CN104774569B - Antistatic surface diaphragm - Google Patents

Antistatic surface diaphragm Download PDF

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Publication number
CN104774569B
CN104774569B CN201410677651.4A CN201410677651A CN104774569B CN 104774569 B CN104774569 B CN 104774569B CN 201410677651 A CN201410677651 A CN 201410677651A CN 104774569 B CN104774569 B CN 104774569B
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methyl
compound
antistatic
film
adhesive layer
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CN104774569A (en
Inventor
长仓毅
岛口龙介
长谷川良
小林弘幸
春日充
新见洋人
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention is provided to the pollution of adherend less and without deterioration, the Antistatic surface diaphragm with excellent antistripping antistatic property, and it is to sequentially pass through：The operation of the adhesive layer (2) that the adhesive composition by the acrylic polymer containing copolymer and then also containing more than (F) two function isocyanate compound, (G) crosslinking accelerator and (H) keto-enol tautomer compound is constituted is formed in the one side of the base material film (1) being made up of transparent resin；By in the stripping film (5) of the one side of resin film (3) peeling agent layer (4) of the stacking containing antistatic additive, the operation on adhesive layer (2) surface is fitted in by peeling agent layer (4) and is made, peeling agent layer (4) is that the polysiloxane-based compound of liquid and the resin combination of antistatic additive are formed by containing the remover using dimethyl polysiloxane as main component, at 20 DEG C, and the stripping electrostatic pressure of adhesive layer (2) is ± below 0.6kV.

Description

Antistatic surface diaphragm
Technical field
Fitting in the optical components such as Polarizer, polarizer, display lens coating the present invention relates to one kind (below, has When be also referred to as " optical film ") surface on Antistatic surface diaphragm.More specifically, there is provided a kind of dirt to adherend Dye less, without deterioration and with the Antistatic surface diaphragm of excellent antistripping antistatic property.
Background technology
At present, when manufacture, carrying Polarizer, polarizer, display lens coating, antireflection film, hard coat film, touch surface The optical film of plate nesa coating etc. and when having used the optical articles such as their display, uses by the optics The surface coating surface diaphragm of film and prevent surface contamination, the scratch in subsequent handling.Surface protection film is entered in order to save The labour and time that are fitted again after peeling off go so as to improve operating efficiency, the visual examination to the optical film as product For, directly implement in the state of surface protection film of also fitting on optical film sometimes.
Since in the past, in order to prevent the attachment of scar and dirt in the manufacturing process of optical articles, base has been generally used in The one side of material film is provided with the surface protection film of adhesive layer.Surface protection film is fitted by the adhesive layer of micro- cohesive force In on optical film.The reason for adhesive layer is set as into micro- cohesive force be, in order to by using the surface protection film for finishing from Optical film sur-face peeling and when removing, can easily be peeled off, and in order to prevent binding agent from adhering to and remain in work It is the phenomenon of the generation of glue residue (so-called prevent) on the optical film of adherend product.
In recent years, in the production process of liquid crystal display panel, due to the surface protection film on optical film will be fitted in The stripping electrostatic pressure produced when peeling off and removing, can destroy the electricity such as the driving IC of display picture for controlling liquid crystal display panel The orientation of circuit unit, also liquid crystal molecule can be damaged, although the number of packages that these phenomenons occur is few but is also occurring.
In addition, the power consumption in order to reduce liquid crystal display panel, the driving voltage of liquid crystal material tends to reducing, and IC is driven therewith Breakdown voltage also tend to reduce.Recently, it is desirable to electrostatic pressure will be peeled off and controlled in the range of+0.7kV~-0.7kV.
Therefore, it is high because peeling off electrostatic pressure during surface protection film in order to prevent from being peeled off from the optical film as adherend A kind of caused defect, it is thus proposed that surface protection film, it uses containing peeling off the antistatic of electrostatic pressure for reducing The adhesive layer of agent.
For example, in patent document 1, disclosing a kind of use by alkyl trimethyl ammonium salt, the acrylic polymer of hydroxyl The surface protection film of compound, the binding agent of PIC composition.
In addition, in patent document 2, disclose a kind of by acroleic acid polymerization that ionic liquid and acid number are less than 1.0 The adhesive composition of thing composition and the bonding sheet class of said composition is used.
In addition, in patent document 3, disclose it is a kind of by acrylate copolymer, polyether polyols, by the moon from The adhesive composition of alkali metal salt that sub- adsorptivity compound treatment is crossed composition and the surface protection of said composition is used Film.
In addition, in patent document 4, it is 0 by ionic liquid, alkali metal salt, glass transition temperature to disclose a kind of The adhesive composition of the polymer composition below DEG C and the surface protection film of said composition is used.
In addition, in patent document 5,6, disclose the admixtured polyether in the adhesive layer of surface protection film and be modified poly- silica The technology contents of alkane.
In above-mentioned patent document 1~4, antistatic additive is added with inside adhesive layer, but the thickness of adhesive layer is thicker, And over time, the amount of the adherend movement that antistatic additive is fitted from adhesive layer to surface protection film can be more It is many.In addition, in the optical film of LR (Low Reflective) Polarizer, AG (Anti Glare)-LR Polarizers etc., due to Anti-pollution treatment is applied with to optical film surface using polysiloxane compound or fluoride etc., therefore, when from as being glued When the surface protection film that the optical film is used is peeled off on the optical film of attached body, peel off electrostatic pressure and uprise.
In addition, as described in patent document 5,6, when Siloxane-Oxyalkylene Copolymers are mixed with adhesive layer, it is difficult to right The cohesive force of surface protection film is finely adjusted.Further, since polyether modified siloxane is mixed with adhesive layer, therefore, when When coating, the condition of dry binder composition change on base material film, the adhesive layer table formed on surface protection film The characteristic in face knifeedge changes.Also, from from the viewpoint of protection optical film surface, it is impossible to make the thickness of adhesive layer It is set as very thin.Therefore, thickness according to adhesive layer is, it is necessary to increase the Siloxane-Oxyalkylene Copolymers of mixing in adhesive layer Addition, as a result easily pollutes adherend surface, and the cohesive force with the time and the contaminative to adherend change.
In recent years, along with the popularization of 3D displays (autostereoscopic display), there is the table in optical films such as Polarizers The situation of face laminating FPR (patterned retarder, Film Patterned Retarder) film.Peel off and used in optics such as Polarizers After the surface protection film that the surface of film is fitted, FPR films of fitting.But, when the optical film surface of Polarizer etc. is protected by surface When binding agent that cuticula is used, antistatic additive pollute, there is a problem of being difficult to be bonded FPR films.Therefore, to being used in the purposes Surface protection film for, it is desirable to its pollution to adherend is few.
On the other hand, in some liquid crystal panel manufacturers, as surface protection film to the contaminative of adherend Evaluation method, is to adopt with the following method：Surface protection film to being fitted on the optical film of Polarizer etc. is once peeled off, Be mixed into the state of bubble and fitted again, to fitting again after object heat under prescribed conditions, then peel off table Surface protective film simultaneously observes the surface of adherend.In this evaluation method, even if the surface contamination of adherend is micro, If there is adherend surface contamination between the part that the part of bubble contacts with the binder phase of surface protection film is mixed into Difference, then can remain as bubble impression (sometimes referred to as " bubble stains ").Accordingly, as the pollution to adherend surface The evaluation method of property, the evaluation method that can be strict.In recent years, even being judged with this strict evaluation method Result, it is also desirable to the surface protection film being had no problem to the surface contamination of adherend aspect.But current situation is, In the surface protection film for having used the adhesive layer containing antistatic additive for being proposed in the past, it is difficult to solve the problem.
Accordingly, it would be desirable to a kind of surface protection film used in optical film, its pollution to adherend it is considerably less and There is no rheological parameters' change with time to the contaminative of adherend (passage does not change over time).Furthermore, it is desirable to will be from adherend The surface protection film that stripping electrostatic pressure during upper stripping suppresses low.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2005-131957 publications
Patent document 2：Japanese Unexamined Patent Publication 2005-330464 publications
Patent document 3：Japanese Unexamined Patent Publication 2005-314476 publications
Patent document 4：Japanese Unexamined Patent Publication 2006-152235 publications
Patent document 5：Japanese Unexamined Patent Publication 2009-275128 publications
Patent document 6：No. 4537450 publications of Japanese Patent Publication No.
The content of the invention
The invention problem to be solved
Studied intensively to solve the problem, the present inventor etc..
The rheological parameters' change with time for reducing for the pollution reduced to adherend and also antistatic property is speculated, it is necessary to reduce It is the addition of the antistatic additive of the reason for polluting adherend.But, when reduce antistatic additive addition when, can cause from Stripping electrostatic pressure when surface protection film is peeled off in adherend is uprised.The present inventor etc. have studied and add not increasing antistatic additive Lower suppress to be peeled off from adherend the method for peeling off electrostatic pressure during surface protection film in the case of the absolute magnitude of dosage. Its result finds, antistatic additive is added not in adhesive composition and is mixed and is formed adhesive layer, but coating is viscous Knot agent composition and be dried and after laminating adhesive layer, by adhesive layer surface assigned appropriate antistatic additive into Point, can lower suppress to be peeled off from the optical film as adherend stripping electrostatic pressure during surface protection film, and base The present invention is completed in above-mentioned discovery.
