WO2017115613A1

WO2017115613A1 - Method for producing resin film-equipped optical member

Info

Publication number: WO2017115613A1
Application number: PCT/JP2016/086047
Authority: WO
Inventors: 弘也中川
Original assignee: 住友化学株式会社
Priority date: 2015-12-28
Filing date: 2016-12-05
Publication date: 2017-07-06
Also published as: TW201727290A; JP2017120328A; TWI709770B

Abstract

[Problem] To provide a method for producing a resin film-equipped optical member that is obtained by adhering a resin film to an optical member by using an adhesive layer, and exhibits favorable adhesion between the adhesive layer and the optical member. [Solution] A method for producing a resin film-equipped optical member that involves: a coating step for forming a coating layer by coating a longitudinally oriented resin film with an adhesive composition; a drying step for obtaining a resin film having an adhesive layer by drying the coating layer, by introducing the coated film to a drying means while continuously transporting said film; a smoothing treatment step for continuously transporting the resin film having the adhesive layer while pressing a mirror surface mold against the outer surface of the adhesive layer; and an adhesion step for continuing to continuously transport the smoothed film, layering a longitudinally oriented optical member on the outer surface of the adhesive layer, and applying pressure to this layered body from above and below.

Description

Manufacturing method of optical member with resin film

This invention relates to the manufacturing method of the optical member with a resin film formed by bonding a resin film to an optical member through an adhesive layer.

Various optical members represented by polarizing plates and the like are sometimes used by being bonded to other members via an adhesive layer (for example, Patent Document 1). For this reason, the optical member may be marketed in the form of an optical member with an adhesive layer in which an adhesive layer is previously provided on one surface thereof. 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

The adhesive layer used to bond the optical member to another member is required to have good adhesion to the optical member. When the adhesiveness of the pressure-sensitive adhesive layer used to bond the optical member to another member is not sufficient, the durability of the composite member formed by bonding the optical member and the other member via the pressure-sensitive adhesive layer And reliability may be reduced.

An object of the present invention is an optical member with a resin film formed by bonding a resin film to an optical member via an adhesive layer, such as an optical member with an adhesive layer provided with the above-described separate film. It is providing the method for manufacturing the optical member with a resin film with favorable adhesiveness of an agent layer and an optical member.

This invention provides the manufacturing method of the optical member with a resin film shown below.
[1] A coating process in which a pressure-sensitive adhesive composition is coated on a long resin film to form a coating layer;
A drying step of obtaining a resin film having a pressure-sensitive adhesive layer by continuously introducing the film after the coating step into a drying means and drying the coating layer,
While continuously transporting the resin film having the pressure-sensitive adhesive layer, a smoothing treatment step of pressing a mirror mold on the outer surface of the pressure-sensitive adhesive layer;
While continuously conveying the resin film after the smoothing treatment step, a long optical member is laminated on the outer surface of the pressure-sensitive adhesive layer, and a laminating step of pressing this laminate from above and below,
The manufacturing method of the optical member with a resin film containing.

[2] The manufacturing method according to [1], further including a curing step of winding the optical member with a resin film obtained in the bonding step into a roll shape and curing the pressure-sensitive adhesive layer in a roll state.

[3] The production method according to [1] or [2], wherein in the smoothing treatment step, the temperature of the pressure-sensitive adhesive layer in contact with the mirror mold is lower than the glass transition temperature of the pressure-sensitive adhesive composition.

[4] The method according to any one of [1] to [3], further including a surface activation step of performing energy irradiation on a bonding surface of the optical member with the pressure-sensitive adhesive layer before the bonding step. Production method.

[5] The method according to any one of [1] to [4], wherein a surface of the optical member that is in contact with an outer surface of the pressure-sensitive adhesive layer contains a (meth) acrylic resin.

[6] The production method according to any one of [1] to [5], wherein the optical member is a polarizing plate.
[7] The production method according to any one of [1] to [6], wherein the resin film is a separate film.

According to the production method of the present invention, it is possible to provide an optical member with a resin film having good adhesion between the pressure-sensitive adhesive layer and the optical member.

It is the schematic which shows an example of the manufacturing method of the optical member with a resin film which concerns on this invention, and a manufacturing apparatus used for it. It is a schematic sectional drawing which shows an example of the resin film which has a coating layer (before drying). It is a schematic sectional drawing which shows an example of the resin film which has an adhesive layer (before smoothing process). It is a schematic sectional drawing which shows an example of the resin film with an adhesive layer. It is a schematic sectional drawing which shows an example of the optical member with a resin film.

