JP2017193678A - Method for producing optical member with separate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an optical member with a separate film that can maintain excellent adhesion between an adhesive layer and an adjacent member even when a flexible display is bent.SOLUTION: A method for producing an optical member with a separate film includes: a coating step for coating a long separate film with an active energy ray-curable adhesive composition to form a coating layer; an exposure step for subjecting the coating layer to pattern exposure by irradiation with active energy rays, while continuously conveying the separate film having the coating layer, to obtain a separate film having an adhesive layer including an exposed first region and a second region with a smaller exposure than that of the first region; and a laminating step for putting a long optical member on the outer surface of the adhesive layer, while still continuously conveying the film after the exposure step, and pressing the resultant laminate vertically.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for manufacturing an optical member with a separate film, which includes a separate film, an adhesive layer, and an optical member in this order.

  Various optical members typified by a polarizing plate or the like may be used by being bonded to another member, for example, an image display cell via an adhesive layer (for example, Patent Document 1). For this reason, an optical member may be marketed with the form of the optical member with an adhesive layer by which the adhesive layer was previously provided in the one surface. In general, a peelable separate film (also referred to as a “release film”) for protecting the surface is temporarily attached to the outer surface of the pressure-sensitive adhesive layer.

JP 2008-275722 A

  As a display including the optical member and the image display cell as described above, a flexible display having flexibility can be installed on a non-planar surface or a folding surface, and can be folded and folded in a portable form as a scroll. Therefore, it is expected to be used in portable devices. In an optical member with an adhesive layer used for a flexible display, even if the flexible display is bent (for example, bent, curved, etc.) or repeatedly bent, the adhesive layer and the adjacent member do not peel off. Sex is required.

  An object of the present invention is an optical member with a separate film, which is a laminate of a separate film with an adhesive layer and an optical member, and is also provided between the adhesive layer and an adjacent member for bending in a flexible display. Another object of the present invention is to provide a method for producing an optical member with a separate film capable of maintaining good adhesion.

This invention provides the manufacturing method of the optical member with a separate film shown below.
[1] A coating process in which an active energy ray-curable pressure-sensitive adhesive composition is coated on a long separate film to form a coating layer;
While continuously transporting a separate film having the coating layer, the coating layer is subjected to pattern exposure by irradiation of active energy rays, and an exposed first region and a second region having a smaller exposure amount than the first region An exposure step of obtaining a separate film having a pressure-sensitive adhesive layer comprising:
While continuously conveying the film after the exposure step, a long optical member is laminated on the outer surface of the pressure-sensitive adhesive layer, and a laminating step for pressing this laminate from above and below,
The manufacturing method of the optical member with a separate film containing this.

  [2] The manufacturing method according to [1], wherein in the exposure step, pattern exposure is performed by irradiation with the active energy ray through a mask.

  [3] The mask has a penetrating portion extending in a direction along the transport direction of the separate film having the coating layer, and the penetrating portion is arranged along the width direction of the separate film having the coating layer. The production method according to [2].

[4] The manufacturing method according to [2], wherein the mask is a gradation mask.
[5] In any one of [1] to [4], further including a curing step of winding the optical member with a separate film obtained in the bonding step into a roll and curing the pressure-sensitive adhesive layer in a roll state. The manufacturing method as described.

  [6] The manufacturing method according to any one of [1] to [5], wherein in the exposure step, the active energy ray is irradiated to the coating layer a plurality of times.

  [7] Surface activation step of performing energy irradiation on at least one of a bonding surface with the pressure-sensitive adhesive layer in the optical member and a bonding surface with the optical member in the pressure-sensitive adhesive layer before the bonding step. The production method according to any one of [1] to [6], further comprising:

  [8] The manufacturing method according to any one of [1] to [7], wherein the optical member is a polarizing plate.

  According to the manufacturing method of the present invention, it is possible to provide an optical member with a separate film that can maintain good adhesion between the pressure-sensitive adhesive layer and a member adjacent thereto even with respect to bending in the applied flexible display. .

It is the schematic which shows an example of the manufacturing method of the optical member with a separate film which concerns on this invention, and a manufacturing apparatus used therewith. It is a schematic sectional drawing which shows an example of the separate film which has a coating layer. It is a schematic sectional drawing which shows an example of the separate film with an adhesive layer. It is the schematic which shows an example of the bending aspect of a flexible display. It is a schematic top view which shows a mode that an active energy ray is irradiated to a coating layer through a mask. It is a schematic top view which shows the example of the arrangement pattern of the 1st area | region and 2nd area | region in an adhesive layer. It is a schematic sectional drawing which shows an example of the irradiation method of the active energy ray using a mask. It is a schematic sectional drawing which shows another example of the irradiation method of the active energy ray using a mask. It is a schematic top view which shows the other example of the arrangement pattern of the 1st area | region and 2nd area | region in an adhesive layer. It is a schematic top view which shows the other example of the arrangement pattern of the 1st area | region and 2nd area | region in an adhesive layer. It is a schematic top view which shows the other example of the arrangement pattern of the 1st area | region and 2nd area | region in an adhesive layer. It is a schematic top view which shows the other example of the arrangement pattern of the 1st area | region and 2nd area | region in an adhesive layer. It is a schematic sectional drawing which shows an example of the optical member with a separate film.

The method for producing an optical member with a separate film according to the present invention includes the following steps:
A coating process in which an active energy ray-curable pressure-sensitive adhesive composition is coated on a long separate film to form a coating layer;
While continuously transporting a separate film having a coating layer, the coating layer is subjected to pattern exposure by irradiation of active energy rays, an exposed first region, and a second region having a smaller exposure amount than the first region, An exposure step of obtaining a separate film having an adhesive layer containing
A laminating step of laminating a long optical member on the outer surface of the pressure-sensitive adhesive layer and continuously pressing the laminated body from above and below while continuously conveying the film after the exposure step;
including. The manufacturing method of the optical member with a separate film which concerns on this invention can further include other processes other than the above. Hereinafter, each process will be described with reference to the drawings. Moreover, below, the separate film which has an adhesive layer which is a film intermediate body bonded by an optical member is also called "separate film with an adhesive layer."

[Coating process]
This step is a step of forming a coating layer 11 by coating an active energy ray-curable pressure-sensitive adhesive composition on a separate film 10 to obtain a separate film 15 having the coating layer 11 (FIG. 1). And FIG. 2). Application of the active energy ray-curable pressure-sensitive adhesive composition can be performed using a coating apparatus 50.

(1) Separate film The separate film 10 is usually a thermoplastic resin film, preferably a light-transmitting (more preferably optically transparent) thermoplastic resin film. Specific examples of the thermoplastic resin include polyolefin resins such as chain polyolefin resins (polyethylene resins, polypropylene resins, etc.) and cyclic polyolefin resins (norbornene resins, etc.); polyvinyl fluoride, polyvinylidene fluoride, polyfluoride Fluorinated polyolefin resins such as fluorinated ethylene; polyester resins such as polyethylene terephthalate resins and polyethylene naphthalate resins; (meth) acrylic resins such as methyl methacrylate resins; triacetyl cellulose [TAC], Cellulose resin such as cellulose acetate resin such as diacetyl cellulose; polycarbonate resin; polyvinyl alcohol resin; polyvinyl acetate resin; polyarylate resin; polyimide resin; polystyrene resin; De resins; poly (ether sulfone) resins; polysulfone resins; and mixtures thereof, including copolymers thereof. In this specification, “(meth) acryl” means acryl and / or methacryl, and “(meth)” when referred to as (meth) acrylate or the like has the same meaning.