The present invention be exactly in view of the foregoing and complete, its problem be provide a kind of pollution to adherend less, And the Antistatic surface with the excellent antistripping antistatic property without deterioration (passage is not deteriorated over time) is protected Cuticula.
The method for solving problem
In order to solve above-mentioned problem, the technological thought of Antistatic surface diaphragm of the present invention is, in applied adhesive group Compound and be dried and after laminating adhesive layer, the surface of the adhesive layer is assigned at appropriate 20 DEG C be liquid poly- silicon Oxygen alkane (silicone, silicone) class compound and antistatic additive, thereby, it is possible to lower suppress the contaminative to adherend, And stripping electrostatic pressure when can lower suppress to be peeled off from the optical film as adherend.
In order to solve above-mentioned problem, the present invention provides a kind of Antistatic surface diaphragm, and it is to sequentially pass through following operations (1)~(2) are fabricated by,
Operation (1)：Formed by adhesive composition structure on the one side of the base material film being made up of the resin with the transparency Into adhesive layer operation,
The adhesive composition includes：Carbon number containing (A) alkyl is (methyl) acrylate monomer of C4~C18 In at least one and carboxylic selected from the copolymerisable monomer by (B) hydroxyl as copolymerisable monomer group, (C) Copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl monomer Or at least one copolymer in the copolymerisable monomer group that is constituted of (methyl) alkyl acrylate monomer containing alkoxy Acrylic polymer；It is also mutual including isocyanate compound more than (F) two function, (G) crosslinking accelerator, (H) keto-enol Tautomeric compound,
Operation (2)：The stripping film of the peeling agent layer containing antistatic additive will be laminated on resin film one side, by institute The operation that peeling agent layer is fitted on the surface of foregoing adhesives layer is stated,
It by containing the remover using dimethyl polysiloxane as main component, at 20 DEG C is liquid that foregoing peeling agent layer is Polysiloxanes (silicone) the class compound of body and the resin combination of foregoing antistatic agents are formed, foregoing adhesives layer Stripping electrostatic pressure is ± below 0.6kV.
Additionally, it is preferred that the copolymerisable monomer of foregoing (B) hydroxyl be selected from by (methyl) acrylic acid 8- hydroxyls monooctyl ester, The own ester of (methyl) acrylic acid 6- hydroxyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates, N- hydroxyls The compound group that (methyl) acrylamide, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide are constituted In at least one more than.
Additionally, it is preferred that foregoing (C) carboxylic copolymerisable monomer is selected from by (methyl) acrylic acid, (methyl) acrylic acid Carboxylic ethyl ester, (methyl) carboxypentyl acrylate, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloyl Epoxide propyl group hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloxy second Base butanedioic acid, 2- (methyl) acryloyl-oxyethyls maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) third It is more than at least one in the compound group that alkene trimethylammonium tetrahydrophthalic acid is constituted.
Additionally, it is preferred that (D) polyalkylene glycol mono (methyl) acrylate monomer is selected from polyalkylene glycol mono (first Base) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl PAG (methyl) acrylate In at least one more than.
Additionally, it is preferred that foregoing acrylic polymer as foregoing copolymerisable monomer group contain foregoing (E) not hydroxyl and It is more than at least one in nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxy.
In addition, for isocyanate compound more than foregoing (F) two function, preferably as two functional isocyanates Compound is non-ring type aliphatic isocyanates compound and diisocyanate cpd is reacted with diol compound and is generated Compound, wherein,
Aliphatic diisocyanate as diisocyanate cpd, be selected from by tetramethylene diisocyanate, Pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, the isocyanic acid of lysine two One kind in the compound group that ester is constituted；
As diol compound it is selected from by 2- methyl 1,3- propane diols, 2,2- dimethyl -1,3- propane diols, 2- first Base -2- propyl group -1,3- propane diols, 2- ethyl -2- butyl -1,3- propane diols, 3- methyl isophthalic acids, 5- pentanediols, 2,2- dimethyl -1, One kind in the compound group that ammediol monohydroxy pivalate, polyethylene glycol, polypropylene glycol are constituted,
As trifunctional isocyanates compound, preferably the isocyanuric acid ester of hexamethylene diisocyanate compound, The isocyanuric acid ester of IPDI compound, the addition product of hexamethylene diisocyanate compound, different Fo Er The addition product of ketone diisocyanate cpd, the biuret of hexamethylene diisocyanate compound, isophorone diisocyanate The biuret of ester compounds, the isocyanuric acid ester of tolunediisocyanate compound, xylylene diisocyanate compound Isocyanuric acid ester, the isocyanuric acid ester of hydrogenated xylylene diisocyanate cpd, tolunediisocyanate compound plus Into thing, the addition product of xylylene diisocyanate compound, hydrogenated xylylene diisocyanate cpd addition product.
In addition, in foregoing adhesives composition, preferably comprising the polyether modified siloxane chemical combination that (I) HLB value is 7~15 Thing.
Additionally, it is preferred that the polysiloxane-based compound in foregoing peeling agent layer is Siloxane-Oxyalkylene Copolymers.
Additionally, it is preferred that the foregoing antistatic agents in foregoing peeling agent layer are alkali metal salt.
In addition, in order to solve above-mentioned problem, the present invention provides a kind of Antistatic surface diaphragm, its be by adhesive layer and The remover film of the peeling agent layer containing antistatic additive is laminated on the one side of resin film, so that the adhesive layer and institute The mode that peeling agent layer is in contact is stated, the one side stacked gradually in the base material film being made up of the resin with the transparency is formed, institute State adhesive layer by the carbon number containing (A) alkyl for (methyl) acrylate monomer of C4~C18 in it is at least one, with And gather selected from the copolymerisable monomer by (B) hydroxyl as copolymerisable monomer group, (C) carboxylic copolymerisable monomer, (D) Alkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl monomer or the (first containing alkoxy Base) at least one copolymer in the copolymerisable monomer group that is constituted of alkyl acrylate monomer acrylic polymer structure Into, the stripping film is to be laminated the peeling agent layer containing antistatic additive on the one side of resin film to form,
It by containing the remover using dimethyl polysiloxane as main component, at 20 DEG C is liquid that foregoing peeling agent layer is The polysiloxane-based compound of body and the resin combination of antistatic additive are formed, the stripping electrostatic pressure of foregoing adhesives layers for ± Below 0.6kV.
Additionally, it is preferred that the polysiloxane-based compound in foregoing peeling agent layer is Siloxane-Oxyalkylene Copolymers.
Additionally, it is preferred that the foregoing antistatic agents in foregoing peeling agent layer are alkali metal salt.
In addition, the present invention provides a kind of optical film, its above-mentioned Antistatic surface diaphragm of laminating is formed.
In addition, the present invention provides a kind of optical component, its above-mentioned Antistatic surface diaphragm of laminating is formed.
Invention effect
Pollution of the Antistatic surface diaphragm of the invention to adherend is few, and to the low stain of adherend without warp Shi Bianhua (will not over time be elapsed and changed).In addition, based on the present invention, using the teaching of the invention it is possible to provide even one kind is attached body surface Face is that LR Polarizers, AG-LR Polarizers etc. are used by the optics that polysiloxane compound, fluoride etc. carried out anti-pollution treatment Film, it is also possible to lower suppress the stripping electrostatic pressure occurred when peeling off Antistatic surface diaphragm from adherend, and have Antistatic surface diaphragm without deterioration and excellent antistripping antistatic property.
Based on Antistatic surface diaphragm of the invention, optical film surface can be reliably protected, therefore, it is possible to realize The raising of production efficiency and the raising of yield rate.
Brief description of the drawings
Fig. 1 is the constructed profile of Antistatic surface diaphragm of the invention.
Fig. 2 is the profile for representing the state that stripping film is peeled from Antistatic surface diaphragm of the invention.
Fig. 3 is the profile of the embodiment for representing optical component of the invention.
The explanation of reference
1 ... base material film；2 ... adhesive layers；3 ... resin films；
4 ... peeling agent layers；5 ... stripping films；
It is the polysiloxane-based compound and antistatic additive of liquid at 7 ... 20 DEG C；
8 ... adherend (optical component)；10 ... Antistatic surface diaphragms；
11 ... peel the Antistatic surface diaphragm after stripping film；
20 ... the optical components for having fitted Antistatic surface diaphragm.
Specific embodiment
Below, the present invention is described in detail based on implementation method.
Fig. 1 is the constructed profile of Antistatic surface diaphragm of the invention.The Antistatic surface diaphragm 10, is saturating The surface of the one side of bright base material film 1 is formed with adhesive layer 2.Stripping film 5 is fitted with the surface of the adhesive layer 2, the stripping It is to form peeling agent layer 4 on the surface of resin film 3 to form from film 5.
