive film. A crack may enter the conductive layer. On the other hand, the absolute value of the difference between the adhesive force P and the adhesive force Q is within the above range, so that the peeling is performed like a manual peeling operation (usually peeling at low speed at the beginning and gradually approaching high speed peeling). Even in the case where the speed is not constant, the film is not broken during the peeling or the transparent conductive layer is cracked, and therefore, the releasability of the carrier film for transparent conductive film is excellent, which is preferable.
　前記粘着力測定時の「被着体」は、透明導電性フィルムであり、透明導電性フィルムが機能層を有さない場合には、被着面は透明導電性フィルムを構成する透明基材の表面であり、透明導電性フィルムが機能層を有する場合には、被着面は当該機能層の表面となる。 The “adhered body” at the time of measuring the adhesive force is a transparent conductive film, and when the transparent conductive film does not have a functional layer, the adherend surface is a transparent substrate constituting the transparent conductive film. When the transparent conductive film has a functional layer, the adherend surface is the surface of the functional layer.
　本発明の透明導電性フィルム用キャリアフィルムは、支持体の少なくとも片面に粘着剤層を有し、前記粘着力を有するものであればよく、粘着剤組成等については特に限定されないが、以下に好ましい組成について説明する。 The carrier film for transparent conductive film of the present invention is not particularly limited as long as it has an adhesive layer on at least one surface of the support and has the above-mentioned adhesive force, and the adhesive composition is not particularly limited. The composition will be described.
（１）粘着剤層
　本発明における粘着剤層は、特に限定されるものではなく、アクリル系、合成ゴム系、ゴム系、シリコーン系等の粘着剤等とすることができるが、透明性、耐熱性等の観点から、（メタ）アクリル系ポリマーをベースポリマーとするアクリル系粘着剤であることが好ましい。 (1) Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer in the present invention is not particularly limited, and may be acrylic, synthetic rubber-based, rubber-based, silicone-based, etc. From the viewpoint of properties and the like, an acrylic pressure-sensitive adhesive having a (meth) acrylic polymer as a base polymer is preferable.
　アクリル系粘着剤のベースポリマーとなる（メタ）アクリル系ポリマーは、アルキル（メタ）アクリレートを含むモノマー成分を重合して得られるものであり、アルキル（メタ）アクリレート、ホモポリマーのガラス転移温度が５０℃未満の水酸基含有モノマー、及びホモポリマーのガラス転移温度が５０℃以上の水酸基含有モノマーを含むモノマー成分を重合して得られた（メタ）アクリル系ポリマーが、高速剥離と低速剥離で粘着力の差が小さくなるため好ましい。 The (meth) acrylic polymer used as the base polymer of the acrylic pressure-sensitive adhesive is obtained by polymerizing a monomer component containing an alkyl (meth) acrylate, and the glass transition temperature of the alkyl (meth) acrylate and homopolymer is 50. (Meth) acrylic polymer obtained by polymerizing a monomer component containing a hydroxyl group-containing monomer having a glass transition temperature of 50 ° C. or higher and a hydroxyl group-containing monomer having a glass transition temperature of 50 ° C. This is preferable because the difference is small.
　前記アルキル（メタ）アクリレートとしては、例えば、炭素数２～１４アルキル基を有するものを用いることができるが、アルキル（メタ）アクリレートの主モノマー成分としては、アルキル基の炭素数が４～１４であるアルキル（メタ）アクリレートが好ましく、炭素数６～１４であるアルキル（メタ）アクリレートがより好ましく、炭素数６～９であるアルキル（メタ）アクリレートが特に好ましい。ここで主モノマーとは、モノマー成分に含まれる「アルキル（メタ）アクリレート」の全量に対して、５０重量％以上であり、より好ましくは６０重量％以上であり、さらに好ましくは８０重量％以上であり、特に好ましくは１００重量％である。 As the alkyl (meth) acrylate, for example, those having an alkyl group having 2 to 14 carbon atoms can be used. As the main monomer component of the alkyl (meth) acrylate, an alkyl group having 4 to 14 carbon atoms can be used. Certain alkyl (meth) acrylates are preferred, alkyl (meth) acrylates having 6 to 14 carbon atoms are more preferred, and alkyl (meth) acrylates having 6 to 9 carbon atoms are particularly preferred. Here, the main monomer is 50% by weight or more, more preferably 60% by weight or more, and still more preferably 80% by weight or more based on the total amount of “alkyl (meth) acrylate” contained in the monomer component. Particularly preferably 100% by weight.
　前記炭素数２～１４であるアルキル基を有するアルキル（メタ）アクリレートとしては、例えば、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート（ＢＡ）、ｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、へキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート（２ＥＨＡ）、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ－デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ－ドデシル（メタ）アクリレート、ｎ－トリデシル（メタ）アクリレート、ｎ－テトラデシル（メタ）アクリレート等を挙げることができ、これらを一種単独で、又は２種以上を混合して使用することができる。これらの中でもｎ－ブチル（メタ）アクリレート（ＢＡ）や２－エチルへキシル（メタ）アクリレート（２ＥＨＡ）が好ましく、特に、２－エチルへキシル（メタ）アクリレート（２ＥＨＡ）が好ましい。 Examples of the alkyl (meth) acrylate having an alkyl group having 2 to 14 carbon atoms include ethyl (meth) acrylate, n-butyl (meth) acrylate (BA), t-butyl (meth) acrylate, isobutyl (meth) ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (2EHA), n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n -Decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, and the like. Mix two or more It is possible to use Te. Among these, n-butyl (meth) acrylate (BA) and 2-ethylhexyl (meth) acrylate (2EHA) are preferable, and 2-ethylhexyl (meth) acrylate (2EHA) is particularly preferable.
　特に、粘着剤層に軽剥離が要求される場合は、前記炭素数６～１４のアルキル基を有するアルキル（メタ）アクリレートを用いることが好ましく、前記炭素数６～１４のアルキル基を有するアルキル（メタ）アクリレートを、アルキル（メタ）アクリレートの全量に対して、５０重量％以上とするのが好ましく、６０重量％以上がより好ましく、８０重量％以上がさらに好ましく、９０重量％以上が特に好ましい。 In particular, when light peeling is required for the pressure-sensitive adhesive layer, the alkyl (meth) acrylate having an alkyl group having 6 to 14 carbon atoms is preferably used, and the alkyl having an alkyl group having 6 to 14 carbon atoms ( The (meth) acrylate is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 80% by weight or more, and particularly preferably 90% by weight or more based on the total amount of the alkyl (meth) acrylate.
　前記アルキル（メタ）アクリレートの含有量は、モノマー成分中６５重量％であることが好ましく、７５重量％以上がより好ましく、８０重量％以上がさらに好ましい。 The content of the alkyl (meth) acrylate is preferably 65% by weight in the monomer component, more preferably 75% by weight or more, and further preferably 80% by weight or more.
　前記ホモポリマーのガラス転移温度が５０℃未満の水酸基含有モノマーとしては、ホモポリマーのガラス転移温度が５０℃未満であって、（メタ）アクリロイル基又はビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつ、水酸基を含有するものを挙げることができる。具体的には、２－ヒドロキシエチルアクリレート（ホモポリマーのＴｇ：－１５℃）、２－ヒドロキシプロピルメタクリレート（ホモポリマーのＴｇ：２６℃）、２－ヒドロキシプロピルアクリレート（ホモポリマーのＴｇ：－７℃）、４－ヒドロキシブチルアクリレート（ホモポリマーのＴｇ：－３２℃）等のヒドロキシアルキル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピルアクリレート（ホモポリマーのＴｇ：１７℃）、１,４－シクロヘキサンジメタノールモノアクリレート（ホモポリマーのＴｇ：１８℃）等の環状構造を有する（メタ）アクリレート、ポリエチレングリコールモノアクリレート（エチレングリコールのモル数：１０、ホモポリマーのＴｇ：－６４℃）、ポリプロピレングリコールモノアクリレート（プロピレングリコールのモル数：６、ホモポリマーのＴｇ：－５９℃）等のアルキレンオキシド構造を有する（メタ）アクリレート等を挙げることができ、これらを１種単独で又は２種以上を組み合わせて使用することができる。これらの中でも、ジッピングが抑制できる点から、４－ヒドロキシブチルアクリレート（ホモポリマーのＴｇ：－３２℃）が好ましい。 As the hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C., the homopolymer has a glass transition temperature of less than 50 ° C. and has an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. And those having a functional group and having a hydroxyl group. Specifically, 2-hydroxyethyl acrylate (homopolymer Tg: −15 ° C.), 2-hydroxypropyl methacrylate (homopolymer Tg: 26 ° C.), 2-hydroxypropyl acrylate (homopolymer Tg: −7 ° C.) ), 4-hydroxybutyl acrylate (homopolymer Tg: −32 ° C.), etc., hydroxyalkyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate (homopolymer Tg: 17 ° C.), 1,4-cyclohexane (Meth) acrylate having a cyclic structure such as dimethanol monoacrylate (homopolymer Tg: 18 ° C.), polyethylene glycol monoacrylate (number of moles of ethylene glycol: 10, homopolymer Tg: −64 ° C.), polypropylene glycol mono Accel Relay (Meth) acrylates having an alkylene oxide structure such as propylene glycol (number of moles of propylene glycol: 6, homopolymer Tg: −59 ° C.), etc., and these may be used alone or in combination of two or more. Can be used. Among these, 4-hydroxybutyl acrylate (homopolymer Tg: −32 ° C.) is preferable from the viewpoint that zipping can be suppressed.
　また、前記水酸基含有モノマーのホモポリマーのガラス転移温度は５０℃未満であればよいが、例えば、３０℃以下であることが好ましく、－４０～３０℃であることがより好ましく、－４０～０℃であることがさらに好ましい。 The glass transition temperature of the homopolymer of the hydroxyl group-containing monomer may be less than 50 ° C., for example, preferably 30 ° C. or less, more preferably −40 to 30 ° C., and −40 to 0 More preferably, the temperature is C.
　前記ホモポリマーのガラス転移温度が５０℃未満の水酸基含有モノマーの含有量は、モノマー成分全量に対して１０～１７重量％であることが好ましく、１０～１５重量％であることがより好ましく、１１～１４重量％であることがさらに好ましい。前記ホモポリマーのガラス転移温度が５０℃未満の水酸基含有モノマーの含有割合が１０重量％未満であると、反応点が少ないため架橋密度が下がり、粘着力が高くなる傾向がある。その場合、透明導電性フィルムに対する再剥離性が低下してしまうため、好ましくない。一方、前記ホモポリマーのガラス転移温度が５０℃未満の水酸基含有モノマーの含有割合が１７重量％を超えると、反応点が多すぎるため架橋密度が上がり、粘着力が下がりすぎてしまう傾向がある。その場合、透明導電性フィルムに対する密着性が低下してしまうため、好ましくない。 The content of the hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C. of the homopolymer is preferably 10 to 17% by weight, more preferably 10 to 15% by weight, based on the total amount of the monomer components. More preferably, it is ˜14% by weight. When the content ratio of the hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C. of the homopolymer is less than 10% by weight, the number of reaction points is small, so that the crosslinking density is lowered and the adhesive strength tends to be increased. In that case, since the removability with respect to a transparent conductive film will fall, it is unpreferable. On the other hand, when the content ratio of the hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C. exceeds 17% by weight, the crosslinking density increases and the adhesive strength tends to decrease too much because there are too many reactive sites. In that case, since the adhesiveness with respect to a transparent conductive film will fall, it is unpreferable.