The method for producing an optical member with a resin film according to the present invention includes the following steps:
A coating process in which a pressure-sensitive adhesive composition is coated on a long resin film to form a coating layer;
A drying step of obtaining a resin film having a pressure-sensitive adhesive layer by introducing it into a drying means while continuously transporting the film after the coating step and drying the coating layer;
A smoothing treatment step of pressing a mirror mold against the outer surface of the pressure-sensitive adhesive layer while continuously conveying the resin film having the pressure-sensitive adhesive layer; and continuously conveying the resin film after the smoothing treatment step, A laminating step of laminating a long optical member on the outer surface of the pressure-sensitive adhesive layer and pressing the laminate from above and below;
including. The manufacturing method of the optical member with a resin film which concerns on this invention can further include other processes other than the above. Hereinafter, each step will be described with reference to FIGS. Moreover, below, the resin film which has an adhesive layer which is a film intermediate body bonded by an optical member is also called "resin film with an adhesive layer."

[Coating process]
This step is a step of forming the coating layer 11 by coating the adhesive composition on the resin film 10 with the coating device 50 to obtain the resin film 15 having the coating layer 11 (FIG. 1). And FIG. 2).

(1) Resin Film The resin film 10 is usually a thermoplastic resin film, preferably a light-transmitting (more preferably optically transparent) thermoplastic resin film. Specific examples of thermoplastic resins 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 the present specification, “(meth) acryl” means acryl and / or methacryl, and “(meth)” when referred to as (meth) acrylate or the like has the same meaning.

The thickness of the resin film 10 is, for example, about 5 to 200 μm, preferably 10 to 150 μm, more preferably 15 to 100 μm.

The resin film with an adhesive layer that is a film intermediate produced in the production method of the present invention can be, for example, a separate film with an adhesive layer. In this case, the resin film 10 can be a separate film in which a release treatment is performed on the surface on which the pressure-sensitive adhesive layer is laminated. Examples of the mold release treatment are silicone treatment, long chain alkyl treatment, fluorine treatment and the like.

The resin film 10 may be an optical member other than a separate film. The resin film 10 which is an optical member other than the separate film may have a single layer structure or a multilayer structure. Specific examples of the resin film 10 that is an optical member include: a polarizing film; an optical functional film such as an optical compensation film (retardation film, etc.), a light diffusion film (sheet), a reflective film (sheet); a protective film for a polarizing film; Including a polarizing plate.

(2) Pressure-sensitive adhesive composition Examples of pressure-sensitive adhesive compositions applied to the resin film 10 include (meth) acrylic pressure-sensitive adhesive compositions, urethane-based pressure-sensitive adhesive compositions, silicone-based pressure-sensitive adhesive compositions, and polyester-based adhesives. Examples thereof include a pressure-sensitive adhesive composition, a polyamide-based pressure-sensitive adhesive composition, a polyether-based pressure-sensitive adhesive composition, a fluorine-based pressure-sensitive adhesive composition, and a rubber-based pressure-sensitive adhesive composition. Of these, a (meth) acrylic pressure-sensitive adhesive having a (meth) acrylic resin as a base polymer is preferably used from the viewpoints of transparency, adhesive strength, reliability, reworkability, and the like.

(2-1) Base polymer Specific examples of the (meth) acrylic resin that can be suitably used as the base polymer of the (meth) acrylic pressure-sensitive adhesive composition include the following formula (I):

(Meth) acrylic resin (A-1) which is a polymer having a structural unit derived from a (meth) acrylic acid ester represented by the formula (containing 50% by weight or more) as a main component.

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 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.

Specific examples of the (meth) acrylic acid ester represented by the formula (I) include a straight chain such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate and lauryl acrylate. Chain alkyl acrylates; Branched alkyl acrylates such as isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate Linear alkyl methacrylates such as n-octyl methacrylate and lauryl methacrylate; branched alkyl esters such as isobutyl methacrylate, 2-ethylhexyl methacrylate and isooctyl methacrylate;

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 the (meth) acrylic acid ester represented by the formula (I) when R ² is an aralkyl group having 7 to 21 carbon atoms include benzyl acrylate, benzyl methacrylate and the like.