As the base material film 1 used in Antistatic surface diaphragm 10 of the invention, using by with the transparency and scratching Property resin constitute base material film.Thereby, it is possible to Antistatic surface diaphragm to be fitted in the optical section as adherend Implement the visual examination of optical component in the state of part.As base material film 1 by the film that is constituted with transparent resins, preferably make With polyethylene terephthalate, PEN, polyethylene glycol isophthalate (polyethylene Isophthalate), the polyester film such as polybutylene terephthalate (PBT).As long as there is required intensity as the base material film and have Optics adaptability, can also use the film being made up of other resins in addition to polyester film.Base material film 1 can not drawn Stretch film, or be subjected to the film being stretched uniaxially or biaxially.Alternatively, it is also possible to by the stretching ratio of stretched film, stretching The orientation angles of the direction of principal axis formed along with crystallization of film are controlled in particular value.
For the thickness of the base material film 1 used in Antistatic surface diaphragm 10 of the invention, not special limit It is fixed, for example, it is preferable to be 12~100 μm or so of thickness；If 20~50 μm or so of thickness is then easily operated, therefore more excellent Choosing.
In addition, as needed, can have on the face of face opposition side of adhesive layer 2 in the formation of base material film 1, it is provided for preventing The only stain-proofing layer of surface contamination, antistatic layer, the hard conating etc. for preventing scratch.In addition, on the surface of base material film 1, it is also possible to real The easily bondingization treatment such as the surface that apply is carried out based on corona discharge is modified, the smearing of silane coupling agent.
In addition, for the adhesive layer 2 used in Antistatic surface diaphragm 10 of the invention, as long as in adherend Surface on be bonded, using can simply be peeled after finishing and be difficult to pollute adherend adhesive layer, and It is not particularly limited, but in view of durability after being fitted on optical film etc., generally using makes (methyl) acrylate common The acrylic adhesive layer of polymers crosslinking.
In particular it is preferred that the host of acrylic adhesive be by the carbon number containing (A) alkyl be C4~C18 At least one in (methyl) acrylate monomer and selected from being total to by (B) hydroxyl as copolymerisable monomer group Polycondensation monomer, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl And in the copolymerisable monomer group that nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxy is constituted The adhesive layer that the acrylic polymer of at least one copolymer is constituted.
More preferably by also containing isocyanates chemical combination more than (F) two function in addition to foregoing acrylic polymer The adhesive layer that the adhesive composition of thing, (G) crosslinking accelerator and (H) ketone-enol tautomers compound is constituted.
It is (methyl) acrylate monomer of C4~C18 as the carbon number of (A) alkyl, can enumerates：(methyl) third Olefin(e) acid butyl ester, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptan Ester, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) acrylic acid nonyl Ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane Base ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) acrylic acid tetradecane base ester, (first Base) acrylic acid pentadecane base ester, (methyl) aliphatic acrylate, (methyl) acrylic acid heptadecane base ester, (methyl) propylene Sour stearyl, (methyl) myristyl ester, the different tetradecane base ester of (methyl) acrylic acid, (methyl) acrylic acid spermaceti Ester, (methyl) acrylic acid isohexadecane base ester, (methyl) stearyl acrylate acyl ester, (methyl) acrylic acid isooctadecane base ester etc..
When the total amount of acrylic polymer of copolymer is set as 100 weight portion, the preferred carbon atom of (A) alkyl Number is 50~95 weight portions for the content of (methyl) acrylate monomer of C4~C18.
As the copolymerisable monomer of (B) hydroxyl, can enumerate：(methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) propylene (methyl) dihydroxypropyls such as the sour own ester of 6- hydroxyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates Alkyl esters；N- hydroxyls (methyl) acrylamide, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide etc. (methyl) acrylic amide containing hydroxyl etc..
It is preferred that the copolymerisable monomer of above-mentioned hydroxyl is selected from by (methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) propylene The sour own ester of 6- hydroxyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates, N- hydroxyls (methyl) acryloyl At least one in the compound group that amine, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide are constituted More than.
When the total amount of acrylic polymer of copolymer is set as 100 weight portion, preferably foregoing (B) hydroxyl The content of copolymerisable monomer is 0.1~10 weight portion.
It is preferred that (C) carboxylic copolymerisable monomer be selected from by (methyl) acrylic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloxy third Base hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloyl-oxyethyl amber Acid, 2- (methyl) acryloyl-oxyethyls maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloyl-oxy It is more than at least one in the compound group that base ethyl tetrahydrophthalic acid is constituted.
When the total amount of acrylic polymer of copolymer is set as 100 weight portion, preferably foregoing (C) is carboxylic The content of copolymerisable monomer is 0~1.0 weight portion.Adhesive composition in adhesive layer of the invention can also not include (C) carboxylic copolymerisable monomer.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, as long as PAG have it is many It is the compound of (methyl) acrylate that a hydroxyl in individual hydroxyl is esterified.It is poly- because (methyl) is acrylate-based Conjunction property base, therefore, it is possible to carry out copolymerization with host polymer.Other hydroxyls, can both keep the state of OH, it is also possible to as first The alkyl ether of ether, ether etc., or saturated carboxylic acid esters such as acetate etc. can be turned into.
The alkylidene having as PAG, can enumerate ethylidene, propylidene, butylidene etc., but not It is defined in these.PAG can also be the two or more poly- alkylene in polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc. The copolymer of base glycol.As the copolymer of PAG, polyethylene glycol propane diols, polyethylene glycol can be enumerated Butanediol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol propane diols-polytetramethylene glycol etc., the copolymer can be block copolymerization Thing, random copolymer.
It is preferred that constituting the alkylene oxide of polyalkylene glycol chain in (D) polyalkylene glycol mono (methyl) acrylate monomer The averaged repeating numbers of (alkylene oxide) are 3~14.So-called " averaged repeating numbers of alkylene oxide ", refer to (D) polyalkylene Alkylene oxide unit weight in contained " polyalkylene glycol chain " part in the molecular structure of glycol list (methyl) acrylate monomer Multiple average.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, polyalkylene glycol mono (first is preferably selected from Base) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl PAG (methyl) acrylate In at least one more than.
More specifically, can enumerate：Polyethylene glycol-mono- (methyl) acrylate, polypropylene glycol-mono- (methyl) acrylic acid Ester, polytetramethylene glycol-mono- (methyl) acrylate, polyethylene glycol propane diols-mono- (methyl) acrylate, polyethylene glycol fourth Glycol-mono- (methyl) acrylate, polypropylene glycol-polytetramethylene glycol-mono- (methyl) acrylate, polyethylene glycol propane diols-poly- Butanediol-mono- (methyl) acrylate；Methoxy poly (ethylene glycol)-(methyl) acrylate, methoxyl group polypropylene glycol-(methyl) third Olefin(e) acid ester, methoxyl group polytetramethylene glycol-(methyl) acrylate, methoxypolyethylene glycol-polypropylene glycol-(methyl) acrylate, Methoxypolyethylene glycol-polytetramethylene glycol-(methyl) acrylate, methoxyl group-polypropylene glycol-polytetramethylene glycol-(methyl) acrylic acid Ester, methoxypolyethylene glycol-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate；Ethyoxyl polyethylene glycol-(methyl) propylene Acid esters, ethyoxyl polypropylene glycol-(methyl) acrylate, ethyoxyl polytetramethylene glycol-(methyl) acrylate, ethyoxyl-poly- second Glycol-polypropylene glycol-(methyl) acrylate, ethyoxyl-polyethylene glycol butanediol-(methyl) acrylate, ethyoxyl- Polypropylene glycol-polytetramethylene glycol-(methyl) acrylate, ethyoxyl-polyethylene glycol propane diols-polytetramethylene glycol-(methyl) propylene Acid esters etc..
When the total amount of acrylic polymer of copolymer is set as 100 weight portion, preferably foregoing (D) polyalkylene The content of glycol list (methyl) acrylate monomer is 0~50 weight portion.Adhesive composition in adhesive layer of the invention (D) polyalkylene glycol mono (methyl) acrylate monomer can also not included.
It is preferred that foregoing acrylic polymer contain as foregoing copolymerisable monomer group, (E) not hydroxyl and it is nitrogenous It is more than at least one in vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxy.