　前記ホモポリマーのガラス転移温度が５０℃以上の水酸基含有モノマーとしては、ホモポリマーのガラス転移温度が５０℃以上であって、（メタ）アクリロイル基又はビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつ、水酸基を含有するものを挙げることができる。具体的には、２－ヒドロキシエチルメタクリレート（ホモポリマーのＴｇ：５５℃）、Ｎ－メチロールアクリルアミド（ホモポリマーのＴｇ：１１０℃）、Ｎ－（２－ヒドロキシエチル）アクリルアミド（ホモポリマーのＴｇ：９８℃）等を挙げることができ、これらを１種単独で又は２種以上を組み合わせて使用することができる。これらの中でも、ジッピングが抑制できる点から、２－ヒドロキシエチルメタクリレート（ホモポリマーのＴｇ：５５℃）が好ましい。 As the hydroxyl group-containing monomer having a glass transition temperature of 50 ° C. or higher of the homopolymer, a polymer having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group having a glass transition temperature of the homopolymer of 50 ° C. or higher. And those having a functional group and having a hydroxyl group. Specifically, 2-hydroxyethyl methacrylate (homopolymer Tg: 55 ° C.), N-methylolacrylamide (homopolymer Tg: 110 ° C.), N- (2-hydroxyethyl) acrylamide (homopolymer Tg: 98) ° C) and the like, and these can be used alone or in combination of two or more. Among these, 2-hydroxyethyl methacrylate (homopolymer Tg: 55 ° C.) is preferable from the viewpoint that zipping can be suppressed.
　また、前記水酸基含有モノマーのホモポリマーのガラス転移温度は５０℃以上であればよいが、例えば、５０～１５０℃であることが好ましく、５０～１００℃であることがより好ましく、５０～９０℃であることがさらに好ましい。 Further, the glass transition temperature of the homopolymer of the hydroxyl group-containing monomer may be 50 ° C. or more, but is preferably 50 to 150 ° C., more preferably 50 to 100 ° C., and more preferably 50 to 90 ° C. More preferably.
　前記ホモポリマーのガラス転移温度が５０℃以上の水酸基含有モノマーの含有量は、モノマー成分全量に対して２～８重量％であることが好ましく、３～６重量％であることがより好ましい。前記ホモポリマーのガラス転移温度が５０℃以上の水酸基含有モノマーの含有割合が２重量％未満であると、高速剥離での粘着力が下がりにくい傾向があり、８重量％を超えると、高速剥離での粘着力が下がりすぎる傾向があり、好ましくない。 The content of the hydroxyl group-containing monomer having a glass transition temperature of 50 ° C. or higher in the homopolymer is preferably 2 to 8% by weight, more preferably 3 to 6% by weight, based on the total amount of the monomer components. When the content ratio of the hydroxyl group-containing monomer having a glass transition temperature of 50 ° C. or higher of the homopolymer is less than 2% by weight, the adhesive force at high-speed peeling tends to be difficult to decrease. There is a tendency that the adhesive strength of the resin tends to decrease too much, which is not preferable.
　前記モノマー成分には、前記アルキル（メタ）アクリレート、水酸基含有モノマー以外のその他の重合性モノマーを含むことができる。前記その他の重合性モノマーとしては、（メタ）アクリル系ポリマーのガラス転移点や剥離性を調整するための重合性モノマー等を、本発明の効果を損なわない範囲で使用することができる。その他の重合性モノマーは単独で用いてもよく、組み合わせて用いても良いが、前記その他の重合性モノマーの配合量としては、モノマー成分全量に対して１０重量％以下が好ましく、５重量％以下がより好ましい。 The monomer component may contain other polymerizable monomer other than the alkyl (meth) acrylate and the hydroxyl group-containing monomer. As said other polymerizable monomer, the polymerizable monomer for adjusting the glass transition point and peelability of a (meth) acrylic-type polymer etc. can be used in the range which does not impair the effect of this invention. Other polymerizable monomers may be used alone or in combination, but the blending amount of the other polymerizable monomer is preferably 10% by weight or less, preferably 5% by weight or less based on the total amount of the monomer components. Is more preferable.
　前記重合性モノマーとしては、カルボキシル基含有モノマーが挙げられる。カルボキシル基含有モノマーは、架橋反応をより効率的に行うことができ、高速剥離での粘着力を下げられる点から用いることができる。カルボキシル基含有モノマーとしては、（メタ）アクリロイル基又はビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつ、カルボキシル基を含有するものを挙げることができ、具体的には、（メタ）アクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等が挙げられる。これらのカルボキシル基含有モノマーの中でも、その重合性や、凝集性、価格、汎用性の点からアクリル酸が好ましい。 Examples of the polymerizable monomer include carboxyl group-containing monomers. The carboxyl group-containing monomer can be used from the viewpoint that the crosslinking reaction can be carried out more efficiently and the adhesive force at high speed peeling can be lowered. Examples of the carboxyl group-containing monomer include those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and containing a carboxyl group. (Meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like. Among these carboxyl group-containing monomers, acrylic acid is preferred from the viewpoints of polymerizability, cohesiveness, cost, and versatility.
　前記カルボキシル基含有モノマーの含有量としては、モノマー成分全量に対して、０．００５～０．１０重量％が好ましく、０．００５～０．０５重量％がより好ましい。カルボキシル基含有モノマーの含有量が前記範囲であることにより、高速剥離での粘着力を下げる効果があるため好ましい。 The content of the carboxyl group-containing monomer is preferably 0.005 to 0.10% by weight, more preferably 0.005 to 0.05% by weight, based on the total amount of the monomer components. It is preferable that the content of the carboxyl group-containing monomer is in the above-mentioned range since there is an effect of reducing the adhesive strength at high speed peeling.
　前記その他の重合性モノマーとしては、例えば、スルホン酸基含有モノマー、リン酸基含有モノマー、シアノ基含有モノマー、ビニルエステルモノマー、芳香族ビニルモノマー等の凝集力・耐熱性向上成分や、酸無水物基含有モノマー、アミド基含有モノマー、アミノ基含有モノマー、エポキシ基含有モノマー、Ｎ－アクリロイルモルホリン、ビニルエーテルモノマー等、架橋化基点として働く官能基を有するモノマー成分を適宜用いることができる。これらのモノマー成分は単独で使用してもよく、また２種以上を混合して使用してもよい。 Examples of the other polymerizable monomers include components for improving cohesion and heat resistance such as sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, and acid anhydrides. A monomer component having a functional group that functions as a crosslinking point, such as a group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, N-acryloylmorpholine, or a vinyl ether monomer, can be used as appropriate. These monomer components may be used alone or in admixture of two or more.
　前記酸無水物基含有モノマーとしては、例えば、無水マレイン酸、無水イタコン酸等が挙げられる。 Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride.
　前記スルホン酸基含有モノマーとしては、例えば、スチレンスルホン酸、アリルスルホン酸、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート、（メタ）アクリロイルオキシナフタレンスルホン酸等が挙げられる。 Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) ) Acrylyloxynaphthalene sulfonic acid and the like.
　前記リン酸基含有モノマーとしては、例えば、２－ヒドロキシエチルアクリロイルホスフェート、メタクリル酸２－（ホスホノオキシ）エチル、メタクリル酸３－クロロ－２－（ホスホノオキシ）プロピル等が挙げられる。 Examples of the phosphoric acid group-containing monomer include 2-hydroxyethylacryloyl phosphate, 2- (phosphonooxy) ethyl methacrylate, 3-chloro-2- (phosphonooxy) propyl methacrylate, and the like.
　前記シアノ基含有モノマーとしては、例えば、アクリロニトリル等が挙げられる。 Examples of the cyano group-containing monomer include acrylonitrile.
　前記ビニルエステルモノマーとしては、例えば、酢酸ビニル、プロピオン酸ビニル、ラウリン酸ビニル等が挙げられる。 Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl laurate, and the like.
　前記芳香族ビニルモノマーとしては、例えば、スチレン、クロロスチレン、クロロメチルスチレン、α－メチルスチレン等が挙げられる。 Examples of the aromatic vinyl monomer include styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, and the like.
　前記アミド基含有モノマーとしては、例えば、アクリルアミド、ジエチルアクリルアミド等が挙げられる。 Examples of the amide group-containing monomer include acrylamide and diethyl acrylamide.
　前記アミノ基含有モノマーとしては、例えば、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート等が挙げられる。 Examples of the amino group-containing monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like.
　前記エポキシ基含有モノマーとしては、例えば、グリシジル（メタ）アクリレート、アリルグリシジルエーテル等が挙げられる。 Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.
　前記ビニルエーテルモノマーとしては、例えば、メチルビニルエーテル、エチルビニルエーテル、イソブチルビニルエーテル等が挙げられる。 Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.
　本発明に用いられる（メタ）アクリル系ポリマーは、前記モノマー成分を重合することにより得られるものであり、その重合方法は、特に制限されるものではなく、溶液重合、乳化重合、塊状重合、懸濁重合等の公知の方法により重合でき、作業性等の観点から、溶液重合がより好ましい。また、得られるポリマーは、ホモポリマーやランダムコポリマー、ブロックコポリマー等いずれでもよい。 The (meth) acrylic polymer used in the present invention is obtained by polymerizing the monomer components, and the polymerization method is not particularly limited, and is solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization. Polymerization can be performed by a known method such as turbid polymerization, and solution polymerization is more preferable from the viewpoint of workability and the like. The obtained polymer may be any of homopolymer, random copolymer, block copolymer and the like.
　本発明に用いられる（メタ）アクリル系ポリマーは、重量平均分子量が３０万～５００万が好ましく、より好ましくは４０万～２００万、特に好ましくは５０万～１００万である。重量平均分子量が３０万より小さい場合は、被着体である（機能層付き）透明導電性フィルムへの濡れ性の向上により、剥離時の粘着力が大きくなるため、剥離工程（再剥離）での被着体損傷の原因になることがあり、また、粘着剤層の凝集力が小さくなることにより糊残りを生じる傾向がある。一方、重量平均分子量が５００万を超える場合は、ポリマーの流動性が低下し、被着体である（機能層付き）透明導電性フィルムへの濡れが不十分となり、被着体と透明導電性フィルム用キャリアフィルムの粘着剤層との間に発生するフクレの原因となる傾向がある。なお、重量平均分子量は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）により測定して得られたものをいう。 The (meth) acrylic polymer used in the present invention preferably has a weight average molecular weight of 300,000 to 5,000,000, more preferably 400,000 to 2,000,000, particularly preferably 500,000 to 1,000,000. When the weight average molecular weight is less than 300,000, the adhesive strength at the time of peeling increases due to the improvement of wettability to the transparent conductive film that is the adherend (with functional layer). This may cause damage to the adherend, and the adhesive force tends to be generated due to the reduced cohesive force of the pressure-sensitive adhesive layer. On the other hand, when the weight average molecular weight exceeds 5,000,000, the fluidity of the polymer is lowered, and the wetness to the transparent conductive film (with the functional layer) becomes insufficient, and the adherend and the transparent conductive There is a tendency to cause blisters generated between the pressure-sensitive adhesive layer of the carrier film for film. In addition, a weight average molecular weight means what was obtained by measuring by GPC (gel permeation chromatography).
　また、粘着性能のバランスが取りやすい理由から、前記（メタ）アクリル系ポリマーのガラス転移温度（Ｔｇ）としては、０℃以下（通常－１００℃以上であり、－７０℃以上が好ましい）が好ましく、－１０℃以下がより好ましく、－２０℃以下が更に好ましく、－３０℃以下が特に好ましい。ガラス転移温度が０℃より高い場合、ポリマーが流動しにくく、被着体である透明導電性フィルムの透明基材への濡れが不十分となり、被着体とキャリアフィルムの粘着剤層との間に発生するフクレの原因となる傾向がある。なお、（メタ）アクリル系ポリマーのガラス転移温度（Ｔｇ）は、用いるモノマー成分や組成比を適宜変えることにより前記範囲内に調整することができる。 In addition, the glass transition temperature (Tg) of the (meth) acrylic polymer is preferably 0 ° C. or lower (usually −100 ° C. or higher, and preferably −70 ° C. or higher) for easy balance of adhesive performance. -10 ° C or lower is more preferable, -20 ° C or lower is further preferable, and -30 ° C or lower is particularly preferable. When the glass transition temperature is higher than 0 ° C., the polymer is difficult to flow, and the transparent conductive film as the adherend is not sufficiently wetted with the transparent base material, and the gap between the adherend and the adhesive layer of the carrier film Tend to cause blisters to occur. In addition, the glass transition temperature (Tg) of a (meth) acrylic-type polymer can be adjusted in the said range by changing the monomer component and composition ratio to be used suitably.