(Meth) acrylic acid ester represented by formula (I) may be used alone or in combination of two or more. Among them, the (meth) acrylic acid ester preferably contains n-butyl acrylate. The (meth) acrylic resin (A-1) preferably contains 50% by weight or more of n-butyl acrylate in all monomers constituting the (meth) acrylic resin (A-1). Of course, in addition to n-butyl acrylate, other (meth) acrylic acid esters represented by the formula (I) may be used in combination.

The (meth) acrylic resin (A-1) usually comprises a (meth) acrylic acid ester of the above formula (I) and at least one other monomer typified by a monomer having a polar functional group. It is a copolymer. The monomer having a polar functional group is preferably a (meth) acrylic acid compound having a polar functional group. Examples of polar functional groups include free carboxyl groups, hydroxyl groups, amino groups, and heterocyclic groups including epoxy groups.

Specific examples of the monomer having a polar functional group include (meth) acrylic acid, a monomer having a free carboxyl group such as β-carboxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, ( 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (2-hydroxyethoxy) ethyl (meth) acrylate, 2- or 3-chloro-2-hydroxypropyl (meth) acrylate , 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 , 4-epoxycyclohe Monomers having a heterocyclic group such as silmethyl (meth) acrylate, glycidyl (meth) acrylate, 2,5-dihydrofuran; aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, dimethyl The monomer etc. which have an amino group different from a heterocyclic ring like aminopropyl (meth) acrylate are included. The monomer which has a polar functional group may be used individually by 1 type, and may use 2 or more types together.

Among the above, from the viewpoint of the reactivity of the (meth) acrylic resin (A-1), a hydroxyl group is one of the polar functional group-containing monomers constituting the (meth) acrylic resin (A-1). It is preferable to use the monomer which has. In addition to the monomer having a hydroxyl group, it is also effective to use a monomer having another polar functional group, for example, a monomer having a free carboxyl group.

The (meth) acrylic resin (A-1) is a monomer having one olefinic double bond and at least one aromatic ring in the molecule (provided that the monomer represented by the above formula (I)). A structural unit derived from a monomer and a monomer having a polar functional group is excluded. Preferable examples include (meth) acrylic acid compounds having an aromatic ring. Suitable examples of the (meth) acrylic acid compound having an aromatic ring include the following formula (II):

A (meth) acrylic acid ester having an aryloxyalkyl group such as a phenoxyethyl group-containing (meth) acrylic acid ester represented by the formula:

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, its carbon number can be about 1 to 9, and when it is an aralkyl group, its carbon number is about 7 to 11, and when it is an aryl group, its 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. Examples of the aralkyl group having 7 to 11 carbon atoms include benzyl, phenethyl, naphthylmethyl, and the like. 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) include 2-methoxyethyl (meth) acrylate, 2- (2-phenoxyethoxy) ethyl (meth) acrylate, 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-phenoxyethyl (meth) acrylate, 2- (o-phenylphenoxy) ethyl (meth) acrylate and / or 2- (2) (meth) acrylic acid. -Phenoxyethoxy) ethyl is preferably included.

The (meth) acrylic resin (A-1) is preferably a structural unit derived from the (meth) acrylic acid ester represented by the above formula (I), preferably 60 to 99. 9% by weight, more preferably 80 to 99.6% by weight of structural units derived from a monomer having a polar functional group, preferably 0.1 to 20% by weight, more preferably 0.8%. 4 to 10% by weight of a structural unit derived from a monomer having one olefinic double bond and at least one aromatic ring in the molecule, preferably 0 to 40% by weight, More preferably, it can be contained in a proportion of 6 to 12% by weight.

The (meth) acrylic resin (A-1) includes a (meth) acrylic acid ester represented by the formula (I), a monomer having a polar functional group, and one olefinic double bond in the molecule. A structural unit derived from a monomer other than the monomer having at least one aromatic ring (hereinafter also referred to as “other monomer”) may be included. Specific examples of other monomers are derived from structural units derived from (meth) acrylic acid esters having an alicyclic structure in the molecule, structural units derived from styrene monomers, and vinyl monomers. The structural unit includes a structural unit derived from a monomer having a plurality of (meth) acryloyl groups in the molecule, a structural unit derived from a (meth) acrylamide monomer, and the like. Other monomers may be used alone or in combination of two or more.

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, ( Examples include methyl cyclohexyl acrylate, trimethyl cyclohexyl (meth) acrylate, tert-butyl cyclohexyl (meth) acrylate, cyclohexyl phenyl (meth) acrylate, cyclohexyl α-ethoxy acrylate, and the like.