In (E), as (E-1) nitrogenous vinyl monomer, can enumerate：Vinyl monomer containing amido link, contain There are the vinyl monomer of amino, the vinyl monomer with nitrogenous heterocycle structure etc..More specifically, can enumerate：N- second Alkenyl -2-Pyrrolidone, NVP, methyl ethylene pyrrolidones, N- vinylpyridines, N- vinylpiperidines Ketone, N- vinyl pyrimidines, N- vinyl piperazine, N- vinylpyrazines, N- vinyl pyrroles, N- vinyl imidazoles, N- vinyl Oxazole, N- polyvinyl morpholinones, N- caprolactams, N- vinyl lauric lactams etc. with N- vinyl substitution it is miscellaneous The ring-type nitrogen vinyl compound of ring structure；N- (methyl) acryloyl morpholine, N- (methyl) acryloylpiperazines, N- (methyl) Propylene acyl group aziridine, N- (methyl) acryloyl groups azetidine, N- (methyl) acryloyl groups pyrrolidines, N- (methyl) acryloyl group Piperidines, N- (methyl) acryloyl groups azepan, N- (methyl) acryloyl group Azacyclooctane etc. with N- (methyl) third The ring-type nitrogen vinyl compound of the heterocycle structure of enoyl- substitution；N- N-cyclohexylmaleimides, N-phenylmaleimide Deng with the ring-type nitrogen vinyl compound that the heterocycle structure of nitrogen-atoms and vinyl-based unsaturated bond is contained within ring；(methyl) Acrylamide, N- methyl (methyl) acrylamide, N- isopropyls (methyl) acrylamide, the N- tert-butyl groups (methyl) acrylamide etc. (methyl) acrylamide of unsubstituted or monoalkyl substitution；N, N- dimethyl (methyl) acrylamide, N, N- diethyl (first Base) acrylamide, N, N- dipropyl acrylamide, N, N- diisopropyls (methyl) acrylamide, N, N- dibutyl (methyl) third Acrylamide, N- ethyl-N-methyls (methyl) acrylamide, N- Methyl-N-propyls (methyl) acrylamide, N- methyl-N-isopropyls third The dialkyl group such as base (methyl) acrylamide replace (methyl) acrylamide；N, N- dimethylaminomethyl (methyl) acrylate, N, N- dimethyl aminoethyl (methyl) acrylate, N, N- dimethylaminopropyls (methyl) acrylate, N, N- dimethyl Amino isopropyl (methyl) acrylate, N, N- dimethrlaminobutyls (methyl) acrylate, N, N- diethylamino methyl (methyl) acrylate, N, N- diethylaminos ethyl (methyl) acrylate, N- ethyl-N-methylaminos ethyl (methyl) third Olefin(e) acid ester, N- methyl-N-propylaminos ethyl (methyl) acrylate, N- methyl-N-isoproylaminos ethyl (methyl) propylene The dialkyl aminos such as acid esters, N, N- Dibutylaminoethyls (methyl) acrylate, t-butylamino ethyl (methyl) acrylate Base (methyl) acrylate；N, N- dimethylaminopropyl (methyl) acrylamide, N, N- diethyl amino propyls (methyl) third Acrylamide, N, N- dipropylaminos propyl group (methyl) acrylamide, N, N- diisopropylaminoethyls propyl group (methyl) acrylamide, N- Ethyl-N-methylamino propyl group (methyl) acrylamide, N- methyl-N-propylaminos propyl group (methyl) acrylamide, N- methyl- The N of N- isopropylaminopropyls (methyl) acrylamide etc., N- dialkyl group substituted-amino propyl group (methyl) acrylamide；N- ethene The N- vinylcarboxylic acid amide types such as base formamide, N- vinyl acetamides, N- vinyl-N-methylacetaniides；N- methoxy methyls Base (methyl) acrylamide, N- ethoxyethyl groups (methyl) acrylamide, N- butoxymethyls (methyl) acrylamide, two acetone (methyl) acrylic amides such as acrylamide, N, N- di-2-ethylhexylphosphine oxides (methyl) acrylamide；The unsaturation carboxylic such as (methyl) acrylonitrile Sour nitrile；Deng.
As (E-1) nitrogenous vinyl monomer, preferred not hydroxyl, more preferably not hydroxyl and carboxyl.As this Monomer, the monomer being preferably illustrated above, for example：Containing N, N- dialkyl group substituted-amino, N, N- dialkyl group substituted amidos Acrylic monomer；The N- vinyl such as NVP, N- caprolactams, N- vinyl -2- piperidones Substituted lactams class；N- (methyl) acryloyl groups such as N- (methyl) acryloyl morpholine, N- (methyl) acryloyl group pyrrolidines take For cyclic amine.
In (E), as (methyl) alkyl acrylate monomer of (E-2) containing alkoxy, can enumerate：(methyl) propylene Sour 2- methoxy acrylates, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid 2- propoxy ethyls, (methyl) acrylic acid 2- isopropoxyethyl cyanoacrylates, (methyl) acrylic acid 2- butoxyethyls, (methyl) acrylic acid 2- methoxyl groups propyl ester, (methyl) acrylic acid 2- ethyoxyls propyl ester, (methyl) acrylic acid 2- propoxyl group propyl ester, (methyl) acrylic acid 2- isopropoxies propyl ester, (methyl) acrylic acid 2- butoxy propyl ester, (methyl) acrylic acid 3- methoxyl groups propyl ester, (methyl) acrylic acid 3- ethyoxyls propyl ester, (methyl) acrylic acid 3- Propoxyl group propyl ester, (methyl) acrylic acid 3- isopropoxies propyl ester, (methyl) acrylic acid 3- butoxy propyl ester, (methyl) acrylic acid 4- Methoxybutyl, (methyl) acrylic acid 4- Ethoxybutyls, (methyl) acrylic acid 4- propoxyl group butyl ester, 4- is different for (methyl) acrylic acid Propoxyl group butyl ester, (methyl) acrylic acid 4- butoxy butyl esters etc..
These (methyl) alkyl acrylate monomers containing alkoxy, with the alkyl in (methyl) alkyl acrylate The structure that atom is replaced by alkoxy.
When the total amount of acrylic polymer of copolymer is set as 100 weight portion, preferably (E-1) not hydroxyl and The content of (methyl) alkyl acrylate monomer of nitrogenous vinyl monomer or (E-2) containing alkoxy is 0~20 weight portion. For (E-1) not (methyl) alkyl acrylate monomer of hydroxyl and nitrogenous vinyl monomer and (E-2) containing alkoxy, Both can respectively can also simultaneously with two or more using one kind.Can not also in the adhesive composition of adhesive layer of the invention Comprising (E) not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxy.
As isocyanate compound more than (F) two function, as long as at least there is two or more in being selected from a molecule Isocyanates (NCO) base polyisocyanate compounds in it is at least one or two more than.PIC chemical combination Thing includes aliphatic category isocyanates, aromatic series kind isocyanate, non-ring type kind isocyanate, ester ring type kind isocyanate decile Class, the present invention can be any kind therein.As the specific example of polyisocyanate compounds, can enumerate：Six methylenes The fat such as group diisocyanate (HDI), IPDI (IPDI), trimethyl hexamethylene diisocyanate (TMDI) Fat same clan isocyanate compound；Methyl diphenylene diisocyanate (MDI), xylylene diisocyanate (XDI), hydrogenation of benzene Diformazan group diisocyanate (H6XDI), dimethyl diphenylene diisocyanate (TOID), toluene di-isocyanate(TDI) (TDI) etc. Aromatic series kind isocyanate compound.
As isocyanate compound more than trifunctional, can enumerate：Two functional isocyanate compounds are (in a molecule In there are the compounds of two NCO bases) biuret modified body or isocyanurate-modified body, with trimethylolpropane (TMP) Or the addition product of polyalcohol (at least having more than three compounds of OH bases in a molecule) more than the trivalent such as glycerine is (polynary Alcohol modified body) etc..
As isocyanate compound more than (F) two function, can only with (F-1) trifunctional isocyanates compound, Or only with (F-2) two functional isocyanate compound.Alternatively, it is also possible to and with (F-1) trifunctional isocyanates compound (F-2) two functional isocyanate compound.
Also, as (F-1) the trifunctional isocyanates compound used in the present invention, preferably include selected from (F-1-1) It is at least one above and selected from (F-1-2) the second aromatic series kind isocyanate in first aliphatic category isocyanate compound group It is more than at least one in compound group, wherein, (F-1-1) first aliphatic category isocyanate compound group is sub- by six The isocyanuric acid ester of methyl diisocyanate compound, the isocyanuric acid ester of IPDI compound, six methylenes The addition product of group diisocyanate compound, the addition product of IPDI compound, the isocyanic acid of hexa-methylene two The biuret of ester compounds, the biuret of IPDI compound are constituted；(F-1-2) second aromatic series Kind isocyanate compound group is isocyanuric acid ester, the xylylene diisocyanate chemical combination by tolunediisocyanate compound The isocyanuric acid ester of thing, the isocyanuric acid ester of hydrogenated xylylene diisocyanate cpd, tolunediisocyanate compound Addition product, the addition product of xylylene diisocyanate compound, the addition of hydrogenated xylylene diisocyanate cpd Thing is constituted.It is preferred that and with (F-1-1) the first aliphatic category isocyanate compound group and (F-1-2) second fragrant same clan's isocyanide Ester compound group.In the present invention, as (F-1) trifunctional isocyanates compound, by and be selected from (F-1-1) first It is at least one above and selected from (F-1-2) the second aromatic series kind isocyanate chemical combination in aliphatic category isocyanate compound group More than at least one in thing group, can further improve the balance of the cohesive force in low speed stripping area and high speed stripping area Property.