  As the separate film 10, the thing which gave the mold release process with respect to the surface by which the adhesive layer is laminated | stacked can be used. Examples of the mold release treatment are silicone treatment, long chain alkyl treatment, fluorine treatment and the like. The thickness of the separate film 10 is, for example, about 5 to 200 μm, preferably 10 to 150 μm, and more preferably 15 to 100 μm.

(2) Active energy ray-curable pressure-sensitive adhesive composition The active energy ray-curable pressure-sensitive adhesive composition is a pressure-sensitive adhesive composition that undergoes a curing reaction upon irradiation with active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays. It is. The active energy ray-curable pressure-sensitive adhesive composition is preferably an ultraviolet curable pressure-sensitive adhesive composition. A suitable example of the ultraviolet curable pressure-sensitive adhesive composition is a (meth) acrylic ultraviolet curable pressure-sensitive adhesive composition containing a (meth) acrylic compound as a main component. In the present invention, any conventionally known active energy ray-curable pressure-sensitive adhesive composition can be used. The active energy ray-curable pressure-sensitive adhesive composition can be a solvent type, a solventless type, a water dispersion type, or the like.

  One example of the active energy ray-curable pressure-sensitive adhesive composition is one or more polymerizable monomers having at least one active energy ray-curable site in the molecule (hereinafter also simply referred to as “polymerizable monomer”). It is an adhesive composition containing. The active energy ray-curable site is, for example, an ethylenic double bond. The active energy ray-curable pressure-sensitive adhesive composition is preferably a (meth) acrylic pressure-sensitive adhesive composition containing a (meth) acrylic compound as a main component. In this case, the polymerizable monomer is preferably an active energy ray. It is a curable (meth) acrylic monomer. A suitable example of the active energy ray-curable (meth) acrylic monomer is a (meth) acrylic monomer having a (meth) acryloyl group, and a specific example thereof is represented by the following formula (I):

(Meth) acrylic acid ester represented by In the above formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 14 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms. It represents an aralkyl group having 7 to 21 carbon atoms which may be substituted with 10 alkoxy groups. R ² is preferably an alkyl group having 1 to 14 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms. The (meth) acrylic acid ester represented by the formula (I) may be used alone or in combination of two or more.

  Specific examples of the (meth) acrylate represented by the formula (I) include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate, and lauryl acrylate. Linear alkyl acrylate ester; branched alkyl acrylate ester such as isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate An alkyl moiety such as n-butyl methacrylate, n-octyl methacrylate or lauryl methacrylate in which the alkyl moiety is linear; an alkyl moiety such as isobutyl methacrylate, 2-ethylhexyl methacrylate or isooctyl methacrylate Branched Containing methacrylic acid alkyl esters.

When R ² is an alkyl group substituted with an alkoxy group, i.e., specific examples of the (meth) acrylic acid ester represented by formula (I) when R ² is an alkoxyalkyl group are acrylic acid 2- Including methoxyethyl, ethoxymethyl acrylate, 2-methoxyethyl methacrylate, ethoxymethyl methacrylate and the like. Specific examples of R ² are (meth) acrylic acid ester represented by formula (I) in the case of an aralkyl group having 7 to 21 carbon atoms include benzyl acrylate, benzyl methacrylate.

  The (meth) acrylic monomer having the (meth) acryloyl group may contain a (meth) acrylic acid ester having an alicyclic structure in the molecule. The alicyclic structure usually has 5 or more carbon atoms, preferably about 5 to 7 carbon atoms. Specific examples of the (meth) acrylic acid ester having an alicyclic structure include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclododecyl (meth) acrylate, ( (Meth) acrylic acid methyl cyclohexyl, (meth) acrylic acid trimethyl cyclohexyl, (meth) acrylic acid tert-butyl cyclohexyl, (meth) acrylic acid cyclohexyl phenyl, α-ethoxyacrylic acid cyclohexyl and the like.

  The polymerizable monomer can include a polymerizable monomer having a polar functional group. The polymerizable monomer having a polar functional group is preferably a (meth) acrylic monomer. Examples of polar functional groups include free carboxyl groups, hydroxyl groups, amino groups, and heterocyclic groups such as epoxy groups.

  Specific examples of the polymerizable monomer having a polar functional group include (meth) acrylic acid, a polymerizable monomer having a free carboxyl group such as β-carboxyethyl (meth) acrylate; (meth) acrylic acid 2-hydroxyethyl, ( 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (2-hydroxyethoxy) ethyl (meth) acrylate, 2- or 3-chloro-2-hydroxypropyl (meth) acrylate , Polymerizable monomers having a hydroxyl group such as diethylene glycol mono (meth) acrylate; acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3 Polymerizable monomers having a heterocyclic group such as 4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, and 2,5-dihydrofuran; aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meta ) And a polymerizable monomer having an amino group different from a heterocyclic ring, such as acrylate and dimethylaminopropyl (meth) acrylate. As the polymerizable monomer having a polar functional group, only one kind may be used alone, or two or more kinds may be used in combination.

  Among the above, the polymerizable monomer having a polar functional group preferably includes a polymerizable monomer having a hydroxyl group and / or a polymerizable monomer having a free carboxyl group.

  The polymerizable monomer is, for example, the following formula (II) in addition to the polymerizable monomer exemplified above:

The (meth) acrylic acid ester which has an aryloxyalkyl group like the phenoxyethyl group containing (meth) acrylic acid ester represented by these can be included. In the above formula (II), R ³ represents a hydrogen atom or a methyl group, n represents an integer of 1 to 8, and R ⁴ represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group. When R ⁴ is an alkyl group, the carbon number can be about 1 to 9, and when it is an aralkyl group, the carbon number is about 7 to 11, and when it is an aryl group, the carbon number is 6 Can be on the order of -10.

Examples of the alkyl group having 1 to 9 carbon atoms constituting R ⁴ in the formula (II) include methyl, butyl and nonyl, and examples of the aralkyl group having 7 to 11 carbon atoms include benzyl, phenethyl and naphthylmethyl. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, naphthyl and the like.

  Specific examples of the phenoxyethyl group-containing (meth) acrylic acid ester represented by the formula (II) are: (meth) acrylic acid 2-phenoxyethyl, (meth) acrylic acid 2- (2-phenoxyethoxy) ethyl, ethylene oxide (Meth) acrylic acid ester of modified nonylphenol, 2- (o-phenylphenoxy) ethyl (meth) acrylate, and the like. Only one type of phenoxyethyl group-containing (meth) acrylic acid ester may be used alone, or two or more types may be used in combination. Among them, phenoxyethyl group-containing (meth) acrylic acid esters include 2-methoxyethyl (meth) acrylate, 2- (o-phenylphenoxy) ethyl (meth) acrylate and / or 2- (2) (meth) acrylic acid. -Phenoxyethoxy) ethyl is preferably included.