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

Specific examples of vinyl monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, and other fatty acid vinyl esters; vinyl chloride, vinyl bromide, such as vinyl bromide; Examples include vinylidene halides such as vinylidene chloride; nitrogen-containing aromatic vinyls such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated diene monomers such as butadiene, isoprene and chloroprene; acrylonitrile, methacrylonitrile and the like.

Specific examples of monomers having a plurality of (meth) acryloyl groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol. 2 (meth) in the molecule such as di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate A monomer having an acryloyl group; a monomer having three (meth) acryloyl groups in the molecule such as trimethylolpropane tri (meth) acrylate.

Specific examples of the (meth) acrylamide compound include N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, and N- (4-hydroxy). Butyl) (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) acrylamide 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) (meta 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.

The (meth) acrylic resin (A-1) contains other monomers in a proportion of usually 0 to 20% by weight, preferably 0 to 10% by weight, based on the total amount of the solid content.

From the viewpoint of adhesion between the pressure-sensitive adhesive layer and the optical member, the (meth) acrylic resin (A-1) has a weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) of 500,000. It is preferable that it is above, and it is more preferable that it is 600,000 or more. The Mw of the (meth) acrylic resin (A-1) is usually 1.7 million or less.

The base polymer of the (meth) acrylic pressure-sensitive adhesive composition may contain two or more types of (meth) acrylic resin (A-1). In addition to the (meth) acrylic resin (A-1), the base polymer is a different (meth) acrylic resin, for example, a structural unit derived from a (meth) acrylic acid ester of the formula (I) And a structural unit derived from a (meth) acrylic resin (A-2) having no polar functional group and a (meth) acrylic acid ester represented by the above formula (I) as a main component, Mw (Meth) acrylic resin (A-3) or the like in the range of from 50,000 to 120,000.

(2-2) Crosslinking agent The pressure-sensitive adhesive composition may further contain a crosslinking agent (B). The crosslinking agent is a compound that reacts with a structural unit derived from a polar functional group-containing monomer in a base polymer such as a (meth) acrylic resin to crosslink the base polymer. 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 at least two functional groups that can react with the polar functional group in the base polymer. Only 1 type may be used for a crosslinking agent (B) individually, and 2 or more types may be used together.

An isocyanate compound is a compound having at least two isocyanato groups (—NCO) in the molecule. Specific examples of the isocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate and the like. In addition, adducts obtained by reacting these isocyanate compounds with polyols such as glycerol and trimethylolpropane, and those obtained by converting isocyanate compounds into dimers, trimers, and the like can also serve as the crosslinking agent (B).

An 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, trimethylolpropane. Including triglycidyl ether, N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, etc. .

An aziridine compound is a compound having at least two three-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 (B) is usually in a proportion of 0.05 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the solid content of the base polymer (the total when two or more are used). Contained. When the content of the crosslinking agent (B) is 0.05 parts by weight or more, the durability of the pressure-sensitive adhesive layer tends to be improved.

(2-3) Ionic Compound The pressure-sensitive adhesive composition can further contain an ionic compound (C) as an antistatic agent. The ionic compound (C) is, for example, a compound having an inorganic cation or an organic cation and an inorganic anion or an organic anion.

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 (C) can be appropriately selected from the combination of the cation component and the anion component. When the examples of the ionic compound (C) having an organic cation are classified according to the structure of the organic cation, the following may be mentioned.

Pyridinium salt:
N-hexylpyridinium hexafluorophosphate,
N-octylpyridinium hexafluorophosphate,
N-octyl-4-methylpyridinium hexafluorophosphate,
N-butyl-4-methylrupyridinium hexafluorophosphate,
Tetrabutylammonium 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 p-toluenesulfonate,
(2-hydroxyethyl) trimethylammonium bis (trifluoromethanesulfonyl) imide,
(2-Hydroxyethyl) trimethylammonium dimethylphosphinate.

Examples of the ionic compound (C) having an inorganic cation include the following.
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 (C) 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 (C) 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 base polymer.

The ionic compound (C) is preferably 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 solid content of the base polymer (the total when two or more are used). It is blended at a ratio of parts. The content of the ionic compound (C) being 0.2 parts by weight or more is advantageous for improving the antistatic property, and the content of 8 parts by weight or less is advantageous for improving the durability of the pressure-sensitive adhesive layer. is there.