Additionally, it is preferred that (F-1) trifunctional isocyanates compound contains selected from foregoing (F-1-1) first aliphatic category isocyanide It is at least one above and selected from foregoing (F-1-2) second aromatic series kind isocyanate compound group in ester compound group More than at least one, its total amount is 0.5~5.0 weight portion relative to the aforementioned copolymer of 100 weight portions.In addition, as choosing From in (F-1-1) first aliphatic category isocyanate compound group at least one more than with selected from (F-1-2) second aromatic series At least one blending ratio above in kind isocyanate compound group, is calculated preferably (F-1-1) with weight ratio meter:(F-1-2) 10%:90%~90%:In the range of 10%.
Also, (F-2) the two functional isocyanate compound used as the present invention, preferably non-ring type aliphatic isocyanide Ester compound and the compound that to be diisocyanate cpd react and generate with diol compound.
For example, when with formula " O=C=N-X-N=C=O " (wherein, X is for divalent group) expression diisocyanate chemical combination Thing, when representing diol compound with formula " HO-Y-OH " (wherein, Y be divalent group), as diisocyanate cpd and two Alcoholic compound reacts generated compound, for example, the compound that following formula Z are represented can be enumerated.
[formula Z]
O=C=N-X- (NH-CO-O-Y-O-CO-NH-X) n-N=C=O
Here, n is more than 0 integer.When n is 0, formula Z is expressed as " O=C=N-X-N=C=O ".As two officials Can non-ring type aliphatic isocyanates compound can also include compound that n in formula Z is 0 (relative to diol compound not The diisocyanate cpd of reaction), preferably as must composition contain the compound of the integer that n is more than 1.Two functions are acyclic The mixture that multiple compounds that formula aliphatic isocyanates compound can also be differed by the n in formula Z are constituted.
The diisocyanate cpd that formula " O=C=N-X-N=C=O " is represented, is aliphatic diisocyanate.It is preferred that X is the aliphatic divalent group of non-ring type.As foregoing aliphatic diisocyanate, preferably by selected from by tetramethylene two Isocyanates, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, bad ammonia One or more in the compound group that sour diisocyanate is constituted are constituted.
Diol compound shown in formula " HO-Y-OH " is aliphatic diol.It is preferred that Y is the aliphatic divalent base of non-ring type Group.As foregoing glycols compound, preferably by selected from by 2- methyl 1,3-PD, 2,2- dimethyl -1,3- the third two Alcohol, 2- methyl-2-propyl -1,3- propane diols, 2- ethyl -2- butyl -1,3- propane diols, 3- methyl isophthalic acids, 5- pentanediols, 2,2- bis- One or two in the compound group that methyl-1,3-propanediol monohydroxy pivalate, polyethylene glycol, polypropylene glycol are constituted More than constitute.
It is preferred that the weight ratio of foregoing (F-1) trifunctional isocyanates compound and (F-2) two functional isocyanate compound (F-1/F-2) it is 1~90.It is more than preferably foregoing (F) two function different relative to 100 weight portion foregoing acrylic polymer Cyanate esters are 0.1~10 weight portion.
Using polyisocyanate compounds as in the case of crosslinking agent, (G) is as long as the crosslinking accelerator of metallo-chelate It is the material of reaction (cross-linking reaction) function as catalyst to aforementioned copolymer and crosslinking agent, Ke Yiju Go out：Aminated compounds, metallo-chelate, organo-tin compound, organo-lead compound, the organic zinc compound of tertiary amine etc. etc. are organic Metallic compound etc..In the present invention, metallo-chelate, organo-tin compound are preferably used as crosslinking accelerator.
It is compound that more than one multidentate ligand L is bonded to central metal atom M as metallo-chelate. Metallo-chelate can both have and can also not have the more than one monodentate ligand X being bonded on metallic atom M.For example, When the formula of the metallo-chelate that metallic atom M is is with M (L)m(X)nDuring expression, m >=1, n >=0.When m is more than 2, m Individual L both can be that identical part can also be different part.When n is more than 2, the X of n both can be that identical is matched somebody with somebody Body can also be different part.
As metallic atom M, Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, Sn etc. can be enumerated.
As multidentate ligand L, can enumerate：Methyl acetoacetate, ethyl acetoacetate, acetoacetate monooctyl ester, acetyl second The 'beta '-ketoester of sour grease, lauryl acetoacetate, acetoacetate stearoyl ester etc.；Acetylacetone,2,4-pentanedione (alias：2,4- pentanediones), 2, The beta-diketon of 4- acetyl butyryls, benzoyl acetone etc..They are ketone-enol tautomers compounds, also may be used in multidentate ligand L Being enolate (for example, acetylacetonate) that enol carries out deprotonation.
As monodentate ligand X, the halogen atoms such as chlorine atom, bromine atoms, valeryl, caproyl, 2- ethyl hexanoyls can be enumerated The acyloxy such as base, caprylyl, pelargonyl group, capryl, Lauroyl, stearyl, methoxyl group, ethyoxyl, positive propoxy, isopropyl Alkoxies such as epoxide, butoxy etc..
As the specific example of metallo-chelate, can enumerate：Three (2,4- pentanediones) iron (III), praseodynium iron, Praseodynium titanium, praseodynium ruthenium, diacetyl acetone zinc, praseodynium aluminium, four acetylacetone,2,4-pentanedione zirconiums, three (2,4- oneself two Ketone) iron (III), double (2,4- acetyl butyryls) zinc, three (2,4- acetyl butyryls) titaniums, three (2,4- acetyl butyryls) aluminium, four (2,4- acetyl butyryls) Zirconium etc..
As organo-tin compound, can enumerate：Dialkyl tin oxide, the soap of dialkyl tin, the fat of stannous Fat hydrochlorate etc..In the past, dibutyltin compound has in most cases been used, but the toxicity of organo-tin compound is asked in recent years Topic is noted, and tributyl tin (TBT) particularly contained in dibutyltin compound is also to make us load as endocrine disruptors The heart.Set out from a security point, preferably the chain alkyl tin compound of dioctyl tin compound etc..As specific organotin Compound, can enumerate di-n-octyltin oxide, tin dilaurate dioctyl tin etc..Although Sn chemical combination can also be used temporarily Thing, but in view of require the trend of safety in utilization material higher in the future, preferably use safe Al, Ti, Fe in Sn Deng metallo-chelate.
As the metallo-chelate in adhesive composition of the invention, preferably containing selected from by aluminium chelate compound, titanium It is more than at least one in the group that chelate, iron chelate, tin chelate (wherein not comprising TBT) are constituted.
Relative to 100 weight portion copolymers, the preferably content of the crosslinking accelerator of (G) metallo-chelate is 0.001~0.5 Weight portion.
As (H) ketone-enol tautomers compound, can enumerate：Methyl acetoacetate, ethyl acetoacetate, second The 'beta '-ketoester of ethyl acetoacetic acid monooctyl ester, acetoacetate grease, lauryl acetoacetate, acetoacetate stearoyl ester etc.；Acetylacetone,2,4-pentanedione, 2, The beta-diketon of 4- acetyl butyryls, benzoyl acetone etc..They are in the binding agent combination using polyisocyanate compounds as crosslinking agent In thing, closed by the NCO with crosslinking agent, can suppress to coordinate adhesive composition after crosslinking agent The excessive rising of viscosity or the phenomenon of gelation, can extend the storage period of adhesive composition.
Relative to the copolymer of 100 weight portions, preferably the content of (H) ketone-enol tautomers compound be 0.1~ 200 weight portions.
(H) there is ketone-enol tautomers compound the suppression opposite with the crosslinking accelerator of (G) metallo-chelate to hand over The effect of connection, it is therefore preferable that suitably crosslinking of setting (H) the ketone-enol tautomers compound phase for (G) metallo-chelate The ratio of accelerator.In order to extend the storage period of adhesive composition, and storage stability is improved, preferably (G):(H) weight Than being 1:1~1:300 scope, more preferably 1:30~1:300, most preferably 1:80~1:300.
Adhesive composition can arbitrarily contain (I) polyether modified siloxane compound.(I) polyether-modified siliconization Compound is the silicone compounds with polyether-based, except common siloxane unit (- SiR1 2- O-) outside, also with comprising The siloxane unit (- SiR of polyether-based1(R2O(R3O)nR4)-O-).Here, R1Represent one or more alkyl or virtue Base, R2And R3Represent one or more alkylidene, R4Represent one or more alkyl, acyl group etc. (terminal groups). Can be enumerated as polyether-based：Polyethylene oxide base ((C2H4O)n) or PPOX base ((C3H6O)n) etc. polyoxyalkyl Base.
It is preferred that (I) polyether modified siloxane compound is the polyether modified siloxane compound that HLB value is 7~15.In addition, Relative to the copolymer of 100 weight portions, the preferably content of (I) polyether modified siloxane compound is 0.01~1.0 weight portion, more Preferably 0.1~0.5 weight portion.
HLB refers to hydrophile-lipophile balance (hydrophily and the oleophylic of the regulations such as such as JIS K3211 (surfactant term) The ratio of property).