　本発明で用いる粘着剤組成物には、前記（メタ）アクリル系ポリマー以外に、架橋剤を添加することが好ましい。架橋剤としては、イソシアネート化合物、エポキシ化合物、メラミン系樹脂、アジリジン誘導体、及び金属キレート化合物等が用いられる。これらの中でも、主に適度な凝集力を得る観点から、イソシアネート化合物が特に好ましく用いられる。これらの化合物は単独で使用してもよく、また２種以上を混合して使用してもよい。 In addition to the (meth) acrylic polymer, it is preferable to add a crosslinking agent to the pressure-sensitive adhesive composition used in the present invention. As the crosslinking agent, an isocyanate compound, an epoxy compound, a melamine resin, an aziridine derivative, a metal chelate compound, or the like is used. Among these, an isocyanate compound is particularly preferably used mainly from the viewpoint of obtaining an appropriate cohesive force. These compounds may be used alone or in combination of two or more.
　前記イソシアネート化合物としては、イソシアネート基を少なくとも２つ有する化合物を挙げることができ、例えば、一般には、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネート等が用いられる。本発明においては、ジッピング抑制と粘着力の点から、脂肪族ポリイソシアネートを好ましく用いることができるが、脂環族ポリイソシアネート、芳香族ポリイソシアネートは、ジッピング抑制と粘着力の点から用いないことが好ましい。 Examples of the isocyanate compound include compounds having at least two isocyanate groups. For example, aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and the like are generally used. In the present invention, aliphatic polyisocyanates can be preferably used from the viewpoint of zipping suppression and adhesive strength, but alicyclic polyisocyanates and aromatic polyisocyanates are not used from the viewpoint of zipping suppression and adhesive strength. preferable.
　脂肪族ポリイソシアネートとしては、例えば、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、１，２－プロピレンジイソシアネート、１，３－ブチレンジイソシアネート、ドデカメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート等が挙げられ、これらの中でも、ジッピング抑制と粘着力の点から、ヘキサメチレンジイソシアネートを含む脂肪族ポリイソシアネートが好ましい。 Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl. Hexamethylene diisocyanate and the like can be mentioned, and among these, aliphatic polyisocyanates containing hexamethylene diisocyanate are preferable from the viewpoints of suppression of zipping and adhesive strength.
　イソシアネート系架橋剤の市販品としては、例えば、商品名「コロネートＨＬ」、「コロネートＨＸ」（以上、日本ポリウレタン工業（株）製）；商品名「タケネートＤ－１６０Ｎ」、「タケネートＤ－１６５Ｎ」、「タケネートＤ－１７０ＨＮ」、「タケネートＤ－１７８Ｎ」（以上、三井化学（株）製）等が挙げられる。これらの化合物は単独で使用してもよく、また２種以上を混合して使用してもよい。 Examples of commercially available isocyanate crosslinking agents include trade names “Coronate HL” and “Coronate HX” (manufactured by Nippon Polyurethane Industry Co., Ltd.); trade names “Takenate D-160N” and “Takenate D-165N”. "Takenate D-170HN", "Takenate D-178N" (above, manufactured by Mitsui Chemicals, Inc.) and the like. These compounds may be used alone or in combination of two or more.
　本発明において、イソシアネート系架橋剤の配合量は、（メタ）アクリル系ポリマー１００重量部に対し、２０重量部を超えることが好ましく、２０重量部を超え３０重量部以下であることがより好ましく、２１～２５重量部であることがさらに好ましく、２２～２４重量部であることが特に好ましい。イソシアネート系架橋剤の配合量を２０重量部より多くすることで、（メタ）アクリル系ポリマーが有する水酸基との反応により、粘着剤層の架橋形成を十分に行い、凝集力を向上させて、ジッピングの発生を抑制する点で好ましい。また、高速剥離と低速剥離で適切な粘着力を発現することができ、高速剥離と低速剥離の粘着力の差が小さくできるため好ましい。また、特にイソシアネート系架橋剤の配合量が、（メタ）アクリル系ポリマーが有する水酸基に対して、ＯＨ／ＮＣＯ当量比で、０．８９～１．２２となる量で添加することが好ましく、０．９５～１．１４となる量で添加することがより好ましい。イソシアネート系架橋剤の配合量を前記範囲にすることで、高速剥離と低速剥離の粘着力の差を小さく制御することができるため好ましい。 In the present invention, the amount of the isocyanate-based crosslinking agent is preferably more than 20 parts by weight, more preferably more than 20 parts by weight and not more than 30 parts by weight based on 100 parts by weight of the (meth) acrylic polymer. The amount is more preferably 21 to 25 parts by weight, and particularly preferably 22 to 24 parts by weight. By adding more than 20 parts by weight of the isocyanate-based crosslinking agent, the pressure-sensitive adhesive layer is sufficiently cross-linked by the reaction with the hydroxyl group of the (meth) acrylic polymer, and the cohesive force is improved. It is preferable at the point which suppresses generation | occurrence | production of this. Moreover, it is preferable because an appropriate adhesive strength can be expressed by high-speed peeling and low-speed peeling, and the difference in adhesive strength between high-speed peeling and low-speed peeling can be reduced. In particular, it is preferable that the isocyanate crosslinking agent is added in an amount of 0.89 to 1.22 in terms of an OH / NCO equivalent ratio with respect to the hydroxyl group of the (meth) acrylic polymer. It is more preferable to add in an amount of .95 to 1.14. By making the compounding quantity of an isocyanate type crosslinking agent into the said range, since the difference of the adhesive force of high speed peeling and low speed peeling can be controlled small, it is preferable.
　これらイソシアネート系架橋剤は、単独で使用してもよく、２種以上混合して使用してもよく、２官能のイソシアネート化合物と３官能以上のイソシアネート化合物を併用して用いることも可能である。 These isocyanate-based crosslinking agents may be used alone or in combination of two or more, and a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound may be used in combination.
　前記エポキシ化合物としては、例えば、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン（商品名：ＴＥＴＲＡＤ－Ｘ、三菱瓦斯化学（株）製）や１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロへキサン（商品名：ＴＥＴＲＡＤ－Ｃ、三菱瓦斯化学（株）製）等が挙げられる。これらの化合物は単独で使用してもよく、また２種以上を混合して使用してもよい。 Examples of the epoxy compound include N, N, N ′, N′-tetraglycidyl-m-xylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like. These compounds may be used alone or in combination of two or more.
　前記メラミン系樹脂としてはヘキサメチロールメラミン等が挙げられる。アジリジン誘導体としては、例えば、市販品としての商品名ＨＤＵ（相互薬工（株）製）、商品名ＴＡＺＭ（相互薬工（株）製）、商品名ＴＡＺＯ（相互薬工（株）製）等が挙げられる。これらの化合物は単独で使用してもよく、また２種以上を混合して使用してもよい。 Examples of the melamine resin include hexamethylol melamine. As an aziridine derivative, for example, a trade name HDU (manufactured by Mutual Yakuko Co., Ltd.), a brand name TAZM (manufactured by Mutual Yakuko Co., Ltd.), a brand name TAZO (manufactured by Mutual Yakuko Co., Ltd.), etc. Is mentioned. These compounds may be used alone or in combination of two or more.
　金属キレート化合物としては、金属成分としてアルミニウム、チタン、ニッケル、ジルコニウム等、キレート成分としてアセチレン、アセト酢酸メチル、アセト酢酸エチル、乳酸エチル、アセチルアセトン等が挙げられる。これらの化合物は単独で用いてもよいし、組み合わせて用いてもよい。 Examples of the metal chelate compound include aluminum, titanium, nickel, zirconium and the like as the metal component, and acetylene, methyl acetoacetate, ethyl acetoacetate, ethyl lactate, acetylacetone and the like as the chelate component. These compounds may be used alone or in combination.
　イソシアネート系架橋剤以外の架橋剤を併用する場合、その使用量は本発明の効果を損なわなければ特に限定されないが、イソシアネート系架橋剤の総量が、（メタ）アクリル系ポリマー１００重量部に対し、２０重量部を超え、かつ、架橋剤全量における、イソシアネート系架橋剤の割合が、５０重量％以上、さらには７０重量％以上、さらには９０重量％以上の範囲で用いることが好ましい。 When the crosslinking agent other than the isocyanate crosslinking agent is used in combination, the amount used is not particularly limited as long as the effects of the present invention are not impaired, but the total amount of the isocyanate crosslinking agent is 100 parts by weight of the (meth) acrylic polymer. It is preferable to use in an amount exceeding 20 parts by weight and the ratio of the isocyanate-based crosslinking agent in the total amount of the crosslinking agent is in the range of 50% by weight or more, further 70% by weight or more, and further 90% by weight or more.
　また、本発明の粘着剤組成物には、前記（メタ）アクリル系ポリマーの他に、放射線反応性不飽和結合を２個以上有する多官能モノマーを配合することができる。多官能モノマーは（メタ）アクリル系ポリマーを調製する際に、モノマー成分として用いることができる。かかる場合には、放射線等を照射することにより（メタ）アクリル系ポリマーを架橋させる。一分子中に放射線反応性不飽和結合を２個以上有する多官能モノマーとしては、例えば、ビニル基、アクリロイル基、メタクリロイル基、ビニルベンジル基等の放射線の照射で架橋処理（硬化）することができる１種又は２種以上の放射線反応性を２個以上有する多官能モノマーが挙げられる。また、前記多官能モノマーとしては、一般的には放射線反応性不飽和結合が１０個以下のものが好適に用いられる。これらの化合物は単独で使用してもよく、また２種以上を混合して使用してもよい。 In addition, the pressure-sensitive adhesive composition of the present invention may contain a polyfunctional monomer having two or more radiation-reactive unsaturated bonds in addition to the (meth) acrylic polymer. The polyfunctional monomer can be used as a monomer component when preparing the (meth) acrylic polymer. In such a case, the (meth) acrylic polymer is crosslinked by irradiating radiation or the like. As a polyfunctional monomer having two or more radiation-reactive unsaturated bonds in one molecule, for example, it can be crosslinked (cured) by irradiation with radiation such as a vinyl group, an acryloyl group, a methacryloyl group, or a vinylbenzyl group. A polyfunctional monomer having two or more kinds of radiation reactivity of one kind or two kinds or more can be mentioned. As the polyfunctional monomer, generally, those having 10 or less radiation-reactive unsaturated bonds are preferably used. These compounds may be used alone or in combination of two or more.
　前記多官能モノマーの具体例としては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６へキサンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジビニルベンゼン、Ｎ，Ｎ’－メチレンビスアクリルアミド等挙げられる。 Specific examples of the polyfunctional monomer include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6 hexane. Examples include diol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, and N, N′-methylenebisacrylamide.
　前記多官能モノマーの配合量は、（メタ）アクリル系ポリマー１００重量部（固形分）に対し、３０重量部以下が好ましい。 The blending amount of the polyfunctional monomer is preferably 30 parts by weight or less with respect to 100 parts by weight (solid content) of the (meth) acrylic polymer.
　放射線としては、例えば、紫外線、レーザー線、α線、β線、γ線、Ｘ線、電子線等が挙げられるが、制御性及び取り扱い性の良さ、コストの点から紫外線が好適に用いられる。より好ましくは、波長２００～４００ｎｍの紫外線が用いられる。紫外線は、高圧水銀灯、マイクロ波励起型ランプ、ケミカルランプ等の適宜光源を用いて照射することができる。なお、放射線として紫外線を用いる場合には粘着剤組成物に光重合開始剤を配合する。 Examples of the radiation include ultraviolet rays, laser rays, α rays, β rays, γ rays, X rays, electron rays, and the like, and ultraviolet rays are preferably used from the viewpoints of controllability, good handleability, and cost. More preferably, ultraviolet rays having a wavelength of 200 to 400 nm are used. Ultraviolet rays can be irradiated using an appropriate light source such as a high-pressure mercury lamp, a microwave excitation lamp, or a chemical lamp. In addition, when using an ultraviolet-ray as a radiation, a photoinitiator is mix | blended with an adhesive composition.