  Another example of the polymerizable monomer that is a (meth) acrylic monomer is a (meth) acrylamide monomer. Specific examples of the (meth) acrylamide monomer include N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (4- Hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl ( (Meth) acrylamide, N-isopropyl (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, N- [2- ( 2-Oxo-1-imidazolidinyl) ethyl] (meth) acrylami 2-acryloylamino-2-methyl-1-propanesulfonic acid, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (meth) acrylamide, N- (1 -Methylethoxymethyl) (meth) acrylamide, N- (1-methylpropoxymethyl) (meth) acrylamide, N- (2-methylpropoxymethyl) (meth) acrylamide [also known as N- (isobutoxymethyl) (meth) Acrylamide], N- (butoxymethyl) (meth) acrylamide, N- (1,1-dimethylethoxymethyl) (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N- (2-ethoxyethyl) ) (Meth) acrylamide, N- (2-propoxyethyl) (me ) Acrylamide, N- [2- (1-methylethoxy) ethyl] (meth) acrylamide, N- [2- (1-methylpropoxy) ethyl] (meth) acrylamide, N- [2- (2-methylpropoxy) Ethyl] (meth) acrylamide [Also known as: N- (2-isobutoxyethyl) (meth) acrylamide], N- (2-butoxyethyl) (meth) acrylamide, N- [2- (1,1-dimethylethoxy) Ethyl] (meth) acrylamide and the like. Only one (meth) acrylamide monomer may be used alone, or two or more may be used in combination.

  The said polymerizable monomer can contain other polymerizable monomers other than a (meth) acrylic-type monomer. Examples of other polymerizable monomers include styrene monomers and vinyl monomers. The polymerizable monomer can contain one or more of the other polymerizable monomers.

  Specific examples of the styrenic monomer include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, alkyl styrene; fluorostyrene Halogenated styrenes such as chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; nitrostyrene, acetylstyrene, methoxystyrene, divinylbenzene and the like.

  Specific examples of the vinyl monomer include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate and the like; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene chloride And vinylidene halides such as vinyl pyridine, vinyl pyrrolidone and vinyl carbazole, nitrogen-containing aromatic vinyls; conjugated diene monomers such as butadiene, isoprene and chloroprene; acrylonitrile, methacrylonitrile and the like.

  The polymerizable monomer may include a monomer having two or more active energy ray-curable sites such as ethylenic double bonds in the molecule. An example of such a polyfunctional monomer is a (meth) acrylic monomer having two or more (meth) acryloyl groups in the molecule.

Specific examples of (meth) acrylic monomers having two or more (meth) acryloyl groups in the molecule are as follows:
1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate,
Ethylene glycol di (meth) acrylate,
Diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate,
Tripropylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate,
Tricyclodecanediyl dimethanol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate,
Both end (meth) acrylic acid adducts of bisphenol A diglycidyl ether,
Polyester di (meth) acrylate,
Di (meth) acrylate of diol which is an adduct of bisphenol A ethylene dioxide or propylene oxide,
Di (meth) acrylate of diol which is an adduct of ethylene oxide or propylene oxide of hydrogenated bisphenol A,
Tricyclodecane dimethanol di (meth) acrylate,
A monomer having two (meth) acryloyl groups in the molecule, such as cyclohexanedimethanol di (meth) acrylate;
Trimethylolpropane tri (meth) acrylate,
Trimethylolpropane trioxyethyl (meth) acrylate,
Pentaerythritol tri (meth) acrylate,
Tris (2-hydroxyethyl) isocyanurate di (meth) acrylate,
A monomer having three (meth) acryloyl groups in the molecule, such as tricyclodecane dimethanol di (meth) acrylate;
A monomer having four (meth) acryloyl groups in the molecule, such as pentaerythritol tetra (meth) acrylate;
An epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A is included.

  In the (meth) acrylic active energy ray-curable pressure-sensitive adhesive composition, the active energy ray-curable component may be composed of only the polymerizable monomer, but preferably in addition to the polymerizable monomer, ) Contains one or more acrylic polymers and / or oligomers.

  The (meth) acrylic polymer and / or oligomer may be a (co) polymer obtained by (co) polymerizing one or more of the above polymerizable monomers. The (meth) acrylic polymer and / or oligomer is preferably composed mainly of a structural unit derived from one or more of (meth) acrylic acid esters represented by the above formula (I). The unit is more preferably 50 parts by weight or more, more preferably 60 parts by weight or more, and particularly preferably 70 parts by weight or more, in 100 parts by weight of all the structural units. Especially, it is preferable that the (meth) acrylic acid ester represented by the said formula (I) contains n-butyl acrylate.

  The (meth) acrylic polymer and / or oligomer preferably includes a structural unit derived from the polymerizable monomer having the polar functional group. Content of the said structural unit is 0.1-20 weight part normally in 100 weight part of all the structural units, Preferably it is 0.4-10 weight part. The (meth) acrylic polymer and / or oligomer itself may have an active energy ray-curable site such as an ethylenic double bond.

  The (meth) acrylic polymer may have a standard polystyrene equivalent weight average molecular weight Mw by gel permeation chromatography (GPC) of, for example, 50,000 to 800,000. The active energy ray-curable pressure-sensitive adhesive composition can contain one or more (meth) acrylic polymers having a Mw of 50,000 to 800,000. The active energy ray-curable pressure-sensitive adhesive composition may further contain a (meth) acrylic polymer or oligomer having an Mw of less than 50,000.

  When the active energy ray-curable pressure-sensitive adhesive composition contains the polymerizable monomer and the (meth) acrylic polymer and / or oligomer, these may be contained as a partial polymer of the polymerizable monomer.

  The active energy ray-curable pressure-sensitive adhesive composition usually contains a photopolymerization initiator. Specific examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-cyclohexylacetophenone, and the like. Benzophenone, 2-chlorobenzophenone, p, p′-dichlorobenzophenone, p, p′-bisdiethylaminobenzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, 4- (2-hydroxyethoxy) Ketones such as phenyl (2-hydroxy-2-propyl) ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin ethers such as ether and benzoin isobutyl ether; thioxanthones such as thioxanthone, 2-chlorothioxanthone and 2-methylthioxanthone; phosphine oxides such as bisacylphosphine oxide and benzoylphosphine oxide; ketals such as benzyldimethyl ketal Quinones such as camphane-2,3-dione and phenanthrenequinone. A photoinitiator may be used individually by 1 type and may use 2 or more types together.

  The content of the photopolymerization initiator is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the active energy ray-curable component such as the polymerizable monomer. .

  The active energy ray-curable pressure-sensitive adhesive composition may further contain a crosslinking agent. The crosslinking agent crosslinks the active energy ray-curable component, such as a compound having two or more functional groups in the molecule that can react with the reactive functional group of the active energy ray-curable component such as the polar functional group described above. A compound. Specific examples include isocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds, and the like. Among these, the isocyanate compound, the epoxy compound, and the aziridine compound have two or more functional groups in the molecule that can react with the polar functional group in the active energy ray-curable component. A crosslinking agent may be used individually by 1 type, and may use 2 or more types together.