(2-4) Silane Compound The pressure-sensitive adhesive composition is used to improve the adhesion between the pressure-sensitive adhesive layer and the glass when the pressure-sensitive adhesive layer of the resin film with the pressure-sensitive adhesive layer is bonded to an optical member made of glass. The silane compound (D) can further be contained.

Examples of the silane compound (D) include vinyltrimethoxysilane, vinyltriethoxysilane, 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-glycidoxypropyltrimeth Shishiran, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl dimethoxymethyl silane, 3-glycidoxypropyl-ethoxy dimethyl silane, and the like. Two or more silane compounds may be used.

The silane compound (D) 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,
3-glycidoxypropyl group-containing copolymers 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,
Copolymers containing methacryloyloxypropyl groups, such as 3-methacryloxyyl propylmethyldiethoxysilane-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 ratio of the silane compound (D) is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the solid content of the base polymer (the total when two or more are used). Contained. The adhesive improvement effect of an adhesive layer and glass is easy to be acquired as content of a silane compound (D) is 0.01 weight part or more. Moreover, the bleeding out of the silane compound (D) from an adhesive layer can be suppressed as content is 10 weight part or less.

(2-5) Other components The pressure-sensitive adhesive composition contains additives such as a crosslinking catalyst, weathering stabilizer, tackifier, plasticizer, softener, dye, pigment, inorganic filler, light scattering fine particles, and tackifier. Can be contained.
In addition, an ultraviolet curable compound can be blended in the pressure-sensitive adhesive composition, and after forming the pressure-sensitive adhesive layer, it can be cured by irradiating with ultraviolet rays to form a harder pressure-sensitive adhesive layer.

The pressure-sensitive adhesive composition is usually prepared as a pressure-sensitive adhesive liquid in which a compounding component is dissolved or dispersed by containing an organic solvent. The organic solvent is preferably selected according to the type of the base polymer. Specific examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and pentane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate and butyl acetate. Including various esters. The concentration of the base polymer in the adhesive liquid is usually 3 to 20% by weight.

(3) Application of pressure-sensitive adhesive composition The method of applying the pressure-sensitive adhesive composition to the resin film 10 using the coating apparatus 50 is not particularly limited. For example, the slot die method, the reverse gravure coating method, and the micro gravure method , Dipping method, roll coating method, flexographic printing method and the like can be used. The thickness of the coating layer 11 which consists of an adhesive composition is adjusted so that the thickness of the adhesive layer 13 of the resin film 25 with an adhesive layer may become the range mentioned later.

As shown in FIG. 1, more specifically, in the coating step, the adhesive composition is continuously applied to one surface of the long resin film 10 that is continuously unwound from the first feeding roll 1. It can be a process. Under the present circumstances, as FIG. 1 shows, you may apply an adhesive composition, winding the resin film 10 on the roll 60 for coating.

For the purpose of improving adhesion between the resin film 10 and the pressure-sensitive adhesive layer, the coated surface of the resin film 10 is subjected to corona treatment, plasma treatment, ultraviolet irradiation treatment, flame (flame) treatment, saponification treatment, primer layer formation treatment, etc. A surface treatment may be applied.

[Drying process]
This step is a step in which the coating layer 11 of the resin film 15 having the coating layer 11 is dried (solvent volatilization) to obtain the resin film 20 having the pressure-sensitive adhesive layer 12 (see FIGS. 1 and 3). With reference to FIG. 1, the drying process can be carried out by continuously conveying the long resin 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.

[Smoothing process]
This step is a step of smoothing the surface by pressing a mirror mold on the outer surface of the pressure-sensitive adhesive layer 12 of the resin film 20 having the pressure-sensitive adhesive layer 12 (see FIGS. 1 and 4). Through this step, the pressure-sensitive adhesive layer-attached resin film 25 having the pressure-sensitive adhesive layer 13 (after the smoothing treatment), which is an intermediate of the optical member with a resin film, is continuously produced. By this smoothing treatment, the adhesiveness of the pressure-sensitive adhesive layer 13 to the optical member can be improved. One of the features of the present invention is that it is subjected to a smoothing treatment without being subjected to the step of curing the pressure-sensitive adhesive layer 12 obtained by drying the coating layer 11 (without sufficiently proceeding with the curing reaction of the pressure-sensitive adhesive). In the point. As a result, it is possible to obtain a more special adhesion improving effect.