　光重合開始剤としては、放射線反応性成分の種類に応じ、その重合反応の引金となり得る適当な波長の紫外線を照射することによりラジカルもしくはカチオンを生成する物質であればよい。 The photopolymerization initiator may be any substance that generates radicals or cations by irradiating ultraviolet rays having an appropriate wavelength that can trigger the polymerization reaction according to the type of the radiation-reactive component.
　光ラジカル重合開始剤として、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ｏ－ベンゾイル安息香酸メチル－ｐ－ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、α－メチルベンゾイン等のベンゾイン類、ベンジルジメチルケタール、トリクロルアセトフェノン、２，２－ジエトキシアセトフェノン、１－ヒドロキシシクロへキシルフェニルケトン等のアセトフェノン類、２－ヒドロキシ－２－メチルプロピオフェノン、２－ヒドロキシ－４’－イソプロピル－２－メチルプロピオフェノン等のプロピオフェノン類、ベンゾフェノン、メチルベンゾフェノン、ｐ－クロルベンゾフェノン、ｐ－ジメチルアミノベンゾフェノン等のベンゾフェノン類、２－クロルチオキサントン、２－エチルチオキサントン、２－イソプロピルチオキサントン等のチオキサントン類、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、（２，４，６－トリメチルベンゾイル）－（エトキシ）－フェニルホスフィンオキサイド等のアシルホスフィンオキサイド類、ベンジル、ジベンゾスベロン、α－アシルオキシムエステル等が挙げられる。これらの化合物は単独で使用してもよく、また２種以上を混合して使用してもよい。 As radical photopolymerization initiators, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, methyl o-benzoylbenzoate-p-benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, benzyl dimethyl ketal, trichloro Acetophenones such as acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-isopropyl-2-methylpropiophenone, etc. Propiophenones, benzophenone, methylbenzophenone, p-chlorobenzophenone, benzophenones such as p-dimethylaminobenzophenone, 2-chlorothioxanthone, 2-ethyl Thioxanthones such as oxanthone and 2-isopropylthioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl)- Examples include acylphosphine oxides such as (ethoxy) -phenylphosphine oxide, benzyl, dibenzosuberone, α-acyloxime ester, and the like. These compounds may be used alone or in combination of two or more.
　光カチオン重合開始剤として、例えば、芳香族ジアゾニウム塩、芳香族ヨードニウム塩、芳香族スルホニウム塩等のオニウム塩や、鉄－アレン錯体、チタノセン錯体、アリールシラノール－アルミニウム錯体等の有機金属錯体類、ニトロベンジルエステル、スルホン酸誘導体、リン酸エステル、リン酸エステル、フェノールスルホン酸エステル、ジアゾナフトキノン、Ｎ－ヒドロキシイミドスルホナート等が挙げられる。これらの化合物は単独で使用してもよく、また２種以上を混合して使用してもよい。光重合開始剤は、（メタ）アクリル系ポリマー１００重量部に対し、通常０．１～１０重量部配合し、０．２～７重量部の範囲で配合するのが好ましい。 Examples of the cationic photopolymerization initiator include onium salts such as aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes, nitro Examples thereof include benzyl ester, sulfonic acid derivative, phosphoric acid ester, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, and N-hydroxyimide sulfonate. These compounds may be used alone or in combination of two or more. The photopolymerization initiator is usually added in an amount of 0.1 to 10 parts by weight and preferably 0.2 to 7 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.
　さらに、アミン類等の光開始重合助剤を併用することも可能である。前記光開始助剤としては、例えば、２－ジメチルアミノエチルベンゾエート、ジメチルアミノアセトフェノン、ｐ－ジメチルアミノ安息香酸エチルエステル、ｐ－ジメチルアミノ安息香酸イソアミルエステル等が挙げられる。これらの化合物は単独で使用してもよく、また２種以上を混合して使用してもよい。重合開始助剤は、（メタ）アクリル系ポリマー１００重量部に対し、０．０５～１０重量部配合するのが好ましく、０．１～７重量部の範囲で配合するのがより好ましい。 Furthermore, it is possible to use a photoinitiated polymerization aid such as amines in combination. Examples of the photoinitiator aid include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and the like. These compounds may be used alone or in combination of two or more. The polymerization initiation assistant is preferably added in an amount of 0.05 to 10 parts by weight, more preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer.
　本発明で用いられる粘着剤組成物には、触媒を添加することができる。触媒の種類は特に限定されず、スズ触媒等、本分野において公知の触媒を用いることができるが、スズ触媒を用いることが好ましい。また、本発明においては、鉄を活性中心とする触媒は含まないことが好ましい。 A catalyst can be added to the pressure-sensitive adhesive composition used in the present invention. The type of the catalyst is not particularly limited, and a catalyst known in this field such as a tin catalyst can be used, but it is preferable to use a tin catalyst. Moreover, in this invention, it is preferable not to contain the catalyst which uses iron as an active center.
　前記スズ触媒としては、ジラウリン酸ジオクチルスズ、ジラウリン酸ジブチルスズ、ジブチルスズジアセテート、ジブチルスズジオクテート、ジブチルスズジオレート、ジフェニルスズジアセテート、ジブチルスズオキサイド、ジブチルスズジメトキサイド、ジブチルビス（トリエトキシシロキシ）スズ、ジブチルスズベンジルマレート、ジオクチルスズジアセテート等を挙げることができ、これらを単独で又は２種以上を混合して使用することができる。これらの中でも、ジラウリン酸ジオクチルスズが好ましい。また、触媒の添加量としては特に限定されるものではないが、例えば、アクリル系ポリマー１００重量部に対して、０．００１～０．５重量部程度であることが好ましい。 Examples of the tin catalyst include dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin diolate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin, dibutyltin benzyl Malate, dioctyltin diacetate, etc. can be mentioned, These can be used individually or in mixture of 2 or more types. Among these, dioctyltin dilaurate is preferable. The amount of the catalyst added is not particularly limited, but for example, it is preferably about 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the acrylic polymer.
　さらに、本発明で用いられる粘着剤組成物には、その他の公知の添加剤を含有していてもよく、例えば、着色剤、顔料等の粉体、界面活性剤、可塑剤、粘着性付与剤、低分子量ポリマー、表面潤滑剤、レベリング剤、酸化防止剤、腐食防止剤、光安定剤、紫外線吸収剤、重合禁止剤、シランカップリング剤、無機又は有機の充填剤、金属粉、粒子状、箔状物等を使用する用途に応じて適宜配合することができる。 Furthermore, the pressure-sensitive adhesive composition used in the present invention may contain other known additives, such as powders such as colorants and pigments, surfactants, plasticizers, and tackifiers. , Low molecular weight polymer, surface lubricant, leveling agent, antioxidant, corrosion inhibitor, light stabilizer, UV absorber, polymerization inhibitor, silane coupling agent, inorganic or organic filler, metal powder, particulate, It can mix | blend suitably according to the use which uses a foil-like thing.
　また、粘着剤組成物の固形分としては、特に限定されるものではなく、２０重量％以上であることが好ましく、３０重量％以上であることがより好ましい。 The solid content of the pressure-sensitive adhesive composition is not particularly limited, and is preferably 20% by weight or more, and more preferably 30% by weight or more.
　本発明において用いられる粘着剤層は、以上のような粘着剤組成物から形成されるものである。また、本発明の（機能層付き）透明導電性フィルム用キャリアフィルムは、かかる粘着剤層を支持体（基材、基材層）上に形成してなるものである。その際、（メタ）アクリル系ポリマーの架橋は、粘着剤組成物の塗布後に行うのが一般的であるが、架橋後の粘着剤組成物からなる粘着剤層を支持体等に転写することも可能である。 The pressure-sensitive adhesive layer used in the present invention is formed from the pressure-sensitive adhesive composition as described above. Moreover, the carrier film for transparent conductive films (with a functional layer) of this invention forms such an adhesive layer on a support body (a base material, a base material layer). At that time, the crosslinking of the (meth) acrylic polymer is generally performed after the application of the pressure-sensitive adhesive composition, but the pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition after crosslinking may be transferred to a support or the like. Is possible.
　支持体（基材、又は基材層ともいう。）上に、粘着剤層を形成する方法は、特に問わないが、例えば、前記粘着剤組成物を支持体に塗布（例えば、固形分としては、２０重量％以上が好ましく、３０重量％以上がより好ましい。）し、重合溶剤等を乾燥除去して粘着剤層を支持体上に形成することにより作製される。その後、粘着剤層の成分移行の調整や架橋反応の調整等を目的として養生をおこなってもよい。また、粘着剤組成物を支持体上に塗布して、透明導電性フィルム用キャリアフィルムを作製する際には、支持体上に均一に塗布できるよう、粘着剤組成物中に重合溶剤以外の一種以上の溶剤を新たに加えてもよい。 A method for forming the pressure-sensitive adhesive layer on the support (also referred to as a base material or a base material layer) is not particularly limited. For example, the pressure-sensitive adhesive composition is applied to the support (for example, as a solid content). 20% by weight or more, and more preferably 30% by weight or more), and the pressure-sensitive adhesive layer is formed on the support by drying and removing the polymerization solvent and the like. Thereafter, curing may be performed for the purpose of adjusting the component transfer of the pressure-sensitive adhesive layer, adjusting the crosslinking reaction, and the like. In addition, when the pressure-sensitive adhesive composition is applied on a support to produce a carrier film for a transparent conductive film, the pressure-sensitive adhesive composition is a kind other than the polymerization solvent so that it can be uniformly applied on the support. The above solvent may be newly added.
　また、前記粘着剤組成物の塗布方法としては、粘着テープ等の製造に用いられる公知の方法が用いられる。具体的には、例えば、ロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、エアーナイフコート法等が挙げられる。 In addition, as a method for applying the pressure-sensitive adhesive composition, a known method used for manufacturing a pressure-sensitive adhesive tape or the like is used. Specifically, for example, roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating and the like can be mentioned.
　支持体に塗布した粘着剤組成物を乾燥する際の乾燥条件は、粘着剤組成物の組成、濃度、組成物中の溶媒の種類等によって適宜決定できるものであり、特に限定されるものではないが、例えば、８０～２００℃で１０秒～３０分程度で乾燥することができる。 The drying conditions for drying the pressure-sensitive adhesive composition applied to the support can be appropriately determined depending on the composition, concentration, type of solvent in the composition, etc., and are not particularly limited. However, it can be dried at 80 to 200 ° C. for about 10 seconds to 30 minutes.
　また、上述のように任意成分とする光重合開始剤を配合した場合には、支持体（基材、基材層)の片面又は両面に塗工した後、光照射することにより粘着剤層を得ることができる。通常は、波長３００～４００ｎｍにおける照度が１～２００ｍＷ／ｃｍ２である紫外線を、光量４００～４０００ｍＪ／ｃｍ２程度照射して光重合させることにより粘着剤層が得られる。 In addition, when a photopolymerization initiator as an optional component is blended as described above, the pressure-sensitive adhesive layer is applied by light irradiation after coating on one side or both sides of the support (base material, base material layer). Obtainable. Usually, the pressure-sensitive adhesive layer is obtained by photopolymerization by irradiating an ultraviolet ray having an illuminance of 1 to 200 mW / cm 2 at a wavelength of 300 to 400 nm with a light amount of about 400 to 4000 mJ / cm 2 .
　本発明の透明導電性フィルム用キャリアフィルムの粘着剤層の厚みは、５～５０μｍが好ましく、より好ましくは１０～３０μｍである。前記範囲内であると、密着性と再剥離性のバランスに優れ、好ましい態様となる。本発明に用いられる支持体(基材層)の少なくとも片面に、上記粘着剤層を塗布等して形成し、フィルム状やシート状、テープ状等の形態としたものである。 The thickness of the pressure-sensitive adhesive layer of the carrier film for transparent conductive film of the present invention is preferably 5 to 50 μm, more preferably 10 to 30 μm. Within the above range, the balance between adhesion and removability is excellent and a preferred embodiment is obtained. The pressure-sensitive adhesive layer is formed on at least one surface of a support (base material layer) used in the present invention by coating or the like to form a film, sheet, tape or the like.