  An isocyanate compound is a compound having at least two isocyanato groups (—NCO) in the molecule. Specific examples of isocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, hydrogenated diphenylmethane diisocyanate. ; Biuret and isocyanurate forms of these isocyanate compounds; adducts obtained by reacting these isocyanate compounds with polyols such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, glycerol and trimethylolpropane Body; two of these isocyanate compounds Body, including those in trimers and the like.

  The epoxy compound is a compound having at least two epoxy groups in the molecule. Specific examples of the epoxy compound include bisphenol A type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, and trimethylolpropane. Including triglycidyl ether, N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, etc. .

  An aziridine-based compound is a compound having at least two 3-membered ring skeletons composed of one nitrogen atom and two carbon atoms, also called ethyleneimine. Specific examples of the aziridine compound include diphenylmethane-4,4′-bis (1-aziridinecarboxamide), toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, isophthaloylbis-1- (2 -Methylaziridine), tris-1-aziridinylphosphine oxide, hexamethylene-1,6-bis (1-aziridinecarboxamide), trimethylolpropane-tris-β-aziridinylpropionate, tetramethylolmethane-tris -Β-aziridinyl propionate and the like.

  Specific examples of metal chelate compounds include compounds in which acetylacetone or ethyl acetoacetate is coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium. Including.

  The crosslinking agent is usually contained in a proportion of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, with respect to 100 parts by weight of the active energy ray-curable component.

  The active energy ray-curable pressure-sensitive adhesive composition can further contain an ionic compound as an antistatic agent. The ionic compound is, for example, a compound having an inorganic cation or an organic cation and an inorganic anion or an organic anion. An ionic compound may be used individually by 1 type, and may use 2 or more types together.

Examples of the inorganic cation include alkali metal ions such as lithium cation [Li ⁺ ], sodium cation [Na ⁺ ], and potassium cation [K ⁺ ], beryllium cation [Be ²⁺ ], and magnesium cation [Mg ²⁺ ]. And alkaline earth metal ions such as calcium cation [Ca ²⁺ ].

  Examples of the organic cation include an imidazolium cation, a pyridinium cation, a pyrrolidinium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation.

  Among the cation components described above, the organic cation component is excellent in compatibility in the pressure-sensitive adhesive composition. Among organic cation components, a pyridinium cation and an imidazolium cation are advantageous in terms of antistatic properties.

Examples of inorganic anions include chloride anions [Cl ⁻ ], bromide anions [Br ⁻ ], iodide anions [I ⁻ ], tetrachloroaluminate anions [AlCl ₄ ⁻ ], heptachlorodialuminate anions [Al ₂ Cl ₇ ⁻ ], tetrafluoroborate anion [BF ₄ ⁻ ], hexafluorophosphate anion [PF ₆ ⁻ ], perchlorate anion [ClO ₄ ⁻ ], nitrate anion [NO ₃ ⁻ ], hexafluoroarsenate anion [AsF _6] ^- ], Hexafluoroantimonate anion [SbF ₆ ⁻ ], hexafluoro niobate anion [NbF ₆ ⁻ ], hexafluoro tantalate anion [TaF ₆ ⁻ ], dicyanamide anion [(CN) ₂ N ⁻ ] and the like. It is done.

Examples of the organic anion include acetate anion [CH ₃ COO ⁻ ], trifluoroacetate anion [CF ₃ COO ⁻ ], methanesulfonate anion [CH ₃ SO ₃ ⁻ ], trifluoromethanesulfonate anion [CF ₃ SO ₃ ⁻ ], p-toluenesulfonate anion [p-CH ₃ C ₆ H ₄ SO ₃ ⁻ ], bis (fluorosulfonyl) imide anion [(FSO ₂ ) ₂ N ⁻ ], bis (trifluoromethanesulfonyl) imide anion [(CF ₃ SO ₂ ) ₂ N ⁻ ], tris (trifluoromethanesulfonyl) methanide anion [(CF ₃ SO ₂ ) ₃ C ⁻ ], dimethyl phosphinate anion [(CH ₃ ) ₂ POO ⁻ ], (poly) hydrofluorofluoride anion [ F (HF) _n ⁻ ] (n is about 1 to 3), thiocyan anion [SC N ^-], perfluorobutane sulfonate anion [C ₄ F ₉ SO ₃ ^-], bis (pentafluoroethane sulfonyl) imide anion _{[(C 2 F 5 SO 2)} 2 N - ], perfluoro butanoate anion [C ₃ F ₇ COO ⁻ ], (trifluoromethanesulfonyl) (trifluoromethanecarbonyl) imide anion [(CF ₃ SO ₂ ) (CF ₃ CO) N ⁻ ], perfluoropropane-1,3-disulfonate anion [ ⁻ O ₃ S (CF ₂ ) ₃ SO ₃ ⁻ ], carbonate anion [CO ₃ ²⁻ ] and the like. Among the anionic components described above, anionic components containing fluorine atoms are advantageous in terms of antistatic properties.

  Specific examples of the ionic compound can be appropriately selected from a combination of the cation component and the anion component. Examples of ionic compounds having an organic cation are listed below according to the structure of the organic cation.

Pyridinium salt:
N-hexylpyridinium hexafluorophosphate,
N-octylpyridinium hexafluorophosphate,
N-octyl-4-methylpyridinium hexafluorophosphate,
N-butyl-4-methylrupyridinium hexafluorophosphate,
N-decylpyridinium bis (fluorosulfonyl) imide,
N-dodecylpyridinium bis (fluorosulfonyl) imide,
N-tetradecylpyridinium bis (fluorosulfonyl) imide,
N-hexadecylpyridinium bis (fluorosulfonyl) imide,
N-dodecyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-tetradecyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-hexadecyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-benzyl-2-methylpyridinium bis (fluorosulfonyl) imide,
N-benzyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-hexylpyridinium bis (trifluoromethanesulfonyl) imide,
N-octylpyridinium bis (trifluoromethanesulfonyl) imide,
N-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide,
N-butyl-4-methyllpyridinium bis (trifluoromethanesulfonyl) imide.

Imidazolium salt:
1-ethyl-3-methylimidazolium hexafluorophosphate,
1-ethyl-3-methylimidazolium p-toluenesulfonate,
1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide,
1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide,
1-butyl-3-methylimidazolium methanesulfonate,
1-butyl-3-methylimidazolium bis (fluorosulfonyl) imide.

Pyrrolidinium salt:
N-butyl-N-methylpyrrolidinium hexafluorophosphate,
N-butyl-N-methylpyrrolidinium bis (fluorosulfonyl) imide,
N-butyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide.

Quaternary ammonium salt:
Tetrabutylammonium hexafluorophosphate,
Tetrabutylammonium p-toluenesulfonate,
(2-hydroxyethyl) trimethylammonium bis (trifluoromethanesulfonyl) imide,
(2-Hydroxyethyl) trimethylammonium dimethylphosphinate.