The smoothing treatment can be carried out by continuously transporting the long resin film 20 having the pressure-sensitive adhesive layer 12 obtained through the drying process and passing it through the smoothing treatment apparatus 80. In the smoothing processing device 80, the mirror mold is pressed against the outer surface of the adhesive layer 12. At this time, the temperature of the pressure-sensitive adhesive layer 12 in contact with the mirror mold is preferably less than the glass transition temperature of the pressure-sensitive adhesive layer composition. By being less than the glass transition temperature, it is possible to prevent the pressure-sensitive adhesive composition from adhering to the surface of the mirror mold when the pressure-sensitive adhesive layer 12 is peeled from the mirror mold. The temperature of the pressure-sensitive adhesive layer 12 can be adjusted by controlling the atmospheric temperature in the smoothing apparatus 80 or the surface temperature of the mirror mold. In order to prevent dew condensation on the surface of the pressure-sensitive adhesive layer and the surface of the mirror mold, it is preferable to keep the inside of the smoothing apparatus 80 in an atmosphere that does not contain moisture such as dry air or nitrogen. The pressing strength of the mirror mold is not particularly limited as long as the surface shape of the mirror mold is transferred, and can be appropriately adjusted according to the degree of progress of curing of the pressure-sensitive adhesive layer 12.

As long as the surface shape of the mirror mold is a mirror surface, the overall shape is not particularly limited, and may be a flat plate shape or a cylindrical or cylindrical roll. From the viewpoint of continuous productivity, a mirror roll which is a columnar or cylindrical mold is preferred. Among the mirror rolls, a cooling roll whose surface temperature can be controlled by a refrigerant inside the roll is preferable.

The material of the base material of the mirror mold is not particularly limited, and can be appropriately selected from metal, glass, carbon, resin, or a composite thereof. From the viewpoint of workability and the like, metal is preferably used. Suitable metal materials include aluminum, iron, or an alloy mainly composed of aluminum or iron from the viewpoint of cost. From the viewpoint of releasability with the pressure-sensitive adhesive layer, a fluororesin is preferably used. The surface of the mirror mold may be subjected to a mold release treatment in order to facilitate separation from the pressure-sensitive adhesive layer. An example of the mold release treatment is fluorine treatment or the like.

In the smoothing apparatus 80, after the surface shape of the mirror mold is transferred to the outer surface of the pressure-sensitive adhesive layer 12, the mirror mold is peeled from the resin film 25 having the pressure-sensitive adhesive layer 13. The peeling method is not particularly limited. For example, when the mirror mold is a mirror roll, a pressure bonding device such as a nip roll is installed at the separation point between the resin film 25 having the adhesive layer 13 and the mirror mold. A method of peeling the resin film 25 having the pressure-sensitive adhesive layer 13 from the mirror mold using the pressure bonding device as a fulcrum is preferably used. Thereby, it becomes possible to peel the resin film 25 which reached the fulcrum efficiently and stably.

The thickness of the pressure-sensitive adhesive layer 13 of the pressure-sensitive adhesive layer-containing resin film 25 obtained through the smoothing treatment step is, for example, 10 to 45 μm, preferably 10 to 35 μm. The thickness of the pressure-sensitive adhesive layer 13 being 45 μm or less is advantageous for adhesion with an optical member. Moreover, the followability of the adhesive layer 13 with respect to the dimensional change of an optical member becomes favorable as the thickness is 10 micrometers or more.

[Bonding process]
This process is the process of bonding the optical member 30 to the outer surface of the adhesive layer 13 of the resin film 25 with an adhesive layer, and obtaining the optical member 40 with a resin film (refer FIG.1 and FIG.5). As shown in FIG. 5, the optical member with resin film 40 is obtained by laminating and bonding the resin film with adhesive layer 25 to the surface of the optical member 30 through the adhesive layer 13. According to the present invention, it is possible to manufacture the optical member 40 with a resin film having good adhesion between the pressure-sensitive adhesive layer 13 and the optical member 30.

Specifically, the bonding process can be performed as follows. The continuous resin film 25 with a long pressure-sensitive adhesive layer obtained through the smoothing process is continuously transported and continuously transported while the long optical member 30 is unwound from the second feeding roll 2, with a pressure-sensitive adhesive layer. The optical member 30 is laminated on the outer surface (smoothing surface) of the pressure-sensitive adhesive layer 13 of the resin film 25 to obtain a laminate. By pressing this laminated body from above and below using a pair of bonding rolls 90 and the like, the optical member 40 with a resin film is continuously produced. From the viewpoint of the adhesiveness between the pressure-sensitive adhesive layer 13 and the optical member 30, the pressure-sensitive adhesive layer-attached resin film 25 obtained through the smoothing process step is not wound once in a roll shape or subjected to other processing. It is preferable to supply it to the bonding step with the optical member 30 as it is.