（２）支持体
　本発明の透明導電性フィルム用キャリアフィルムを構成する支持体（基材）（図１中の２）として、特に制限されないが、例えば、紙等の紙系支持体；布、不織布、ネット等の繊維系支持体（その原料としては、特に制限されず、例えば、マニラ麻、レーヨン、ポリエステル、パルプ繊維等を適宜選択することができる）；金属箔、金属板等の金属系支持体；プラスチックのフィルムやシート等のプラスチック系支持体；ゴムシート等のゴム系支持体；発泡シート等の発泡体や、これらの積層体（例えば、プラスチック系支持体と他の支持体との積層体や、プラスチックフィルム（又はシート）同士の積層体等）等の適宜な薄葉体を用いることができる。 (2) Support The support (base material) (2 in FIG. 1) constituting the carrier film for transparent conductive film of the present invention is not particularly limited. For example, a paper-based support such as paper; Non-woven fabrics, nets and other fiber-based supports (the raw materials are not particularly limited, for example, Manila hemp, rayon, polyester, pulp fibers, etc. can be selected as appropriate); metal-based supports such as metal foils and metal plates Body; Plastic support such as plastic film or sheet; Rubber support such as rubber sheet; Foam such as foam sheet or laminate thereof (for example, lamination of plastic support and other support) A suitable thin leaf body such as a body or a laminate of plastic films (or sheets) can be used.
　前記プラスチックのフィルムやシートにおける素材としては、例えば、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、エチレン－プロピレン共重合体、エチレン－酢酸ビニル共重合体（ＥＶＡ）等のα－オレフィンをモノマー成分とするオレフィン系樹脂；ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリブチレンテレフタレート（ＰＢＴ）等のポリエステル系樹脂；ポリカーボネート系樹脂；ポリ塩化ビニル（ＰＶＣ）；酢酸ビニル系樹脂；ポリフェニレンスルフィド（ＰＰＳ）；ポリアミド（ナイロン）、全芳香族ポリアミド（アラミド）等のアミド系樹脂；ポリイミド系樹脂；環状ないしノルボルネン構造を有するポリオレフィン系樹脂；ポリエーテルエーテルケトン（ＰＥＥＫ）等が挙げられる。これらの素材は単独で又は２種以上を組み合わせて使用することができる。これらの中でも特に、前記ポリエステル系樹脂は、強靭性、加工性、透明性等を有するため、これを透明導電性フィルム用のキャリアフィルムに使用することにより、作業性・検査性が向上することとなり、より好ましい態様となる。 As a material for the plastic film or sheet, for example, α-olefin such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) is used as a monomer component. Olefin resins: Polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); polycarbonate resins; polyvinyl chloride (PVC); vinyl acetate resins; polyphenylene sulfide (PPS) Amide resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); polyimide resins; polyolefin resins having a cyclic or norbornene structure; polyether ether ketone (PEEK) It is. These materials can be used alone or in combination of two or more. Among these, the polyester-based resin has toughness, workability, transparency, and the like, and therefore, by using it as a carrier film for a transparent conductive film, workability and testability are improved. This is a more preferable embodiment.
　前記ポリエステル系樹脂としては、シート状やフィルム状等に形成できるものであれば特に限定されるものでなく、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート、ポリブチレンテレフタレート等のポリエステルフィルムが挙げられる。これらのポリエステル系樹脂は単独（ホモポリマー）で使用してもよく、また２種以上を混合・重合（コポリマー等）して使用してもよい。特に、本発明においては、透明導電性フィルム用キャリアフィルムとして用いるため、支持体として、ポリエチレンテレフタレートが好ましく用いられる。ポリエチレンテレフタレートを用いることにより、強靭性、加工性、透明性に優れた透明導電性フィルム用キャリアフィルムとなり、作業性が向上し、好ましい態様となる。 The polyester resin is not particularly limited as long as it can be formed into a sheet shape or a film shape, and examples thereof include polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate. . These polyester resins may be used alone (homopolymer), or two or more kinds may be mixed and polymerized (copolymers, etc.). In particular, in the present invention, since it is used as a carrier film for a transparent conductive film, polyethylene terephthalate is preferably used as a support. By using polyethylene terephthalate, it becomes a carrier film for a transparent conductive film excellent in toughness, workability, and transparency, and workability is improved, which is a preferred embodiment.
　前記支持体の厚みは、２５～３００μｍが一般的に用いられるが、７５～２００μｍが好ましく、より好ましくは８０～１４０μｍであり、特に好ましくは９０～１３０μｍである。前記範囲内であると、透明導電性フィルム用キャリアフィルムを、（機能層付き）透明導電性フィルムに貼付して使用することにより、コシがなく、撓みやすい前記透明導電性フィルムの形状を保持することができ、加工工程や搬送工程等において、シワやキズ等の不具合の発生を防止でき、有用である。 The thickness of the support is generally 25 to 300 μm, preferably 75 to 200 μm, more preferably 80 to 140 μm, and particularly preferably 90 to 130 μm. Within the above range, the transparent conductive film carrier film is attached to a transparent conductive film (with a functional layer) and used to maintain the shape of the transparent conductive film that is flexible and flexible. This is useful because it can prevent the occurrence of defects such as wrinkles and scratches in the processing step and the conveying step.
　また、前記支持体には、必要に応じて、シリコーン系、フッ素系、長鎖アルキル系もしくは脂肪酸アミド系の離型剤、シリカ粉等による離型及び防汚処理や酸処理、アルカリ処理、プライマー処理、コロナ処理、プラズマ処理、紫外線処理等の易接着処理、塗布型、練り込み型、蒸着型等の静電防止処理をすることもできる。特に静電防止処理を行う際には、支持体と粘着剤層の間に静電防止層を設けることが好ましい。 In addition, the support may include a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, release with a silica powder, antifouling treatment, acid treatment, alkali treatment, primer, if necessary. Anti-adhesive treatment such as treatment, corona treatment, plasma treatment, ultraviolet treatment, coating type, kneading type, vapor deposition type, etc. can also be performed. In particular, when performing antistatic treatment, it is preferable to provide an antistatic layer between the support and the pressure-sensitive adhesive layer.
　なお、粘着剤層と支持体間の密着性を向上させるため、支持体の表面にはコロナ処理等を行ってもよい。また、支持体には背面処理を行ってもよい。 In addition, in order to improve the adhesion between the pressure-sensitive adhesive layer and the support, the surface of the support may be subjected to corona treatment or the like. Moreover, you may perform a back surface process to a support body.
　本発明の（機能層付き）透明導電性フィルム用キャリアフィルムは、必要に応じて粘着面を保護する目的で粘着剤表面にシリコーン系、フッ素系、長鎖アルキル系又は脂肪酸アミド系等の離型剤処理されたセパレータを貼り合わせることが可能である。セパレータを構成する基材としては、紙やプラスチックフィルムがあるが、表面平滑性に優れる点からプラスチックフィルムが好適に用いられる。そのフィルムとしては、前記粘着剤層を保護し得るフィルムであれば特に限定されず、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン－酢酸ビニル共重合体フィルム等が挙げられる。 The carrier film for a transparent conductive film (with a functional layer) of the present invention is a silicone-based, fluorine-based, long-chain alkyl-based, or fatty acid amide-based release agent on the pressure-sensitive adhesive surface for the purpose of protecting the pressure-sensitive adhesive surface as necessary. It is possible to bond a separator treated with an agent. As the substrate constituting the separator, there are paper and plastic film, but a plastic film is preferably used from the viewpoint of excellent surface smoothness. The film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer. Examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
　また、前記セパレータ用の支持体には、必要に応じて、アルカリ処理、プライマー処理、コロナ処理、プラズマ処理、紫外線処理等の易接着処理、塗布型、練り込み型、蒸着型等の静電防止処理をすることもできる。特に、静電防止処理を行う場合には、支持体と離型剤の間に静電防止処理層を設けることが好ましい。 In addition, the support for the separator may be subjected to anti-static treatment such as alkali treatment, primer treatment, corona treatment, plasma treatment, ultraviolet treatment, coating type, kneading type, vapor deposition type, etc., if necessary. It can also be processed. In particular, when an antistatic treatment is performed, it is preferable to provide an antistatic treatment layer between the support and the release agent.
２．（機能層付き）透明導電性フィルム
　透明導電性フィルム６は、図２、３に示すように、透明導電層４と透明基材５を有するフィルムを挙げることができる。 2. (With a functional layer) Transparent conductive film The transparent conductive film 6 can mention the film which has the transparent conductive layer 4 and the transparent base material 5, as shown in FIG.
　透明基材５としては、樹脂フィルムや、ガラス等からなる基材（例えば、シート状やフィルム状、板状の基材（部材）等）等が挙げられ、特に、樹脂フィルムを挙げることができる。透明基材５の厚さは、特に限定されないが、１０～２００μｍ程度が好ましく、１５～１５０μｍ程度がより好ましい。 Examples of the transparent substrate 5 include a resin film and a substrate made of glass or the like (for example, a sheet-like, film-like, or plate-like substrate (member)). In particular, a resin film can be mentioned. . The thickness of the transparent substrate 5 is not particularly limited, but is preferably about 10 to 200 μm, more preferably about 15 to 150 μm.
　前記樹脂フィルムの材料としては、特に制限されないが、透明性を有する各種のプラスチック材料が挙げられる。例えば、その材料として、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂、アセテート系樹脂、ポリエーテルスルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリオレフィン系樹脂、（メタ）アクリル系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、ポリスチレン系樹脂、ポリビニルアルコール系樹脂、ポリアリレート系樹脂、ポリフェニレンサルファイド系樹脂等が挙げられる。これらの中で特に好ましいのは、ポリエステル系樹脂、ポリイミド系樹脂及びポリエーテルスルホン系樹脂である。 The material of the resin film is not particularly limited, and various plastic materials having transparency can be mentioned. For example, the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins. , Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Of these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.
　また、前記透明基材５には、表面に予めスパッタリング、コロナ放電、火炎、紫外線照射、電子線照射、化成、酸化等のエッチング処理や下塗り処理を施して、この上に設けられる透明導電層４等の前記透明基材５に対する密着性を向上させるようにしてもよい。また、透明導電層４を設ける前に、必要に応じて溶剤洗浄や超音波洗浄等により除塵、清浄化してもよい。 Further, the transparent base material 5 is subjected to an etching process such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, or undercoating treatment on the surface in advance, and the transparent conductive layer 4 provided thereon. You may make it improve the adhesiveness with respect to the said transparent base materials 5, such as. Further, before the transparent conductive layer 4 is provided, dust may be removed and cleaned by solvent cleaning, ultrasonic cleaning, or the like, if necessary.
　前記透明導電層４の構成材料としては特に限定されず、インジウム、スズ、亜鉛、ガリウム、アンチモン、チタン、珪素、ジルコニウム、マグネシウム、アルミニウム、金、銀、銅、パラジウム、タングステンからなる群より選択される少なくとも１種の金属の金属酸化物が用いられる。当該金属酸化物には、必要に応じて、さらに上記群に示された金属原子を含んでいてもよい。例えば酸化スズを含有する酸化インジウム（ＩＴＯ）、アンチモンを含有する酸化スズ等が好ましく用いられ、ＩＴＯが特に好ましく用いられる。ＩＴＯとしては、酸化インジウム８０～９９重量％及び酸化スズ１～２０重量％を含有することが好ましい。 The constituent material of the transparent conductive layer 4 is not particularly limited, and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten. A metal oxide of at least one metal is used. The metal oxide may further contain a metal atom shown in the above group, if necessary. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, or the like is preferably used, and ITO is particularly preferably used. ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.
　前記透明導電層４の厚みは特に制限されないが、１０～３００ｎｍであることがより好ましく、１５～１００ｎｍであることがさらに好ましい。 The thickness of the transparent conductive layer 4 is not particularly limited, but is preferably 10 to 300 nm, and more preferably 15 to 100 nm.