Examples of ionic compounds having inorganic cations are as follows.
Lithium bromide,
Lithium iodide,
Lithium tetrafluoroborate,
Lithium hexafluorophosphate,
Lithium thiocyanate,
Lithium perchlorate,
Lithium trifluoromethanesulfonate,
Lithium bis (fluorosulfonyl) imide,
Lithium bis (trifluoromethanesulfonyl) imide,
Lithium bis (pentafluoroethanesulfonyl) imide,
Lithium tris (trifluoromethanesulfonyl) methanide,
Lithium p-toluenesulfonate,
Sodium hexafluorophosphate,
Sodium bis (fluorosulfonyl) imide,
Sodium bis (trifluoromethanesulfonyl) imide,
Sodium p-toluenesulfonate,
Potassium hexafluorophosphate,
Potassium bis (fluorosulfonyl) imide,
Potassium bis (trifluoromethanesulfonyl) imide,
Potassium p-toluenesulfonate.

  The ionic compound preferably has a melting point of 30 ° C. or higher, more preferably 35 ° C. or higher, from the viewpoint of sustaining antistatic properties. On the other hand, the ionic compound preferably has a melting point of 90 ° C. or less, more preferably 70 ° C. or less, and still more preferably less than 50 ° C., from the viewpoint of compatibility with the active energy ray-curable component.

  The ionic compound is preferably blended in an amount of 0.2 to 8 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the active energy ray-curable component. When the content of the ionic compound is 0.2 parts by weight or more, it is advantageous for improving the antistatic property, and when it is 8 parts by weight or less, it is advantageous for improving the durability of the pressure-sensitive adhesive layer.

  The active energy ray-curable pressure-sensitive adhesive composition improves the adhesion between the pressure-sensitive adhesive layer 12 and the glass when the pressure-sensitive adhesive layer 12 of the pressure-sensitive adhesive layer-attached separate film 20 is bonded to the optical member 30 made of glass. In order to make it contain, a silane compound can be further contained. A silane compound may be used individually by 1 type, and may use 2 or more types together.

  Examples of the silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl dimethoxymethyl silane, 3-glycidoxypropyl-ethoxy dimethyl silane, and the like.

  The silane compound may be of a silicone oligomer type. As a silicone oligomer, the following can be mentioned, for example.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer,
3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer,
3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer,
A copolymer containing a mercaptopropyl group, such as 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer;
Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer,
Mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer,
Mercaptomethyltriethoxysilane-tetramethoxysilane copolymer,
A mercaptomethyl group-containing copolymer such as a mercaptomethyltriethoxysilane-tetraethoxysilane copolymer;
3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer,
3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer,
3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer,
3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer,
3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,
Copolymers containing 3-glycidoxypropyl groups, such as 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;
3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer,
3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer,
3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer,
3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer,
3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,
A methacryloyloxypropyl group-containing copolymer such as 3-methacryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;
3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer,
3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer,
3-acryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer,
3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer,
3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,
Copolymers containing acryloyloxypropyl groups, such as 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;
Vinyltrimethoxysilane-tetramethoxysilane copolymer,
Vinyltrimethoxysilane-tetraethoxysilane copolymer,
Vinyltriethoxysilane-tetramethoxysilane copolymer,
Vinyltriethoxysilane-tetraethoxysilane copolymer,
Vinylmethyldimethoxysilane-tetramethoxysilane copolymer,
Vinylmethyldimethoxysilane-tetraethoxysilane copolymer,
Vinylmethyldiethoxysilane-tetramethoxysilane copolymer,
Vinyl group-containing copolymers such as vinylmethyldiethoxysilane-tetraethoxysilane copolymer;
3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer,
3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer,
3-aminopropyltriethoxysilane-tetramethoxysilane copolymer,
3-aminopropyltriethoxysilane-tetraethoxysilane copolymer,
3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer,
Amino group-containing copolymers such as 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer.

  The silane compound is usually contained in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the active energy ray-curable component. When the content of the silane compound is 0.01 parts by weight or more, an effect of improving the adhesion between the pressure-sensitive adhesive layer 12 and the glass is easily obtained. Further, when the content is 10 parts by weight or less, bleeding out of the silane compound from the pressure-sensitive adhesive layer 12 can be suppressed.

  Active energy ray-curable pressure-sensitive adhesive compositions include solvents (aromatic hydrocarbons, aliphatic hydrocarbons, ketones, esters, etc.), crosslinking catalysts, weathering stabilizers, tackifiers, plasticizers, softeners, dyes 1 type, or 2 or more types of other additives, such as a pigment, an inorganic filler, light-scattering microparticles | fine-particles, and a tackifier, can be contained.

(3) Application of active energy ray-curable pressure-sensitive adhesive composition The method for applying the active energy ray-curable pressure-sensitive adhesive composition to the separate film 10 using the coating apparatus 50 is not particularly limited. Method, reverse gravure coating method, micro gravure method, dipping method, roll coating method, flexographic printing method and the like can be used. The thickness of the coating layer 11 made of the active energy ray-curable pressure-sensitive adhesive composition is adjusted such that the thickness of the pressure-sensitive adhesive layer 12 of the pressure-sensitive adhesive layer-attached separate film 20 falls within the range described below.

  As shown in FIG. 1, more specifically, in the coating process, an active energy ray-curable pressure-sensitive adhesive composition is formed on one surface of a long separate film 10 that is continuously unwound from the first feeding roll 1. It can be a process of continuously applying an object. At this time, as shown in FIG. 1, the active energy ray-curable pressure-sensitive adhesive composition may be applied while the separate film 10 is wound around a coating roll 60.

[Exposure process]
In this step, while the separate film 15 having the coating layer 11 is continuously conveyed, the coating layer 11 is subjected to pattern exposure by irradiating active energy rays, and the pressure-sensitive adhesive layer having the pressure-sensitive adhesive layer 12. This is a step of obtaining the attached separate film 20 (see FIGS. 1 and 3). Through this step, a separate film 20 with an adhesive layer having an adhesive layer 12 that is an intermediate of the optical member with a separate film is continuously produced. The active energy ray is preferably ultraviolet rays.

  The exposed first area 12a and the second area 12b having a smaller exposure amount than the first area 12a are formed in the pressure-sensitive adhesive layer 12 by pattern exposure by irradiation with active energy rays (FIG. 3). The second region 12b may be a region that is not exposed, but is preferably a region that is exposed to some extent as long as the exposure amount is smaller than that of the first region 12a, and in which the curing reaction by irradiation with active energy rays proceeds to some extent. is there.

  The arrangement pattern of the 1st area | region 12a and the 2nd area | region 12b in the adhesive layer 12 can be selected according to the bending aspect of the flexible display applied. An example of the bending mode of the flexible display is shown in FIG. 4A shows a flexible display that can be wound, and FIG. 4B shows a flexible display that can be folded.