(I) polyether modified siloxane compound, for example, can obtain by the following method：By hydrosilylation reactions, make Organic compound with unsaturated bond and polyoxyalkylene be grafted on the main chain of the polysiloxane with silylation and Obtain.Specifically, can enumerate：Dimethyl siloxane-methyl (polyethylene glycol oxide) silicone copolymers, dimethyl silica Alkane-methyl (polyethylene glycol oxide) siloxane-methyl (PPOX) silicone copolymers, dimethyl siloxane-methyl (polyoxy Change propylene) silicone copolymers etc..
Adhesive composition is matched with by by (I) polyether modified siloxane compound, the bonding of binding agent can be improved Power and cycling processability.When adhesive composition is free of polyether modified siloxane compound, cost can be made lower.
Also, as other compositions, the copolymerizable (first containing alkylene oxide (alkylene oxide) can be mated properly into Base) acrylic monomers, (methyl) acrylamide monomer, dialkyl group substituted acrylamide monomer, surfactant, solidification promote The known additive such as agent, plasticizer, filler, curing inhibitors, processing aid, age resister, antioxidant.These both may be used To be used alone, it is also possible to be used in combination of two or more.
As the copolymer of host used by adhesive composition of the invention, can be by by the carbon number of (A) alkyl Hydroxyl is contained by (B) at least one in (methyl) acrylate monomer of C4~C18 and selected from as copolymerisable monomer group The copolymerisable monomer of base, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) Not hydroxyl and copolymerizable list that nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxy are constituted At least one in body group carries out copolymerization to synthesize.To the polymerization of copolymer, there is no particular limitation, it is possible to use solution The appropriate polymerization such as polymerization, emulsion polymerization.
Adhesive composition of the invention, can be by the isocyanates more than cooperation (F) two function in above-mentioned copolymer Compound, the crosslinking accelerator of (G) metallo-chelate, (H) ketone-enol tautomers compound, there is appropriate any add Plus agent is prepared.
It is preferred that aforementioned copolymer is acrylic polymer, (methyl) acrylate of 50~100 weight % is preferably comprised The acrylic monomer such as monomer or (methyl) acrylic acid, (methyl) acrylic amide.
Additionally, it is preferred that the acid number of acrylic polymer is 0.01~8.0.Thereby, it is possible to improving contaminative and improving The performance for preventing glue residue phenomenon from occurring.
It is with required for neutralizing the polymer that 1g contains carboxyl here, " acid number " is one of the index for representing acid content The mg numbers of potassium hydroxide are represented.
It is preferred that making bonding of the adhesive layer of foregoing adhesives composition crosslinking under low peeling rate 0.3m/min Power is 0.05~0.1N/25mm, and the cohesive force under peeling rate 30m/min high is below 1.0N/25mm.Thereby, it is possible to obtain Cohesive force is obtained with the small performance of the change of peeling rate, even can also be peeled off rapidly in the case where high speed is peeled off.Also, Even if temporarily peel off surface protection film to re-paste, without excessive strength, it is easy to peeled off from adherend.
It is preferred that making the surface resistivity of the adhesive layer of foregoing adhesives composition crosslinking 5.0 × 10+12Ω/□ Hereinafter, it is " ± below 0.6kV " to peel off electrostatic pressure.Additionally, in the present invention, so-called " ± below 0.6kV's " is meant that " 0 ~-0.6kV " and " 0~+0.6kV ", i.e. " -0.6~+0.6kV ".If surface resistivity is big, produced because powered during to peeling off The poor performance that raw electrostatic is discharged, therefore, by making surface resistivity sufficiently small, can reduce and be shelled with from adherend Stripping electrostatic pressure produced by the electrostatic occurred during from adhesive layer, can suppress the shadow of electric control circuit to adherend etc. Ring.
It is preferred that making the gel point of the adhesive layer (binding agent after crosslinking) of adhesive composition crosslinking of the invention Number is 95~100%.Because gel fraction is so high, cohesive force will not become too much in the case of low peeling rate, reduce The phenomenon of dissolution unconverted monomer or oligomer from copolymer such that it is able to improve resistance under re-workability, high temperature/high humidity Long property, and suppress the pollution of adherend.
Adhesive film of the invention be resin film single or double formed adhesive layer form, the adhesive layer is to make Adhesive composition crosslinking of the invention is formed.In addition, surface protection film of the invention is the one side formation bonding in resin film Oxidant layer is formed, and the adhesive layer is to form adhesive composition crosslinking of the invention.In adhesive composition of the invention In, due to being combined with each composition of above-mentioned (A)~(H) with good balance, so with excellent antistatic property, low The balance of the cohesive force under peeling rate and peeling rate high is excellent, and endurance quality and cycling processability (use ball Pen is not transferred the pollution after adhesive layer is described on surface protection film to adherend) it is also excellent.Therefore, may be used Surface protection film purposes preferably as Polarizer is used.
The thickness of the adhesive layer 2 to being used in Antistatic surface diaphragm 10 of the invention, is not particularly limited, For example, it is preferable to be 5~40 μm or so of thickness, more preferably 10~30 μm or so of thickness.When being Antistatic surface diaphragm Peel strength (cohesive force) to adherend surface is 0.03~0.3N/25mm or so, the binding agent with micro- cohesive force It is operational excellent during stripping Antistatic surface diaphragm from adherend during layer 2, therefore preferably.In addition, being based on quiet from resisting Ammeter surface protective film 10 peels operational excellent viewpoint during stripping film 5, and preferably stripping film 5 is peeled from adhesive layer 2 Peeling force is below 0.2N/50mm.
In addition, being the list in resin film 3 for the stripping film 5 used in Antistatic surface diaphragm 10 of the invention Form peeling agent layer 4 on face to form, the peeling agent layer 4 is to use the stripping containing using dimethyl polysiloxane as main component Agent, to be the polysiloxane-based compound of liquid and the resin combination of antistatic additive at 20 DEG C form.
As resin film 3, polyester film, PA membrane, polyethylene film, polypropylene screen, polyimide film etc. can be enumerated, from From the viewpoint of excellent transparency or less expensive, particularly preferably polyester film.Resin film both can be unstretching film, Can be monadic stretching membrane or biaxially-stretched film.Alternatively, it is also possible to by the stretching ratio of stretched film, stretched film along with crystal The orientation angles for changing formed direction of principal axis are controlled in particular value.
Thickness to resin film 3 is not particularly limited, for example, it is preferable to be 12~100 μm or so of thickness；If 20 ~50 μm or so of thickness is then easily operated, therefore more preferably.
In addition, on the surface of resin film 3, it is also possible to which the surface for implementing to be carried out based on corona discharge as needed is modified, bottom The easily bondingization treatment such as smearing of paint.
As constitute peeling agent layer 4, using dimethyl polysiloxane as the remover of main component, addition can be enumerated The known polysiloxane-based remover of response type, condensation reaction type, cationic polymerization type, radical polymerization mould assembly etc..As plus Into the commercially available product of the polysiloxane-based remover of response type, for example, can enumerate：KS-776A、KS-847T、KS-779H、KS- 837th, KS-778, KS-830 (Shin-Etsu Chemial Co., Ltd's manufacture)；SRX-211、SRX-345、SRX-357、SD7333、 SD7220, SD7223, LTC-300B, LTC-350G, LTC-310 (Dow Corning Toray Co., Ltd (Dow Corning Toray Co., Ltd.) manufacture) etc..As the commercially available product of condensation reaction type, for example, SRX-290, SYLOFF- can be enumerated 23 (Dow Corning Toray Co., Ltd's manufactures) etc..In carrying out commercially available product as cationic polymerization type, for example, can enumerate TPR-6501, TPR-6500, UV9300, UV9315, UV9430 (MomentivePerformanceMaterials (Momentive Performance Materials Inc.) manufacture), X62-7622 (Shin-Etsu Chemial Co., Ltd's manufacture) etc..As radical polymerization mould assembly city The product sold, for example, X62-7205 (Shin-Etsu Chemial Co., Ltd's manufacture) etc. can be enumerated.
As the polysiloxane-based compound at 20 DEG C that constitute peeling agent layer 4 being liquid, can enumerate polyether-modified poly- Siloxanes, alkyl-modified polysiloxanes, methyl alcohol high-grade aliphatic ester modified polyorganosiloxane etc..In the present invention, it is viscous in order to improve The antistatic behaviour on knot oxidant layer surface, uses the state mixed in using dimethyl polysiloxane as the peeling agent layer of main component 20 DEG C at be liquid polysiloxane-based compound.From for purposes of the invention, preferably modified polyorganosiloxane compound In Siloxane-Oxyalkylene Copolymers.Polyether chain in Siloxane-Oxyalkylene Copolymers is by ethylene oxide (oxirane), oxidation third Alkene (expoxy propane) etc. is constituted, for example, the molecular weight of the polyethylene glycol oxide by selecting to be used in side chain, can adjust and poly- silicon The physical properties such as intermiscibility, the antistatic effect of oxygen alkane remover.