　前記透明導電層４の形成方法としては特に限定されず、従来公知の方法を採用することができる。具体的には、例えば真空蒸着法、スパッタリング法、イオンプレーティング法を例示できる。また、必要とする膜厚に応じて適宜の方法を採用することもできる。 The method for forming the transparent conductive layer 4 is not particularly limited, and a conventionally known method can be employed. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified. In addition, an appropriate method can be adopted depending on the required film thickness.
　また、透明導電層４と透明基材５との間に、必要に応じて、アンダーコート層、オリゴマー防止層等を設けることができる。 Moreover, an undercoat layer, an oligomer prevention layer, etc. can be provided between the transparent conductive layer 4 and the transparent base material 5 as necessary.
　また、前記透明導電層４を有する透明導電性フィルム６は、光学デバイス用基材（光学部材）として用いることができる。光学デバイス用基材としては、光学的特性を有する基材であれば、特に限定されないが、例えば、表示装置（液晶表示装置、有機ＥＬ（エレクトロルミネッセンス）表示装置、ＰＤＰ（プラズマディスプレイパネル）、電子ペーパー等）、入力装置（タッチパネル等）等の機器を構成する基材（部材）又はこれらの機器に用いられる基材（部材）が挙げられる。これらの光学デバイス用基材は近年の薄膜化の傾向に伴い、コシがなくなり、加工工程や搬送工程等において、撓みや形状の変形を生じ易かった。本発明の透明導電性フィルム用キャリアフィルムを貼付して使用することにより、形状を保持することができ、不具合の発生を抑制でき、好ましい態様となる。 Moreover, the transparent conductive film 6 having the transparent conductive layer 4 can be used as a substrate for optical devices (optical member). The substrate for an optical device is not particularly limited as long as it is a substrate having optical characteristics. For example, a display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic Paper, etc.), base materials (members) constituting devices such as input devices (touch panels, etc.) or base materials (members) used in these devices. These substrate materials for optical devices have become stiff due to the recent trend of thinning, and have been prone to bend and deform in shape during processing and transporting processes. By sticking and using the carrier film for transparent conductive films of this invention, a shape can be hold | maintained and generation | occurrence | production of a malfunction can be suppressed and it becomes a preferable aspect.
　図３に示すように、前記透明導電性フィルム６の透明導電層５を設けていない側の面には、機能層７を設けることができる。 As shown in FIG. 3, a functional layer 7 can be provided on the surface of the transparent conductive film 6 where the transparent conductive layer 5 is not provided.
　前記機能層としては、例えば、視認性の向上を目的とした防眩処理（ＡＧ）層、反射防止（ＡＲ）層、ハードコート（ＨＣ）、アンチブロッキング（ＡＢ）層等を挙げることができる。 Examples of the functional layer include an antiglare treatment (AG) layer, an antireflection (AR) layer, a hard coat (HC), and an antiblocking (AB) layer for the purpose of improving visibility.
　前記防眩処理層の構成材料としては特に限定されず、例えば電離放射線硬化型樹脂、熱硬化型樹脂、熱可塑性樹脂等を用いることができる。防眩処理層の厚みは０．１～３０μｍが好ましい。前記反射防止層としては、酸化チタン、酸化ジルコニウム、酸化ケイ素、フッ化マグネシウム等が用いられる。反射防止層は複数層を設けることができる。 The constituent material of the antiglare treatment layer is not particularly limited, and for example, an ionizing radiation curable resin, a thermosetting resin, a thermoplastic resin, or the like can be used. The thickness of the antiglare treatment layer is preferably from 0.1 to 30 μm. As the antireflection layer, titanium oxide, zirconium oxide, silicon oxide, magnesium fluoride, or the like is used. The antireflection layer can be provided with a plurality of layers.
　前記ハードコート（ＨＣ）層の形成材料としては、例えば、メラミン系樹脂、ウレタン系樹脂、アルキド系樹脂、アクリル系樹脂、シリコーン系樹脂等の硬化型樹脂からなる硬化被膜が好ましく用いられる。ハードコート層の厚さとしては、０．１～３０μｍが好ましい。厚さを０．１μｍ以上とすることが、硬度を付与するうえで好ましい。また、前記ハードコート層上に、前記防眩処理層や反射防止層やアンチブロッキング層を設けることができる。また、防眩機能、反射防止機能、アンチブロッキング機能、オリゴマー防止機能を有するハードコート層を用いることができる。 As the material for forming the hard coat (HC) layer, for example, a cured film made of a curable resin such as a melamine resin, a urethane resin, an alkyd resin, an acrylic resin, or a silicone resin is preferably used. The thickness of the hard coat layer is preferably from 0.1 to 30 μm. The thickness is preferably 0.1 μm or more for imparting hardness. Further, the antiglare treatment layer, the antireflection layer, and the antiblocking layer can be provided on the hard coat layer. Further, a hard coat layer having an antiglare function, an antireflection function, an antiblocking function, and an oligomer prevention function can be used.
　アンチブロッキング層としては、硬化型樹脂層中に微粒子を含有させたものや、硬化型樹脂組成物として相分離する２種以上の成分を含有するコーティング組成物を用いたもの、あるいはこれらを併用することによって、表面に凹凸が形成されたものが好適に用いられる。硬化型樹脂層の成分としては、熱硬化型樹脂、紫外線硬化型樹脂、電子線硬化型樹脂等を挙げることができる。また、相分離する２種以上の成分を含有するコーティング組成物としては、例えば国際公開第２００５／０７３７６３号パンフレットに記載の組成物を好適に用いることができる。アンチブロッキング層の厚さとしては、０．１～３０μｍが好ましい。 As the anti-blocking layer, a curable resin layer containing fine particles, a curable resin composition using a coating composition containing two or more components that are phase-separated, or a combination thereof are used. Thus, those having irregularities formed on the surface are preferably used. Examples of the component of the curable resin layer include a thermosetting resin, an ultraviolet curable resin, and an electron beam curable resin. Moreover, as a coating composition containing 2 or more types of components which phase-separate, the composition as described in the international publication 2005/073763 pamphlet can be used suitably, for example. The thickness of the anti-blocking layer is preferably 0.1 to 30 μm.
　前記機能層付き透明導電性フィルム（機能層を含む）の厚みとしては、２１０μｍ以下が好ましく、１５０μｍ以下がより好ましい。前記範囲内の透明導電性フィルム（被着体）に対して、本発明の（機能層付き）透明導電性フィルム用キャリアフィルムを使用することにより、透明導電性フィルムが非常に薄い場合でもその形状を保持することができ、シワやキズ等の不具合の発生を抑制でき、好ましい態様となる。 The thickness of the transparent conductive film with a functional layer (including the functional layer) is preferably 210 μm or less, and more preferably 150 μm or less. By using the carrier film for transparent conductive film of the present invention (with functional layer) for the transparent conductive film (adhered body) within the above range, even if the transparent conductive film is very thin, its shape It can hold | maintain, generation | occurrence | production of malfunctions, such as a wrinkle and a crack, can be suppressed, and becomes a preferable aspect.
３．積層体
　また、本発明は、透明導電性フィルム用キャリアフィルム３と、前記透明導電性フィルム用キャリアフィルム３に積層された透明導電性フィルム６を有する積層体９であって、
　前記透明導電性フィルム用キャリアフィルム３が本明細書に記載された透明導電性フィルム用キャリアフィルムであり、
　前記透明導電性フィルム６は透明導電層４及び透明基材５を有し、
　前記透明基材５の前記透明導電層４と接触する面とは反対側の表面に、前記透明導電性フィルム用キャリアフィルム３の粘着剤層１の粘着面が貼り合わされていることを特徴とする積層体９に関する（例えば、図２）。 3. Laminated body Moreover, this invention is the laminated body 9 which has the transparent conductive film 6 laminated | stacked on the carrier film 3 for transparent conductive films, and the said carrier film 3 for transparent conductive films,
The carrier film for transparent conductive film 3 is a carrier film for transparent conductive film described in the present specification,
The transparent conductive film 6 has a transparent conductive layer 4 and a transparent substrate 5,
The adhesive surface of the adhesive layer 1 of the carrier film 3 for transparent conductive film is bonded to the surface of the transparent substrate 5 opposite to the surface that contacts the transparent conductive layer 4. Regarding the laminated body 9 (for example, FIG. 2).
　さらに、本発明は、透明導電性フィルム用キャリアフィルム３と、前記透明導電性フィルム用キャリアフィルム３に積層された透明導電性フィルム６を有する積層体であって、
　前記透明導電性フィルム用キャリアフィルム３が本明細書に記載された透明導電性フィルム用キャリアフィルムであり、
　前記透明導電性フィルム３は透明導電層４及び透明基材５を有し、さらに前記透明基材の前記透明導電層と接触する面とは反対側の表面に機能層７を有しており、
　前記機能層７の前記透明基材５と接触する面とは反対側の表面に、前記透明導電性フィルム用キャリアフィルム３の粘着剤層１の粘着面が貼り合わされていることを特徴とする積層体に関する（例えば、図３）。 Furthermore, the present invention is a laminate having a transparent conductive film carrier film 3 and a transparent conductive film 6 laminated on the transparent conductive film carrier film 3,
The carrier film for transparent conductive film 3 is a carrier film for transparent conductive film described in the present specification,
The transparent conductive film 3 has a transparent conductive layer 4 and a transparent substrate 5, and further has a functional layer 7 on the surface of the transparent substrate opposite to the surface in contact with the transparent conductive layer,
A laminate in which the adhesive surface of the adhesive layer 1 of the carrier film 3 for transparent conductive film is bonded to the surface of the functional layer 7 opposite to the surface in contact with the transparent substrate 5. Related to the body (eg, FIG. 3).
　本発明の積層体に用いられる透明導電性フィルム用キャリアフィルム、（機能層付き）透明導電性フィルムについては、前述のものを挙げることができる。 Examples of the carrier film for transparent conductive film used in the laminate of the present invention and the transparent conductive film (with a functional layer) include those described above.
　以下、本発明の構成と効果を具体的に示す実施例等について説明するが、本発明はこれらに限定されるものではない。なお、実施例等における評価項目は下記のようにして測定を行った。配合内容については、表１及び表２に示し、評価結果については、表２に示す。 Hereinafter, examples and the like specifically showing the configuration and effects of the present invention will be described, but the present invention is not limited thereto. In addition, the evaluation item in an Example etc. measured as follows. The blending contents are shown in Table 1 and Table 2, and the evaluation results are shown in Table 2.
　製造例１　
（アクリル系ポリマーの調整）
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つロフラスコに、２－エチルヘキシルアクリレート（２ＥＨＡ）８２．９９重量部、４－ヒドロキシブチルアクリレート（４ＨＢＡ）１４重量部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）３重量部、アクリル酸０．０１重量部、重合開始剤として２，２’－アゾビスイソブチロニトリル０．２重量部、酢酸エチル１８６重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を６０℃付近に保って約６時間重合反応を行い、アクリル系ポリマー（Ａ１）溶液（約３５重量％）を調製した。前記アクリル系ポリマー（Ａ１）の重量平均分子量は６５万であり、Ｔｇは－６３℃であった。 Production Example 1
(Adjustment of acrylic polymer)
Into a four-flask equipped with a stirring blade, thermometer, nitrogen gas introduction tube, and condenser, 82.99 parts by weight of 2-ethylhexyl acrylate (2EHA), 14 parts by weight of 4-hydroxybutyl acrylate (4HBA), hydroxyethyl methacrylate ( HEMA) 3 parts by weight, 0.01 parts by weight of acrylic acid, 0.22 parts by weight of 2,2′-azobisisobutyronitrile and 186 parts by weight of ethyl acetate as a polymerization initiator, and nitrogen gas with gentle stirring And the polymerization temperature was kept at around 60 ° C. for about 6 hours to prepare an acrylic polymer (A1) solution (about 35% by weight). The acrylic polymer (A1) had a weight average molecular weight of 650,000 and a Tg of −63 ° C.