FIG. 1 shows an example in which the resin film 25 with an adhesive layer is bonded to one side of the optical member 30, but the resin film 25 with an adhesive layer may be bonded to both surfaces of the optical member 30. When bonding the resin film 25 with an adhesive layer on both surfaces of the optical member 30, the resin film 25 with an adhesive layer of both surfaces may be bonded simultaneously, and may be bonded in steps.

The optical member 30 can be a single-layer or multilayer optical film or the like. Specific examples of the optical film include: a polarizing film; an optical functional film such as an optical compensation film (retardation film, etc.), a light diffusion film (sheet), a reflective film (sheet); a protective film for a polarizing film; a polarizing plate; (Including glass sheet and glass substrate); Separate film; Substrate film for protective film. The optical member 30 is preferably a polarizing plate. In addition, when the resin film 25 with an adhesive layer is a separate film with an adhesive layer, and the optical member 30 is a separate film, as the optical member 40 with a resin film, an adhesive layer with a double-sided separate film (adhesive sheet) Is obtained. Moreover, when the resin film 25 with an adhesive layer is a separate film with an adhesive layer, and the optical member 30 is a base film for a protective film, a protective film with a separate film is obtained as the optical member 40 with a resin film. It is done.

The protective film (also referred to as “surface protective film”) is a peelable film temporarily attached to the optical member for the purpose of protecting the surface of the optical member from scratches and dirt, and is usually made of a thermoplastic resin. It is comprised from a base film and the adhesive layer laminated | stacked on it.

The material of the surface of the optical member 30 that is in contact with the outer surface of the pressure-sensitive adhesive layer 13 is not particularly limited, but the pressure-sensitive adhesive layer 13 and the optical member 30 are still subjected to energy irradiation treatment such as corona treatment on the surface that is normally performed. The manufacturing method according to the present invention is particularly effective when the surface material is such that sufficient adhesion cannot be obtained. Examples of the surface of the optical member 30 in which sufficient adhesion with the pressure-sensitive adhesive layer 13 is difficult to obtain without the smoothing treatment include a surface containing (typically) a (meth) acrylic resin. Can be mentioned. When the optical member 30 is a polarizing plate, such a surface is often formed by a protective film bonded to a polarizing film, an optical compensation film (such as a retardation film), or the like.

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 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, 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, preferably 1 to 5 μm.

When protective films are bonded to both surfaces of the polarizing film, these protective films may be composed of the same kind of thermoplastic resin or different kinds 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 the protective film is bonded to one side of the polarizing film or when the cured resin layer is laminated, the pressure-sensitive adhesive layer 13 of the pressure-sensitive adhesive layer-attached resin film 25 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.

The 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 and an aqueous two-component urethane emulsion adhesive. 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.

In the case of using a water-based adhesive, it is preferable to perform a drying step for removing water contained in the water-based adhesive after pasting the polarizing film and the protective film. After the drying step, for example, a curing step 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 protective films are bonded to both surfaces of the polarizing film, the adhesive for bonding these protective films may be the same type of adhesive or different types of adhesives.

[Other processes]
The manufacturing method of the present invention can further include a surface activation step of irradiating energy on the bonding surface of the optical member 30 with the pressure-sensitive adhesive layer 13. From the viewpoint of adhesiveness between the pressure-sensitive adhesive layer 13 and the optical member 30, energy irradiation is performed in the surface activation process, and then the laminate is pressed using a pair of bonding rolls 90 and the like in the bonding process. The time until is preferably 5 seconds or less. The energy irradiation treatment can be, for example, a corona treatment, a plasma treatment, an ultraviolet irradiation treatment, or the like. Among these, the corona treatment is preferably used from the viewpoint of improving the adhesion and the simplicity of the equipment.

The manufacturing method of the present invention includes a winding process in which a long optical member with a resin film 40 obtained through the bonding process is wound around the winding roll 3 to be wound into a roll shape. (See FIG. 1). Moreover, the manufacturing method of this invention can also include the curing process which performs the curing (aging) of the adhesive layer 13 in the roll state after a winding-up process. By performing the curing process, the curing reaction of the pressure-sensitive adhesive layer 13 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) while the pressure-sensitive adhesive layer 13 is in close contact with the optical member 30, interaction with the optical member 30 (including a chemical reaction) and pressure-sensitive adhesive for the optical member 30 are performed. Therefore, the adhesion between the pressure-sensitive adhesive layer 13 and the optical member 30 can be further enhanced. The curing temperature is, for example, 20 to 45 ° C.