In addition, as the commercially available product of Siloxane-Oxyalkylene Copolymers, for example, can enumerate：KF-351A、KF-352A、KF- 353rd, KF-354L, KF-355A, KF-642 (Shin-Etsu Chemial Co., Ltd's manufacture)；SH8400, SH8700, SF8410 (pottery The healthy and free from worry Dongli Ltd.'s manufacture of family name)；TSF-4440, TSF-4441, TSF-4445, TSF-4446, TSF-4450 (step figure high-new Materials Co., Ltd (Momentive Performance Materials Inc.) manufactures)；BYK-300、BYK-306、BYK-307、 BYK-320, BYK-325, BYK-330 (manufacture of BYK-Chemie companies) etc..
It is the polysiloxane-based compound phase of liquid at 20 DEG C for the stripping using dimethyl polysiloxane as main component It is different and different from the intermiscibility degree of remover according to the species of polysiloxane compound from the addition of agent, as long as In view of when Antistatic surface diaphragm is peeled off from adherend it is required peel off electrostatic pressure, the contaminative to adherend, Bonding characteristic etc. and set.
As the antistatic additive for constituting peeling agent layer 4, preferably for the stripping using dimethyl polysiloxane as main component From the favorable dispersibility of agent solution, and resisting using dimethyl polysiloxane as the solidification of the remover of main component is not hindered Electrostatic agent.As such antistatic additive, preferred as alkali salt.
As alkali metal salt, can enumerate：Comprising lithium, sodium, potassium slaine, specifically, for example, it is preferable to using passing through Comprising Li+、Na+、K+Deng cation with comprising Cl-、Br-、I-、BF4 -、PF6 -、SCN-、ClO4 -、CF3SO3 -、(CF3SO2)2N-、 (C2F5SO2)2N-、(CF3SO2)3C-Deng the slaine that is constituted of anion.Wherein, particularly preferably using LiBr, LiI, LiBF4、LiPF6、LiSCN、LiClO4、LiCF3SO3、Li(CF2SO2)2N、Li(C2F5SO2)2N、Li(CF3SO2)3The lithium salts such as C.This A little alkali metal salts both may be used singly or in combination of two or more.For the stabilisation of ionic substance, it is also possible to Compound of the addition containing polyoxyalkyl based structures.
Antistatic additive, relative to the addition using dimethyl polysiloxane as the remover of main component, is according to anti-quiet The species of electric agent is different and different from the degree of the compatibility of remover, but antistatic in view of being peeled off from adherend Stripping electrostatic pressure, the contaminative to adherend, bonding characteristic required during surface protection film etc. are set.
For the remover using dimethyl polysiloxane as main component and Siloxane-Oxyalkylene Copolymers and antistatic additive Mixed method for, be not particularly limited.Can be using any one method in following mixed method：With dimethyl Polysiloxanes as in the remover of main component, after addition Siloxane-Oxyalkylene Copolymers and antistatic additive are mixed, addition Remover solidification catalyst and the method for being mixed；Organic solvent diluting is used in advance using dimethyl polysiloxane as master After wanting the remover of composition, add Siloxane-Oxyalkylene Copolymers and antistatic additive and remover solidification catalyst and mixed The method of conjunction；After using organic solvent diluting using polysiloxanes as the remover of main component in advance, add catalyst and enter Row mixing, then, addition Siloxane-Oxyalkylene Copolymers and antistatic additive and the method that is mixed etc..In addition, as needed, The material of the auxiliary antistatic effect of the adhesion promotors such as silane coupler, the compound containing polyoxyalkylene etc. can be added Material.
For remover and Siloxane-Oxyalkylene Copolymers and antistatic additive using dimethyl polysiloxane as main component Blending ratio for, be not particularly limited, but relative to the remover using dimethyl polysiloxane as main component Solid constituent 100, preferred, polyethers modified polyorganosiloxane and antistatic additive are calculated as 5~100 or so ratio with solid constituent.Phase For the solid constituent 100 using dimethyl polysiloxane as the remover of main component, if Siloxane-Oxyalkylene Copolymers and anti- The ratio of the addition less than 5 converted with solid constituent of electrostatic agent, then transfer amount of the antistatic additive to adhesive layer surface Tail off, it is difficult to adhesive layer is played anlistatig function.In addition, relative to using dimethyl polysiloxane as main component The solid constituent 100 of remover, if the addition converted with solid constituent of Siloxane-Oxyalkylene Copolymers and antistatic additive exceedes 100 ratio, then cause together with Siloxane-Oxyalkylene Copolymers and antistatic additive using dimethyl polysiloxane as main component Remover can also be transferred to adhesive layer surface, accordingly, it is possible to the bonding characteristic of adhesive layer can be reduced.
Method and the laminating stripping of adhesive layer 2 are formed in the present invention on the base material film 1 of Antistatic surface diaphragm 10 From the method for film 5, can be carried out using known method, there is no particular limitation.Specifically, can enumerate：(1) will use In the resin combination for forming adhesive layer 2, coat on the one side of base material film 1 and be dried, pasted after forming adhesive layer The method for closing stripping film 5；(2) will coat on the surface of stripping film 5 and done for forming the resin combination of adhesive layer 2 It is dry, after forming adhesive layer, method of base material film 1 etc. of fitting.Any one method therein can be used.
In addition, when adhesive layer 2 is formed at into 1 surface of base material film, can be carried out using known method.It is specific and Speech, can be strangled rod (Mayer bar) and be applied using reverse coating, comma scraper coating, intaglio plate coating, slit extrusion coated, wheat The known coating method such as cloth, airblade coating.
In addition, similarly, when peeling agent layer 4 is formed at into resin film 3, can be carried out using known method.Tool For body, the known coating methods such as rod coating, airblade coating can be strangled using intaglio plate coating, wheat.
Fig. 2 is to represent the profile that the state after stripping film is peeled from Antistatic surface diaphragm of the invention.
Peeled from the Antistatic surface diaphragm 10 shown in Fig. 1 by by stripping film 5, the institute of peeling agent layer 4 of stripping film 5 It is the polysiloxane-based compound of liquid and a part for antistatic additive (reference 7) at 20 DEG C for containing, is transferred (attachment) To the surface of the adhesive layer 2 of Antistatic surface diaphragm 10.Therefore, in fig. 2, with the spot of reference 7 schematically Show the polysiloxane-based chemical combination surface of adhesive layer 2, at 20 DEG C being liquid for being transferred to Antistatic surface diaphragm Thing and antistatic additive.
For Antistatic surface diaphragm of the invention, when by the anti-quiet of the state for having peeled stripping film shown in Fig. 2 Ammeter surface protective film 11 is fitted in when in adherend, poly- silicon being transferred to the surface of adhesive layer 2, at 20 DEG C being liquid Oxygen alkyl compound and antistatic additive are contacted with adherend surface.Thereby, it is possible to lower suppress again from being attached Stripping electrostatic pressure during Antistatic surface diaphragm is peeled on body.
Fig. 3 is the profile of the embodiment for representing optical component of the invention.
Stripping film 5 is being peeled the state that exposes so as to adhesive layer 2 from Antistatic surface diaphragm 10 of the invention Under, fitted on the optical component 8 as adherend by the adhesive layer 2.
That is, figure 3 illustrates the optical component 20 for being fitted with Antistatic surface diaphragm 10 of the present invention.As optical section Part, can enumerate Polarizer, polarizer, lens coating, the Polarizer for being also used as polarizer, be also used as the Polarizer of lens coating Deng optical film.This optical component is used as the liquid crystal display devices such as liquid crystal display panel, various metrical instrument class optical systems The component parts that bulk cargo is put etc..In addition, as optical component, antireflection film, hard coat film, touch panel can also be enumerated with transparent The optical films such as conducting film.Particularly, can be preferably used as fitting in surface being entered with polysiloxane compound, fluorine compounds etc. Went anti-pollution treatment low reflection process Polarizer (LR Polarizers), it is anti-dazzle it is low reflection treatment Polarizer (AG-LR Polarizers) Deng the Antistatic surface diaphragm being applied with the face of anti-pollution treatment of optical film.
Based on optical component of the invention, when using Antistatic surface diaphragm 10 from the optical component as adherend When peeling off removal on (optical film), can will fully peel off electrostatic pressure and suppress in low-level, therefore, without worrying to destroy Drive the circuit block of IC, TFT element, gate line drive circuit etc., it is possible to increase in the operation such as manufacture liquid crystal display panel Production efficiency, it is ensured that the reliability of production process.Embodiment
Below, the present invention is further illustrated by embodiment.