  As shown in FIG. 1, the adhesive layer 12 including the first region 12 a and the second region 12 b applies an active energy ray from an exposure device (active energy ray irradiation device) 80 through a mask 81. 11 can be formed by a method of irradiating 11. Irradiation of active energy rays to the coating layer 11 may be performed a plurality of times. By appropriately selecting the slit shape and characteristics of the mask 81 to be used, the method of irradiating active energy rays through the mask 81, and the like, the arrangement pattern of the first region 12a and the second region 12b can be made a desired pattern. . Specific examples of the arrangement pattern of the first region 12a and the second region 12b, the method of irradiating active energy rays through the mask 81, and the like are as follows.

  a) FIG. 5 is a schematic top view showing a state in which active energy rays are irradiated onto the coating layer 11 through the light shielding mask 81a. The arrow indicates the transport direction of the separate film 15 having the coating layer 11. The light-shielding mask 81a has a plurality of slits (penetrating portions) 85 extending in the direction along the longitudinal direction (conveying direction) of the separate film 15 having the coating layer 11, and the plurality of slits 85 has a film width. Arranged along the direction. The exposure apparatus (active energy ray irradiation apparatus) 80 is fixed with respect to the light shielding mask 81a. When the separate film 15 having the coating layer 11 is irradiated with active energy rays from the exposure apparatus 80 through the light shielding mask 81a, the first region 12a and the second region 12b are arranged as shown in FIG. 6A, for example. The obtained pressure-sensitive adhesive layer 12 can be obtained. This arrangement pattern is advantageous for the rollable flexible display shown in FIG. 4A, and the first region 12a and the first region extending in a direction substantially perpendicular to the winding direction as shown in FIG. By alternately arranging the two regions 12b, the stress at the time of winding can be relaxed, thereby maintaining good adhesion between the pressure-sensitive adhesive layer 12 and the members adjacent thereto. Can do.

  b) If a mask 81 is used in which all other portions are penetrating portions (slits), leaving the central portion in the width direction, the first region 12a and the second region 12b are arranged as shown in FIG. 6B, for example. The pressure-sensitive adhesive layer 12 can be obtained. This arrangement pattern is advantageous for the foldable flexible display shown in FIG. 4B, and by providing the second region 12b at a position corresponding to the foldable portion, the stress during folding can be relaxed, Thereby, the adhesiveness between the adhesive layer 12 and the member adjacent to this can be maintained favorable.

  c) When an active energy ray is irradiated once using a light-shielding mask having a slit like the mask 81a shown in FIG. 5, the light-shielded region becomes the second region 12b that is not exposed (the exposure amount is zero). . On the other hand, as shown in FIG. 7, after irradiating the active energy ray through the light shielding mask 81a having the slit 85 (FIG. 7A), the active energy ray is applied to the entire surface of the coating layer 11 without passing through the mask. Irradiating (FIG. 7B) According to the multiple irradiation method, the second region 12b can be an exposed region. The order of the process of FIG. 7B and the process of FIG. 7A may be reversed.

  d) As shown in FIG. 8, when the active energy ray is irradiated through the halftone mask 81b, the second region 12b exposed by one irradiation can be formed. The halftone mask 81b refers to a mask having a region 82 where the amount of transmission of active energy rays is larger and a region 83 which is smaller (not zero).

  e) FIGS. 9 to 12 show other examples of arrangement patterns of the first region 12a and the second region 12b. The direction in which the first region 12a and the second region 12b extend may be parallel to the film transport direction (or, for example, the short-side direction when the optical member 40 with a separate film is a sheet body) (see FIG. 9).

  The widths of the first region 12a and the second region 12b are not particularly limited, and when there are a plurality of these, they may be the same (FIG. 10A) or may be different (FIG. 10B). )). The ratio of the first region 12a in the surface of the pressure-sensitive adhesive layer 12 is not particularly limited, and the distance (pitch) between the adjacent first regions 12a may be shortened (FIG. 11 (a)) or increased. It is also possible (FIG. 11B). Further, as shown in FIG. 12, the exposure amount of the first region 12a and / or the second region 12b may gradually change along a certain direction. When such gradation is given, it becomes possible to reduce the change (difference) in the storage elastic modulus of the adhesive layer 12 at the boundary between the first region 12a and the second region 12b. The durability of the layer 12 can be increased. The first region 12a and / or the second region 12b in which the exposure amount gradually changes can be formed by irradiating active energy rays through a gradation mask. A gradation mask is a mask in which the amount of transmission of active energy rays gradually changes along a certain direction.

  Although the light source of the active energy ray irradiated to the coating layer 11 is not particularly limited, ultraviolet light having a light emission distribution at a wavelength of 400 nm or less is preferable, and specifically, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical A lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, an LED type ultraviolet lamp, or the like can be used.

The irradiation intensity of the active energy ray to the coating layer 11 is, for example, 1 to 1000 mW / cm ² . Moreover, the integrated light quantity expressed as the product of the light irradiation intensity and the light irradiation time is, for example, 10 to 5000 mJ / cm ² .

  The thickness of the pressure-sensitive adhesive layer 12 of the pressure-sensitive adhesive layer-attached separate film 20 obtained through the exposure process is, for example, 1 to 200 μm, preferably 5 to 35 μm. The thickness of the pressure-sensitive adhesive layer 12 being 200 μm or less is advantageous in terms of thinning the display and the efficiency of irradiation with active energy rays. Further, when the thickness is 5 μm or more, it is advantageous in terms of stress relaxation when the flexible display is bent, and the adhesion with an adjacent optical member is improved.

[Bonding process]
This step is a step of bonding the optical member 30 to the outer surface of the pressure-sensitive adhesive layer 12 of the pressure-sensitive adhesive layer-attached film 20 to obtain the optical member 40 with a separate film (see FIGS. 1 and 13). As shown in FIG. 13, the optical member 40 with a separate film is obtained by laminating and laminating the separate film 20 with a pressure-sensitive adhesive layer on the surface of the optical member 30 through the pressure-sensitive adhesive layer 12. According to the optical member 40 with a separate film obtained by the present invention, there is a flexible display formed by peeling and removing the separate film 10 and bonding it to another optical member such as an image display cell through the exposed adhesive layer 20. Even if it is bent, it is possible to maintain good adhesion between the pressure-sensitive adhesive layer and members adjacent thereto (optical member 30 and other optical members such as image display cells). Therefore, the flexible display to which the optical member with a separate film 40 obtained by the present invention is applied can be excellent in durability and reliability.

  Specifically, the bonding step can be performed as follows. The continuous adhesive film 20 with a long pressure-sensitive adhesive layer obtained through the exposure process is continuously transported and continuously transported while the long optical member 30 is unwound from the second feeding roll 2 to separate the adhesive film with a pressure-sensitive adhesive layer. The optical member 30 is laminated on the outer surface of the 20 pressure-sensitive adhesive layers 12 to form a laminate. The laminated film optical member 40 is continuously manufactured by pressing the laminated body from above and below using a pair of bonding rolls 90 and the like. From the viewpoint of adhesiveness between the pressure-sensitive adhesive layer 12 and the optical member 30, the separate film 20 with the pressure-sensitive adhesive layer obtained through the exposure step is supplied to the bonding step with the optical member 30 without being wound into a roll. It is preferable that the surface activation treatment or the like is performed as necessary, and then supplied to the bonding step with the optical member 30.

  FIG. 1 shows an example in which the adhesive film with adhesive layer 20 is bonded to one side of the optical member 30, but the adhesive film with adhesive layer 20 may be bonded to both surfaces of the optical member 30. When bonding the adhesive film with an adhesive layer 20 on both surfaces of the optical member 30, the double-sided adhesive film with an adhesive layer 20 may be bonded simultaneously, or may be bonded stepwise.