　製造例２～１２
　製造例１において、表１に示すように、アクリル系ポリマーの調製に用いたモノマーの種類、その使用割合を変えた以外は、製造例１と同様の方法により、アクリル系ポリマー（Ａ２）～（Ａ８）、（Ａ１１）～（Ａ１４）の溶液を調製した。 Production Examples 2 to 12
In Production Example 1, as shown in Table 1, the acrylic polymers (A2) to (A) were prepared in the same manner as in Production Example 1 except that the type of monomer used for the preparation of the acrylic polymer and the use ratio thereof were changed. Solutions of (A8) and (A11) to (A14) were prepared.
Figure JPOXMLDOC01-appb-T000001
 表１中の略記は、それぞれ以下の通りである。
　２ＥＨＡ：２－エチルヘキシルアクリレート
　ＢＡ：ブチルアクリレート
　４ＨＢＡ：４－ヒドロキシブチルアクリレート
　ＨＥＭＡ：２－ヒドロキシエチルメタリレート
　ＨＰＡ：２－ヒドロキシプロピルアクリレート
　ＡＡ：アクリル酸
Figure JPOXMLDOC01-appb-T000001
 Abbreviations in Table 1 are as follows.
2EHA: 2-ethylhexyl acrylate BA: butyl acrylate 4HBA: 4-hydroxybutyl acrylate HEMA: 2-hydroxyethyl metallate HPA: 2-hydroxypropyl acrylate AA: acrylic acid
　＜アクリル系ポリマーの重量平均分子量（Ｍｗ）の測定＞
　作製したポリマーの重量平均分子量は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）により測定した。
　装置：ＨＬＣ－８２２０ＧＰＣ、東ソー（株）製
　カラム：
　サンプルカラム：ＴＳＫｇｕａｒｄｃｏｌｕｍｎ　Ｓｕｐｅｒ　ＨＺ－Ｈ（１本）＋ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｈ（２本）　東ソー（株）製
　リファレンスカラム：ＴＳＫｇｅｌ　Ｓｕｐｅｒ　Ｈ－ＲＣ（１本）東ソー（株）製
　流量：０．６ｍl／ｍｉｎ
　注入量：１０μＬ
　カラム温度：４０℃
　溶離液：ＴＨＦ
　注入試料濃度：０．２重量％
　検出器：示差屈折計
　なお、重量平均分子量はポリスチレン換算により算出した。 <Measurement of weight average molecular weight (Mw) of acrylic polymer>
The weight average molecular weight of the produced polymer was measured by GPC (gel permeation chromatography).
Apparatus: HLC-8220GPC, manufactured by Tosoh Corporation Column:
Sample column: TSKguardcolumn Super HZ-H (1) + TSKgel Super HZM-H (2) manufactured by Tosoh Corporation Reference column: TSKgel Super H-RC (1) manufactured by Tosoh Corporation Flow rate: 0.6 ml / min
Injection volume: 10 μL
Column temperature: 40 ° C
Eluent: THF
Injection sample concentration: 0.2% by weight
Detector: differential refractometer The weight average molecular weight was calculated in terms of polystyrene.
　＜アクリル系ポリマーのガラス転移温度（Ｔｇ）の測定＞
　ガラス転移温度（Ｔｇ）（℃）は、各モノマーによるホモポリマーのガラス転移温度Ｔｇｎ（℃）として下記の文献値を用い、下記の式により求めた。 <Measurement of glass transition temperature (Tg) of acrylic polymer>
The glass transition temperature (Tg) (° C.) was determined by the following formula using the following literature values as the glass transition temperature Tg n (° C.) of the homopolymer of each monomer.
　式：１／（Ｔｇ＋２７３）＝Σ[Ｗｎ／（Ｔｇｎ＋２７３）]
（式中、Ｔｇ（℃）は共重合体のガラス転移温度、Ｗｎ（－）は各モノマーの重量分率、Ｔｇｎ（℃）は各モノマーによるホモポリマーのガラス転移温度、ｎは各モノマーの種類を表す。）
　ブチルアクリレート（ＢＡ）：－５５℃
　２－エチルヘキシルアクリレート（２ＥＨＡ）：－７０℃
　４－ヒドロキシブチルアクリレート（４ＨＢＡ）：－３２℃
　２－ヒドロキシエチルメタリレート（ＨＥＭＡ）：５５℃
　２－ヒドロキシプロピルアクリレート（ＨＰＡ）：－７℃
　アクリル酸：１０６℃
　なお、文献値として「アクリル樹脂の合成・設計と新用途開発」（中央経営開発センター出版部発行）、メーカーカダログを参照した。 Formula: 1 / (Tg + 273) = Σ [Wn / (Tg n +273)]
Where Tg (° C.) is the glass transition temperature of the copolymer, Wn (−) is the weight fraction of each monomer, Tg n (° C.) is the glass transition temperature of the homopolymer of each monomer, and n is the Represents the type.)
Butyl acrylate (BA): -55 ° C
2-Ethylhexyl acrylate (2EHA): -70 ° C
4-hydroxybutyl acrylate (4HBA): -32 ° C
2-Hydroxyethyl metallate (HEMA): 55 ° C
2-hydroxypropyl acrylate (HPA): -7 ° C
Acrylic acid: 106 ° C
Reference values of “Synthesis / design of acrylic resin and development of new applications” (published by Central Management Development Center Publishing Department) and manufacturer Kadalog were used as literature values.
　実施例１
　（粘着剤溶液の調整）
　製造例１で得られたアクリル系ポリマー（Ａ１）溶液（約３５重量％）を酢酸エチルで２９重量％に希釈し、この溶液のアクリル系ポリマー１００重量部（固形分）に対して、ヘキサメチレンジイソシアネートのイソシアヌレート体（商品名：コロネートＨＸ、日本ポリウレタン工業（株）製）２２重量部、スズ触媒としてジラウリン酸ジオクチルスズ０．０１５重量部を加えて、２５℃付近に保って約１分間混合撹拌を行い、アクリル系粘着剤組成物（１）を調製した。 Example 1
(Adjustment of adhesive solution)
The acrylic polymer (A1) solution (about 35% by weight) obtained in Production Example 1 was diluted to 29% by weight with ethyl acetate, and hexamethylene was added to 100 parts by weight (solid content) of the acrylic polymer in this solution. Add 22 parts by weight of isocyanurate of diisocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.), 0.015 part by weight of dioctyltin dilaurate as a tin catalyst, and keep it at around 25 ° C for about 1 minute. Stirring was performed to prepare an acrylic pressure-sensitive adhesive composition (1).
　（透明導電性フィルム用キャリアフィルムの作製）
　上記アクリル系粘着剤組成物（１）を、ポリエチレンテレフタレート（ＰＥＴ）基材（厚さ１２５μｍ、支持体）の片面に塗布し、１５０℃で９０秒間加熱して、厚さ２０μｍの粘着剤層を形成した。次いで、前記粘着剤層の表面に、片面にシリコーン処理を施したＰＥＴ剥離ライナー（厚さ２５μｍ）のシリコーン処理面を貼り合せ、５０℃で１日間保存して、透明導電性フィルム用キャリアフィルムを作製した。なお、使用時には、前記剥離ライナーは除去して使用した。 (Preparation of carrier film for transparent conductive film)
The acrylic pressure-sensitive adhesive composition (1) is applied to one side of a polyethylene terephthalate (PET) substrate (thickness 125 μm, support) and heated at 150 ° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 20 μm. Formed. Next, the surface of the pressure-sensitive adhesive layer was bonded with a silicone-treated surface of a PET release liner (thickness 25 μm) that had been subjected to silicone treatment on one side, and stored at 50 ° C. for 1 day to obtain a carrier film for transparent conductive film. Produced. In use, the release liner was removed before use.
　実施例２～１０、比較例１～６
　表２に示すように、アクリル系ポリマーの種類や、粘着剤組成物を構成する架橋剤又はその配合量を変更し、さらに、比較例３、４では、スズ触媒に代えて鉄触媒（アセチルアセトン第二鉄）を用いた以外は、実施例１と同様の方法にて、透明導電性フィルム用キャリアフィルムを作製した。 Examples 2 to 10, Comparative Examples 1 to 6
As shown in Table 2, the type of acrylic polymer, the cross-linking agent constituting the pressure-sensitive adhesive composition, or the blending amount thereof was changed. Further, in Comparative Examples 3 and 4, an iron catalyst (acetylacetone first) was used instead of the tin catalyst. A carrier film for a transparent conductive film was produced in the same manner as in Example 1 except that diiron) was used.
　実施例、及び比較例で得られた透明導電性フィルム用キャリアフィルムについて下記評価を行った。 The following evaluation was performed about the carrier film for transparent conductive films obtained by the Example and the comparative example.
　＜粘着力測定＞
　被着体として、ＳＵＳ板（ＳＵＳ４３０ＢＡ）に固定された幅５０ｍｍ、長さ１００ｍｍの透明導電性フィルム（商品名：Ｖ１５０－ＯＦＪ、ＰＥＴフィルムの片面に透明導電層を有し、他の片面にアンチブロッキング層（０．８μｍのアクリル粒子を５重量％未満含有する、アモルファスシリカ、アクリル系モノマー、光開始剤、添加剤で構成される塗コーティング組成物から形成されている）を有するフィルム、日東電工（株）製）のアンチブロッキング層面に、透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面を貼り合せた（貼り合わせ機にて圧着：０．２５ＭＰａ、圧着速度２．０ｍ／分）。次いで、１４０℃で９０分間加熱し、その後３０分以上、常温（２５℃）で放置した後、同環境下で万能引張試験機を用いて、剥離速度０．３ｍ／分（低速剥離）、及び、１０ｍ／分（高速剥離）、剥離角度１８０°の条件で透明導電性フィルムから透明導電性フィルム用キャリアフィルムを剥離し、このときの剥離力（Ｎ／５０ｍｍ）を測定した。 <Adhesion measurement>
As an adherend, a transparent conductive film (trade name: V150-OFJ, PET film having a width of 50 mm and a length of 100 mm, fixed to a SUS plate (SUS430BA), has a transparent conductive layer on one side and an anti-surface on the other side. Nitto Denko film having a blocking layer (formed from a coating composition composed of amorphous silica, acrylic monomer, photoinitiator and additives containing less than 5% by weight of 0.8 μm acrylic particles) The pressure-sensitive adhesive layer of the carrier film for transparent conductive film was bonded to the surface of the anti-blocking layer (manufactured by Co., Ltd.) (pressure bonding with a bonding machine: 0.25 MPa, pressure bonding speed 2.0 m / min). Next, after heating at 140 ° C. for 90 minutes and then leaving at room temperature (25 ° C.) for 30 minutes or longer, using a universal tensile tester in the same environment, a peeling speed of 0.3 m / min (low speed peeling), and The carrier film for transparent conductive film was peeled from the transparent conductive film under the conditions of 10 m / min (high speed peeling) and a peeling angle of 180 °, and the peeling force (N / 50 mm) at this time was measured.