Moreover, the manufacturing method of this invention is the optical member 30 (this optical member is also called a "1st optical member") bonded to the adhesive layer 13 of the resin film 25 with an adhesive layer in the bonding process. A replacement step of replacing with another optical member (this optical member is also referred to as “second optical member”) can be included.

Specifically, for example, when the resin film 25 with the pressure-sensitive adhesive layer is a separate film with a pressure-sensitive adhesive layer and the first optical member is a separate film, the replacing step peels and removes the separate film that is the first optical member. A peeling process and the bonding process (2nd bonding process) which bonds the 2nd optical member, such as a polarizing plate, for example to the adhesive layer 13 of the resin film 25 with an adhesive layer can be included subsequently. . After the peeling step and before the second bonding step, at least one of the pressure-sensitive adhesive layer 13 and the bonding surface of the second optical member is subjected to corona treatment, plasma treatment, ultraviolet irradiation treatment, frame (flame) treatment, and saponification. Surface treatment such as treatment or primer layer formation treatment may be performed.

As described above, according to the present invention, the adhesiveness between the pressure-sensitive adhesive layer 13 of the resin film 25 with the pressure-sensitive adhesive layer and the optical member 30 (first optical member) can be improved. Due to the smoothing process being performed in a state where the curing reaction of the agent layer 12 has not sufficiently progressed, the adhesive property between the second optical member replacing the first optical member and the adhesive layer 13 is also improved. Can increase.

Moreover, the manufacturing method of this invention peels and removes the resin film 10 of the optical member 40 with a resin film obtained through the bonding process like the case where the resin film 10 is a separate film, and exposed the adhesive layer The process of bonding the optical member different from the optical member 30 on the outer surface of 13 can be included. For example, when the resin film 25 with an adhesive layer is a separate film with an adhesive layer and the optical member 30 is a base film for a protective film, a protective film with a separate film is obtained as the optical member 40 with a resin film. However, the separation film is peeled and removed therefrom, and a polarizing plate with a protective film can be obtained by bonding the polarizing plate to the exposed outer surface of the pressure-sensitive adhesive layer 13.

1 First feeding roll, 2nd feeding roll, 3 winding roll, 10 resin film, 11 coating layer, 12 adhesive layer (before energy irradiation), 13 adhesive layer (after smoothing treatment), 15 coating Resin film having a layer, 20 resin film having an adhesive layer (before smoothing treatment), 25 resin film with an adhesive layer, 30 optical member, 40 optical member with a resin film, 50 coating device, 60 coating roll , 70 drying means, 80 smoothing apparatus, 90 bonding roll.

Claims

A coating process in which a pressure-sensitive adhesive composition is coated on a long resin film to form a coating layer;
A drying step of obtaining a resin film having a pressure-sensitive adhesive layer by continuously introducing the film after the coating step into a drying means and drying the coating layer,
While continuously transporting the resin film having the pressure-sensitive adhesive layer, a smoothing treatment step of pressing a mirror mold on the outer surface of the pressure-sensitive adhesive layer;
While continuously conveying the resin film after the smoothing treatment step, a long optical member is laminated on the outer surface of the pressure-sensitive adhesive layer, and a laminating step of pressing this laminate from above and below,
The manufacturing method of the optical member with a resin film containing.
The manufacturing method according to claim 1, further comprising a curing step of winding the optical member with a resin film obtained by the bonding step into a roll shape and curing the pressure-sensitive adhesive layer in a roll state.
The method according to claim 1 or 2, wherein, in the smoothing treatment step, the temperature of the pressure-sensitive adhesive layer in contact with the mirror mold is lower than the glass transition temperature of the pressure-sensitive adhesive composition.
The production method according to any one of claims 1 to 3, further comprising a surface activation step of irradiating energy on a bonding surface of the optical member with the pressure-sensitive adhesive layer before the bonding step.
The method according to any one of claims 1 to 4, wherein a surface of the optical member that is in contact with an outer surface of the pressure-sensitive adhesive layer contains a (meth) acrylic resin.
The manufacturing method according to any one of claims 1 to 5, wherein the optical member is a polarizing plate.
The production method according to any one of claims 1 to 6, wherein the resin film is a separate film.