  The optical member 30 is an optical member that can be incorporated into a flexible display, and may be, for example, an optical film having a single layer structure or a multilayer structure. Specific examples of the optical film include: a polarizing film; an optical compensation film (such as a retardation film), an antireflection film (sheet), a light diffusion film (sheet), a reflective film (sheet), etc .; an optical functional film; Film; polarizing plate; glass film (including glass sheet and glass substrate) and the like. The optical member 30 is preferably a polarizing plate.

  The polarizing plate can be obtained by bonding a protective film to at least one surface of the polarizing film via an adhesive layer. This protective film may also serve as an optical compensation film such as a retardation film. The polarizing plate may be obtained by laminating a cured resin layer formed of a curable resin on at least one surface of the polarizing film. Further, for example, another optical functional film such as a retardation film or a brightness enhancement film may be laminated on the polarizing film or the protective film or the cured resin layer via an adhesive layer or an adhesive layer. .

  A protective film may be laminated on the polarizing film or on the protective film or the cured resin layer. A protective film is a peelable film temporarily attached to an optical member for the purpose of protecting the surface of the optical member from scratches and dirt, and is usually a base film made of a thermoplastic resin and a pressure-sensitive adhesive laminated thereon. Composed of layers.

  A polarizing film is a film having a function of extracting linearly polarized light from incident natural light, and a suitable example is that a dichroic dye such as iodine or a dichroic dye is adsorbed and oriented on a uniaxially stretched polyvinyl alcohol resin film. It is what. The thickness of the polarizing film is not particularly limited, but is usually 2 to 35 μm.

  The protective film can be a thermoplastic resin film having translucency (preferably optically transparent). Specific examples of thermoplastic resins include polyolefin resins such as chain polyolefin resins (polypropylene resins, etc.) and cyclic polyolefin resins (norbornene resins, etc.); polyester resins (polyethylene terephthalate resins, etc.); ) Acrylic resin (methyl methacrylate resin, etc.); Cellulosic resin (cellulose acetate resin such as triacetyl cellulose and diacetyl cellulose); Polycarbonate resin; Polyvinyl alcohol resin; Polyvinyl acetate resin; Polyarylate Polystyrene resin; Polyether sulfone resin; Polysulfone resin; Polyamide resin; Polyimide resin; and mixtures and copolymers thereof. The thickness of the protective film is, for example, about 5 to 200 μm, preferably 10 to 150 μm, and more preferably 15 to 100 μm.

  The cured resin layer is formed from a curable resin such as a thermosetting resin or an active energy ray curable resin. The curable resin may contain a thermopolymerizable compound, may contain a cationically polymerizable compound, or may contain a radically polymerizable compound. May be included. The thickness of the cured resin layer is, for example, about 0.1 to 10 μm, and preferably 1 to 5 μm.

  In the case where protective films are bonded to both surfaces of the polarizing film, these protective films may be made of the same kind of thermoplastic resin or may be made of different types of thermoplastic resins. Moreover, the thickness may be the same or different. When the cured resin layers are laminated on both surfaces of the polarizing film, these cured resin layers may be formed of the same kind of curable resin or different kinds of curable resins. Moreover, the thickness may be the same or different. The protective film or the cured resin layer may have a surface treatment layer (coating layer) such as a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, an antistatic layer, an antifouling layer, or a conductive layer. Good. When a protective film is bonded to one side of the polarizing film or a cured resin layer is laminated, the pressure-sensitive adhesive layer 12 of the pressure-sensitive adhesive layer-attached separate film 20 may be directly bonded to the surface of the polarizing film.

  The retardation film is an optical film exhibiting optical anisotropy, and is a uniaxial or biaxially stretched film of a thermoplastic resin film composed of a resin or the like that can be used for the protective film, or a liquid crystal on a thermoplastic resin film. It can be a film that exhibits optical anisotropy by coating / orienting a functional compound, a film that exhibits optical anisotropy by coating an inorganic layered compound on a thermoplastic resin film, and the like.

  A protective film (or retardation film or the like) can be bonded to the polarizing film via an adhesive layer. As the adhesive forming the adhesive layer, a water-based adhesive, an active energy ray-curable adhesive, or a thermosetting adhesive can be used, and a water-based adhesive and an active energy ray-curable adhesive are preferable.

  Examples of the water-based adhesive include an adhesive made of a polyvinyl alcohol-based resin aqueous solution, an aqueous two-component urethane emulsion adhesive, and the like. Among these, a water-based adhesive composed of a polyvinyl alcohol-based resin aqueous solution is preferably used. Polyvinyl alcohol resins include vinyl alcohol homopolymers obtained by saponifying polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith. A polyvinyl alcohol copolymer obtained by saponifying a polymer, or a modified polyvinyl alcohol polymer obtained by partially modifying the hydroxyl group thereof can be used. The water-based adhesive can contain a crosslinking agent such as an aldehyde compound (glyoxal, etc.), an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, an amine compound, and a polyvalent metal salt.

  When using a water-based adhesive, it is preferable to carry out a drying step for removing water contained in the water-based adhesive after pasting the polarizing film and the protective film. After the drying process, for example, a curing process for curing at a temperature of about 20 to 45 ° C. may be provided.

  The active energy ray-curable adhesive refers to an adhesive that cures by irradiating active energy rays such as ultraviolet rays, visible rays, X-rays, and electron beams, for example, a polymerizable compound and a photopolymerization initiator. The curable composition containing, the curable composition containing photoreactive resin, the curable composition containing binder resin and a photoreactive crosslinking agent, etc. can be mentioned. An ultraviolet curable adhesive is preferable. Examples of the polymerizable compound include photopolymerizable monomers such as photocurable epoxy monomers, photocurable (meth) acrylic monomers, and photocurable urethane monomers, and oligomers derived from the photopolymerizable monomers. it can. As a photoinitiator, what contains the substance which generate | occur | produces active species like a neutral radical, an anion radical, and a cation radical by irradiation of an active energy ray can be mentioned. As an active energy ray-curable adhesive containing a polymerizable compound and a photopolymerization initiator, a curable composition containing a photocurable epoxy monomer and a cationic photopolymerization initiator, a photocurable (meth) acrylic monomer, and light Preferably, a curable composition containing a radical polymerization initiator, a photocurable epoxy monomer, a photocurable (meth) acrylic monomer, a photocationic polymerization initiator, and a photoradical polymerization initiator are preferably used. it can.

  When using an active energy ray-curable adhesive, after bonding the polarizing film and the protective film, a drying step is performed as necessary (however, the active energy ray-curable adhesive is substantially free of solvent components). It may be a non-solvent-free adhesive.) Next, a curing step of curing the active energy ray-curable adhesive by irradiating active energy rays is performed. The light source of the active energy ray is not particularly limited, but ultraviolet light having a light emission distribution at a wavelength of 400 nm or less is preferable. Specifically, the low pressure mercury lamp, the medium pressure mercury lamp, the high pressure mercury lamp, the ultrahigh pressure mercury lamp, the chemical lamp, the black light lamp, the micro A wave excitation mercury lamp, a metal halide lamp, etc. can be used.

  Prior to the bonding of the protective film, in order to improve adhesion, corona treatment, plasma treatment, ultraviolet irradiation treatment, flame (flame) treatment, saponification treatment is applied to at least one of the polarizing film and the protective film. A surface activation treatment such as a primer layer forming treatment may be performed.