＜ジッピング＞
　被着体として、ＳＵＳ板（ＳＵＳ４３０ＢＡ）に固定された幅５０ｍｍ、長さ１００ｍｍの透明導電性フィルム（商品名：Ｖ１５０－ＯＦＪ、ＰＥＴフィルムの片面に透明導電層を有し、他の片面にアンチブロッキング層（０．８μｍのアクリル粒子を５重量％未満含有する、アモルファスシリカ、アクリル系モノマー、光開始剤、添加剤で構成される塗コーティング組成物から形成されている）を有するフィルム、日東電工（株）製）のアンチブロッキング層面に、透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面を貼り合せた（貼り合わせ機にて圧着：０．２５ＭＰａ、圧着速度２．０ｍ／分）。次いで、１４０℃で９０分間加熱し、その後３０分以上、常温（２５℃）で放置した後、同環境下で万能引張試験機を用いて、剥離速度０．３ｍ／分、剥離角度１８０°の条件で透明導電性フィルムから透明導電性フィルム用キャリアフィルムを８０ｍｍ剥離し、このときの剥離力（Ｎ／５０ｍｍ）を測定した。上記剥離力の後半６０ｍｍ分の測定データを用いて、下記の式によりジッピングの有無を評価した。
　〇：ΔＦ／Ｆ（Ａｖｅ）＜１５％（ジッピングが発生しない）
　×：ΔＦ／Ｆ（Ａｖｅ）≧１５％（ジッピングが発生する）
　ΔＦ：Ｆ（Ｍａｘ）－Ｆ（Ｍｉｎ）
（上記式中、Ｆ（Ｍａｘ）は、最大剥離力であり、Ｆ（Ｍｉｎ）は、最小剥離力である）
　Ｆ（Ａｖｅ）：平均剥離力 <Zipping>
As an adherend, a transparent conductive film (trade name: V150-OFJ, PET film having a width of 50 mm and a length of 100 mm, fixed to a SUS plate (SUS430BA), has a transparent conductive layer on one side and an anti-surface on the other side. Nitto Denko film having a blocking layer (formed from a coating composition composed of amorphous silica, acrylic monomer, photoinitiator and additives containing less than 5% by weight of 0.8 μm acrylic particles) The pressure-sensitive adhesive layer of the carrier film for transparent conductive film was bonded to the surface of the anti-blocking layer (manufactured by Co., Ltd.) (pressure bonding with a bonding machine: 0.25 MPa, pressure bonding speed 2.0 m / min). Next, after heating at 140 ° C. for 90 minutes and then leaving at room temperature (25 ° C.) for 30 minutes or longer, using a universal tensile tester in the same environment, a peeling speed of 0.3 m / min and a peeling angle of 180 ° The carrier film for transparent conductive film was peeled 80 mm from the transparent conductive film under the conditions, and the peel force (N / 50 mm) at this time was measured. Using the measurement data for the latter half 60 mm of the peeling force, the presence or absence of zipping was evaluated by the following formula.
○: ΔF / F (Ave) <15% (Zipping does not occur)
×: ΔF / F (Ave) ≧ 15% (zipping occurs)
ΔF: F (Max) -F (Min)
(In the above formula, F (Max) is the maximum peel force and F (Min) is the minimum peel force)
F (Ave): Average peel force
Figure JPOXMLDOC01-appb-T000002
 　表２中、
　Ａ１～Ａ１４は、それぞれ、製造例１～１２で製造された（メタ）アクリル系ポリマーであり、
Ｃ／ＨＸは、イソシアネート系架橋剤（ヘキサメチレンジイソシアネートのイソシアヌレート体、商品名：コロネートＨＸ、日本ポリウレタン工業（株）製）、
Ｃ／Ｌは、イソシアネート系架橋剤（トリメチロールプロパン／トリレンジイソシアネート３量体付加物、商品名：コロネートＬ、日本ポリウレタン工業（株）製）、
スズ触媒は、ジラウリン酸ジオクチルスズ、
鉄触媒は、アセチルアセトン第二鉄
を示す。
Figure JPOXMLDOC01-appb-T000002
 In Table 2,
A1 to A14 are (meth) acrylic polymers produced in Production Examples 1 to 12, respectively.
C / HX is an isocyanate crosslinking agent (isocyanurate of hexamethylene diisocyanate, trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.)
C / L is an isocyanate crosslinking agent (trimethylolpropane / tolylene diisocyanate trimer adduct, trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.),
The tin catalyst is dioctyltin dilaurate,
The iron catalyst refers to ferric acetylacetone.
　１　　粘着剤層
　２　　支持体（基材）
　３　　透明導電性フィルム用キャリアフィルム
　４　　透明導電層
　５　　透明基材
　６　　透明導電性フィルム
　７　　機能層
　８　　機能層付透明導電性フィルム
　９　　積層体
　Ａ　　粘着面 DESCRIPTION OF SYMBOLS 1 Adhesive layer 2 Support body (base material)
DESCRIPTION OF SYMBOLS 3 Carrier film for transparent conductive films 4 Transparent conductive layer 5 Transparent base material 6 Transparent conductive film 7 Functional layer 8 Transparent conductive film with a functional layer 9 Laminate A Adhesive surface

Claims (10)

  1. 　支持体の少なくとも片面に粘着剤層を有する透明導電性フィルム用キャリアフィルムであって、
    　前記キャリアフィルムの前記粘着剤層を被着体に貼り合せた状態で１４０℃、９０分間加熱した後、前記キャリアフィルムを被着体から引張速度０．３ｍ／分で剥離した時の粘着力Ｐ、及び、引張速度１０ｍ／分で剥離した時の粘着力Ｑが、いずれも０．７Ｎ／５０ｍｍ以下であり、かつ
    　前記粘着力Ｐと粘着力Ｑの差の絶対値が、０．２Ｎ／５０ｍｍ以下であることを特徴とする透明導電性フィルム用キャリアフィルム。     A carrier film for a transparent conductive film having an adhesive layer on at least one side of a support,
    The adhesive strength P when the carrier film was peeled off from the adherend at a tensile rate of 0.3 m / min after heating at 140 ° C. for 90 minutes with the pressure-sensitive adhesive layer of the carrier film bonded to the adherend. The adhesive strength Q when peeled at a tensile speed of 10 m / min is 0.7 N / 50 mm or less, and the absolute value of the difference between the adhesive strength P and the adhesive strength Q is 0.2 N / 50 mm. A carrier film for a transparent conductive film, characterized in that:
  2. 　前記粘着剤層が、アルキル（メタ）アクリレート、ホモポリマーのガラス転移温度が５０℃未満の水酸基含有モノマー、及びホモポリマーのガラス転移温度が５０℃以上の水酸基含有モノマーを含むモノマー成分を重合して得られる（メタ）アクリル系ポリマーを含む粘着剤組成物から形成されたものであることを特徴とする請求項１に記載の透明導電性フィルム用キャリアフィルム。 The pressure-sensitive adhesive layer polymerizes a monomer component containing an alkyl (meth) acrylate, a hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C., and a hydroxyl group-containing monomer having a glass transition temperature of the homopolymer of 50 ° C. or more. The carrier film for a transparent conductive film according to claim 1, wherein the carrier film is formed from a pressure-sensitive adhesive composition containing the obtained (meth) acrylic polymer.
  3. 　前記ホモポリマーのガラス転移温度が５０℃未満の水酸基含有モノマーの配合量が、前記モノマー成分全量に対して１０～１７重量％であり、
    　前記ホモポリマーのガラス転移温度が５０℃以上の水酸基含有モノマーの配合量が、前記モノマー成分全量に対して２～８重量％であることを特徴とする請求項２に記載の透明導電性フィルム用キャリアフィルム。     The amount of the hydroxyl group-containing monomer having a glass transition temperature of less than 50 ° C. of the homopolymer is 10 to 17% by weight based on the total amount of the monomer components,
    3. The transparent conductive film according to claim 2, wherein the amount of the hydroxyl group-containing monomer having a glass transition temperature of 50 ° C. or higher of the homopolymer is 2 to 8% by weight based on the total amount of the monomer components. Carrier film.
  4. 　前記モノマー成分が、さらにカルボキシル基含有モノマーを含み、当該カルボキシル基含有モノマーの配合量が、前記モノマー成分全量に対して０．００５～０．１０重量％であることを特徴とする請求項２又は３に記載の透明導電性フィルム用キャリアフィルム。 The monomer component further contains a carboxyl group-containing monomer, and the blending amount of the carboxyl group-containing monomer is 0.005 to 0.10% by weight with respect to the total amount of the monomer component. 3. The carrier film for transparent conductive films according to 3.
  5. 　前記粘着剤組成物が、さらに架橋剤を含み、当該架橋剤の配合量が、前記（メタ）アクリル系ポリマー１００重量部に対して２０重量部を超えることを特徴とする請求項２～４のいずれかに記載の透明導電性フィルム用キャリアフィルム。 The pressure-sensitive adhesive composition further comprises a crosslinking agent, and the amount of the crosslinking agent exceeds 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. The carrier film for transparent conductive films according to any one of the above.
  6. 　前記架橋剤が、脂肪族ポリイソシアネート系架橋剤であることを特徴とする請求項５に記載の透明導電性フィルム用キャリアフィルム。 The carrier film for a transparent conductive film according to claim 5, wherein the crosslinking agent is an aliphatic polyisocyanate crosslinking agent.
  7. 　前記脂肪族ポリイソシアネート系架橋剤が、ヘキサメチレンジイソシアネートを含有することを特徴とする請求項６に記載の透明導電性フィルム用キャリアフィルム。 The carrier film for a transparent conductive film according to claim 6, wherein the aliphatic polyisocyanate crosslinking agent contains hexamethylene diisocyanate.
  8. 　請求項１～７のいずれかに記載の透明導電性フィルム用キャリアフィルムと、前記透明導電性フィルム用キャリアフィルムに積層された透明導電性フィルムを有する積層体であって、
    　前記透明導電性フィルムの少なくとも片方の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされていることを特徴とする積層体。     A laminate comprising a carrier film for a transparent conductive film according to any one of claims 1 to 7 and a transparent conductive film laminated on the carrier film for a transparent conductive film,
    A laminate, wherein an adhesive surface of an adhesive layer of the carrier film for transparent conductive film is bonded to at least one surface of the transparent conductive film.
  9. 　前記透明導電性フィルムは、透明導電層及び透明基材を有し、
    　前記透明基材の前記透明導電層と接触する面とは反対側の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされていることを特徴とする請求項８に記載の積層体。     The transparent conductive film has a transparent conductive layer and a transparent substrate,
    The pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer of the carrier film for transparent conductive film is bonded to the surface of the transparent substrate opposite to the surface that contacts the transparent conductive layer. The laminated body of description.
  10. 　前記透明導電性フィルムは透明導電層及び透明基材を有し、さらに前記透明基材の前記透明導電層と接触する面とは反対側の表面に機能層を有しており、
    　前記機能層の前記透明基材と接触する面とは反対側の表面に、前記透明導電性フィルム用キャリアフィルムの粘着剤層の粘着面が貼り合わされていることを特徴とする請求項８に記載の積層体。     The transparent conductive film has a transparent conductive layer and a transparent substrate, and further has a functional layer on the surface of the transparent substrate opposite to the surface in contact with the transparent conductive layer,
    The pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer of the carrier film for transparent conductive film is bonded to the surface of the functional layer opposite to the surface in contact with the transparent substrate. Laminated body.
PCT/JP2016/063160 2015-04-30 2016-04-27 Carrier film for transparent electroconductive film, and laminate WO2016175232A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012021164A (en) * 2011-09-15 2012-02-02 Hitachi Chem Co Ltd Adhesive film
JP2013256559A (en) * 2012-06-11 2013-12-26 Soken Chem & Eng Co Ltd Method for producing adhesive sheet and method for producing laminate for touch panel
JP2014115348A (en) * 2012-12-06 2014-06-26 Nippon Carbide Ind Co Inc Adhesive composition for polarizing plates, polarizing plate with adhesive, and display device
JP2015004072A (en) * 2014-09-25 2015-01-08 チェイル インダストリーズ インコーポレイテッド Adhesive composition and optical member using the same
JP2015048394A (en) * 2013-08-30 2015-03-16 日東電工株式会社 Carrier film for transparent conductive film, and laminate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012021164A (en) * 2011-09-15 2012-02-02 Hitachi Chem Co Ltd Adhesive film
JP2013256559A (en) * 2012-06-11 2013-12-26 Soken Chem & Eng Co Ltd Method for producing adhesive sheet and method for producing laminate for touch panel
JP2014115348A (en) * 2012-12-06 2014-06-26 Nippon Carbide Ind Co Inc Adhesive composition for polarizing plates, polarizing plate with adhesive, and display device
JP2015048394A (en) * 2013-08-30 2015-03-16 日東電工株式会社 Carrier film for transparent conductive film, and laminate
JP2015004072A (en) * 2014-09-25 2015-01-08 チェイル インダストリーズ インコーポレイテッド Adhesive composition and optical member using the same

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