  When a protective film is bonded to both surfaces of a polarizing film, the adhesive for bonding these protective films may be the same type of adhesive or a different type of adhesive.

[Other processes]
(1) Drying process The manufacturing method which concerns on this invention has a drying process which dries (solvent volatilizes) the coating layer 11 of the separate film 15 which has the coating layer 11 between a coating process and an exposure process. It may be. This drying step is usually performed when the coating layer 11 (active energy ray-curable pressure-sensitive adhesive composition) contains a solvent. With reference to FIG. 1, the drying process can be carried out by continuously conveying the long separate film 15 having the coating layer 11 obtained by the coating process and passing it through the drying means 70 (introduction).

  The drying means 70 is not particularly limited as long as it can volatilize the solvent, and is, for example, a drying furnace (heating furnace). The drying furnace may further include a decompression means in addition to the heating means. The drying conditions such as the amount of hot air supplied to the drying furnace, the temperature and pressure in the drying furnace, take into account the type of solvent contained in the coating layer 11 and the surface condition after drying such as smoothness and condensation. Is set appropriately. The drying temperature (for example, the temperature in the drying furnace) is usually 50 to 120 ° C, preferably 60 to 110 ° C.

(2) Surface activation process The manufacturing method according to the present invention is more specifically bonded to the pressure-sensitive adhesive layer 12 in the optical member 30 between the exposure process and the bonding process prior to the bonding process. The surface activation process which performs energy irradiation to at least one of the bonding surface with the optical member 30 in the surface and the adhesive layer 12 can be further included. The surface activation treatment in the surface activation step can be a corona treatment, a plasma treatment, an ultraviolet irradiation treatment, a flame (flame) treatment, a saponification treatment, or the like.

  When surface activation treatment is performed on both the bonding surface of the optical member 30 with the pressure-sensitive adhesive layer 12 and the bonding surface of the pressure-sensitive adhesive layer 12 with the optical member 30, these surface activation treatments are performed with the pressure-sensitive adhesive layer 12. From the viewpoint of adhesion between the optical member 30 and the optical member 30, preferably, the time until the adhesive layer-attached separate film 20 after the exposure step reaches the bonding step and the optical member 30 after the surface activation treatment are bonded. It is performed at a timing such that the time to reach the process is the same or approximately the same. Moreover, from the viewpoint of the adhesiveness between the pressure-sensitive adhesive layer 12 and the optical member 30, after performing energy irradiation in the surface activation step, the laminate is used in the bonding step using a pair of bonding rolls 90 and the like. The time until pressing is preferably 5 seconds or less. You may perform a surface activation process in multiple times with respect to the said bonding surface.

(3) Winding process and curing process The manufacturing method according to the present invention winds the optical member 40 with a long separate film obtained through the bonding process around the winding roll 3 in a roll shape. A winding step for forming a film roll can be included (see FIG. 1). Moreover, the manufacturing method which concerns on this invention can also include the curing process which performs the curing (aging) of the adhesive layer 12 in the roll state after a winding-up process. By performing the curing step, the curing reaction of the pressure-sensitive adhesive layer 12 is promoted, and the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer 13 can be increased. Further, by performing curing (adhesive curing reaction) in a state where the pressure-sensitive adhesive layer 12 is in close contact with the optical member 30, interaction with the optical member 30 (including chemical reaction) and pressure-sensitive adhesive for the optical member 30 are performed. Therefore, the adhesion between the pressure-sensitive adhesive layer 12 and the optical member 30 can be further enhanced. The curing temperature is, for example, 20 to 45 ° C.

(4) Bonding process with other optical member The manufacturing method according to the present invention includes a peeling process for peeling and removing the separate film 10 from the optical member 40 with a separate film, and a surface of the pressure-sensitive adhesive layer 12 exposed by the peeling process. It can include the bonding process (2nd bonding process) which bonds other optical members other than an optical member. After the peeling step and before the second bonding step, at least one of the pressure-sensitive adhesive layer 12 and the bonding surface of the other optical member is subjected to corona treatment, plasma treatment, ultraviolet irradiation treatment, frame (flame) treatment, Ken Surface treatment such as crystallization treatment or primer layer formation treatment may be performed.

  Said other optical member is an optical member which can be integrated in a flexible display, and an image display cell is illustrated. The image display cell is, for example, a flexible liquid crystal cell, an organic EL display element, or the like. When the other optical member is an image display cell, the optical laminate obtained through the pasting step (second pasting step) has an image display cell / adhesive layer 12 / optical member 30 (for example, a polarizing plate). It has a layer structure including this order. In a flexible display including an optical layered body having such a configuration, the stress generated in the pressure-sensitive adhesive layer 12 in a bent state can be relieved, so that even if the display is bent, the pressure-sensitive adhesive layer and a member adjacent thereto Good adhesion can be maintained between the optical member 30 and the other optical member.

  DESCRIPTION OF SYMBOLS 1 1st delivery roll, 2nd 2nd delivery roll, 3 winding roll, 10 separate film, 11 coating layer, 12 adhesive layer, 12a 1st area | region, 12b 2nd area | region, 15 Separate film which has a coating layer, 20 Separate film with pressure-sensitive adhesive layer, 30 optical member, 40 optical member with separate film, 50 coating device, 60 coating roll, 70 drying means, 80 exposure device (active energy ray irradiation device), 81 mask, 81a light shielding Mask, 81b Halftone mask, 82, 83 Halftone mask area, 85 slit, 90 bonding roll.

Claims (8)

A coating process in which an active energy ray-curable pressure-sensitive adhesive composition is coated on a long separate film to form a coating layer;
While continuously transporting a separate film having the coating layer, the coating layer is subjected to pattern exposure by irradiation of active energy rays, and an exposed first region and a second region having a smaller exposure amount than the first region An exposure step of obtaining a separate film having a pressure-sensitive adhesive layer comprising:
While continuously conveying the film after the exposure step, a long optical member is laminated on the outer surface of the pressure-sensitive adhesive layer, and a laminating step for pressing this laminate from above and below,
The manufacturing method of the optical member with a separate film containing this.   The manufacturing method of Claim 1 which performs the pattern exposure by irradiation of the said active energy ray through a mask in the said exposure process.   The mask has a penetrating portion extending in a direction along a transport direction of a separate film having the coating layer, and the penetrating portion is arranged along a width direction of the separate film having the coating layer. Item 3. The manufacturing method according to Item 2.   The manufacturing method according to claim 2, wherein the mask is a gradation mask.   The manufacturing of any one of Claims 1-4 which further includes the curing process which winds up the optical member with a separate film obtained by the said bonding process in roll shape, and cures the said adhesive layer in a roll state. Method.   The manufacturing method according to any one of claims 1 to 5, wherein in the exposure step, the active energy ray is irradiated to the coating layer a plurality of times.   Before the said bonding process, the surface activation process which performs energy irradiation to at least one of the bonding surface with the said adhesive layer in the said optical member and the bonding surface with the said optical member in the said adhesive layer is further included. The manufacturing method of any one of Claims 1-6.   The manufacturing method according to claim 1, wherein the optical member is a polarizing plate.