<The manufacture of adhesive composition>
[embodiment 1]
To nitrogen is imported in the reaction unit equipped with agitator, thermometer, reflux condenser and nitrogen ingress pipe, so as to use nitrogen Gas has replaced the air in reaction unit.Then, to added in reaction unit 100 weight portions 2-EHA, The acrylic acid 8- hydroxyls monooctyl ester of 3.0 weight portions, the polypropylene glycol mono acrylic ester of 10 weight portions (constitute polyalkylene glycol chain The averaged repeating numbers n=12 of alkylene oxide), and the solvent (ethyl acetate) of 60 weight portions is added simultaneously.Then, by 2 hours The weight portion of azodiisobutyronitrile 0.1 dripped as polymerization initiator, reacts 6 hours at a temperature of 65 DEG C, is divided equally again The acrylic acid copolymer soln of the embodiment 1 of son amount 500,000.To the acrylic acid copolymer soln, 8.5 weight portion levulinics are added Ketone and after being stirred, adds 2.0 weight portion Coronate HX (U ロ ネ ー ト HX, hexamethylene diisocyanate compound Isocyanuric acid ester), 0.1 weight portion praseodynium titanium and be stirred mixing, obtain the binding agent combination of embodiment 1 Thing.
[embodiment 2~6 and comparative example 1~2]
In addition to each composition of adhesive composition of embodiment 1 is have adjusted as described in Tables 1 and 2, with embodiment 1 Similarly operated, obtained the adhesive composition of embodiment 2~6 and comparative example 1~2.
Table 1
Table 2
Tables 1 and 2 be would indicate that each components matching than whole table be divided into two tables of part, the equal table of numerical value in bracket Show the numerical value of each Parts by Ingredients that the total amount organized with (A) is set to 100 weight portions and obtained.In addition, will with Tables 1 and 2 in The corresponding compound name of abbreviation of each composition for using is shown in table 3 and table 4.Additionally, Coronate (U ロ ネ ー ト, registration Trade mark) HX, Coronate HL and Coronate L are Nippon Polyurethane Industry Co., Ltd. (Nippon Polyurethane Industry Co., Ltd.s) trade name, Takenate (タ ケ ネ ー ト, registration mark) D-140N, D-127N, D-110N It is the trade name of Mitsui Chemicals, Inc, Desmodur (デ ス モ ジ ュ ー Le, registration mark) N3400 is Sumika The trade name of Bayer Urethane Co., Ltd. (firmly changing バ イ エ Le ウ レ タ Application Co., Ltd.).
Table 3
Table 4
The synthesis ＞ of the functional isocyanate compounds of ＜ bis-
Two functional isocyanate compounds of synthesis example 1,2 are synthesized using following methods.I.e., as shown in table 5 and table 6, will Diisocyanate and diol compound are mixed with the ratio of mol ratio NCO/OH=16, are reacted 3 hours at 120 DEG C, then, are adopted Remove unreacted diisocyanate under reduced pressure with thin film evaporation unit, obtain desired two functional isocyanates chemical combination Thing.
Table 5
The F-1 of synthesis example 1 The F-2 of synthesis example 2
Diisocyanate cpd HDI HDI
Diol compound K-1 K-2
Table 6
<The manufacture of Antistatic surface diaphragm>
[embodiment 1]
By the addition reaction-type polysiloxanes of 5 weight portions, (name of product is SRX-345, Dow Corning Toray Co., Ltd (Dow Corning Toray Co., Ltd.) is manufactured), (name of product is for the Siloxane-Oxyalkylene Copolymers of 0.15 weight portion SH8400, Dow Corning Toray Co., Ltd (Dow Corning Toray Co., Ltd.s) manufacture), the perchloric acid of 5 weight portions Lithium be 10% ethyl acetate solution, the toluene of 95 weight portions and ethyl acetate be 1:1 mixed solvent and 0.05 weight portion Platinum catalyst (name of product be SRX-212Catalyst (catalyst), Dow Corning Toray Co., Ltd manufacture) be blended in Together and mixing is stirred, has prepared the coating of the peeling agent layer for forming embodiment 1.Rod is strangled using wheat, shape will be used for Into the coating of the peeling agent layer of embodiment 1, to make dried thickness turn into the way of in the of 0.2 μm, it is 38 μm to be coated on thickness The surface of polyethylene terephthalate film, and dried 1 minute in 120 DEG C of heated air circulation type baker, implemented The stripping film of example 1.
By the adhesive composition of embodiment 1, to make dried thickness turn into the way of in the of 20 μm, it is 38 to be coated on thickness μm polyethylene terephthalate film surface after, in 100 DEG C of heated air circulation type baker dry 2 minutes, formed Adhesive layer.Then, on the surface of the adhesive layer, the peeling agent layer of the stripping film of the embodiment 1 of above-mentioned manufacture of having fitted (polysiloxanes process face).Resulting adhesive film is incubated 5 days in the environment of 40 DEG C, so that binding agent solidifies, is obtained The Antistatic surface diaphragm of embodiment 1.
[embodiment 2~6]
In addition to each adhesive composition of embodiment 1 is adjusted into the adhesive composition of embodiment 2~6 respectively, Operated similarly to Example 1, obtained the Antistatic surface diaphragm of embodiment 2~6.
[comparative example 1]
By the addition reaction-type polysiloxanes of 5 weight portions, (name of product is SRX-345, Dow Corning Toray Co., Ltd Manufacture), the toluene of 95 weight portions and ethyl acetate be 1:Platinum catalyst (the ProductName of 1 mixed solvent and 0.05 weight portion Referred to as SRX-212Catalyst, Dow Corning Toray Co., Ltd's manufacture) mix and be stirred mixing, prepare Coating for forming the peeling agent layer of comparative example 1.Rod is strangled using wheat, by the coating of the peeling agent layer for forming comparative example 1, To make dried thickness turn into the way of in the of 0.2 μm, the table of the polyethylene terephthalate film that thickness is 38 μm is coated on Face, and dried 1 minute in 120 DEG C of heated air circulation type baker, obtain the stripping film of comparative example 1.
By the adhesive composition of comparative example 1, to make dried thickness turn into the way of in the of 20 μm, it is 38 to be coated on thickness μm polyethylene terephthalate film surface after, in 100 DEG C of heated air circulation type baker dry 2 minutes, formed Adhesive layer.Then, on the surface of the adhesive layer, the remover of the stripping film of above-mentioned manufactured comparative example 1 of having fitted Layer (polysiloxanes process face).Resulting adhesive film is incubated 5 days in the environment of 40 DEG C, so that binding agent solidifies, is obtained The Antistatic surface diaphragm of comparative example 1.
[comparative example 2]
In addition to the adhesive composition of comparative example 1 to be adjusted to the adhesive composition of comparative example 2, with comparative example 1 Similarly operated, obtained the Antistatic surface diaphragm of comparative example 2.
The composition and thickness of the peeling agent layer in the Antistatic surface diaphragm of embodiment 1~6 and comparative example 1,2 are shown in In table 7.
Table 7
<Test method and evaluation>
In the environment of 23 DEG C, 50%RH, after aging 7 days of the surface protection film of embodiment 1~6 and comparative example 1,2, stripping Fall stripping film (scribbling the PET film of silicone (polysiloxanes) resin), so that adhesive layer exposes, and as measure sheet resistance The sample of rate.
And then, the surface protection film that the adhesive layer is exposed is fitted in by adhesive layer and has been pasted onto liquid crystal cells On polarisation plate surface, place 1 day after carried out under 50 DEG C, 5 atmospheric pressure pressure cooker process 20 minutes, further at room temperature After placing 12 hours, as the sample for determining cohesive force, peeling off electrostatic pressure and re-workability.
<Cohesive force>
Using cupping machine, with low peeling rate (0.3m/min) and peeling rate high (30m/min), to 180 ° of directions Above-mentioned resulting measure sample (25mm surface protection films wide are fitted in the sample of polarisation plate surface) is peeled off, is determined Peel strength, and using the peel strength as cohesive force.
<Surface resistivity>
After weathering, before laminating Polarizer, peel stripping film (scribbling the PET film of silicone resin) off and make outside adhesive layer Dew, using resistivity meter HirestaUP-HT450 (Ha イ レ ス タ UP-HT450, Mitsubishi of Co., Ltd. chemical analysis technology (Mitsubishi Chemical Analytech Co., Ltd.s) manufactures), determine the surface resistivity of adhesive layer.
<Peel off electrostatic pressure>
Using high accuracy electrostatic transducer SK-035, SK-200 (Co., Ltd.'s Keyemce (Keyence Corporation) Manufacture), determine the Polarizer band when 180 ° of strippings are carried out with the draw speed of 30m/min to above-mentioned resulting measure sample Electricity and produce voltage (electrostatic pressure), using the maximum of measured value as peel off electrostatic pressure.
<Re-workability>
Described that (load is 500g, back and forth 3 on the surface protection film of measure sample obtained above with ball pen It is secondary) after, surface protection film is peeled off from Polarizer, the surface of Polarizer is observed, it is confirmed whether to be transferred the pollution to Polarizer.Evaluate mesh Mark benchmark："○" is evaluated as when not transferred the pollution to Polarizer；When confirmation along the track of ball pen description at least to office Portion is evaluated as " △ " when displaced pollution；There is pollution transportation and from adhesive surface when the track for confirming to describe along ball pen Also confirm to be evaluated as "×" when having the disengaging of binding agent.
Evaluation result is shown in Table 8.In addition, in surface resistivity, " m × 10 are represented by " mE+n "+n" (its In, m is arbitrary real number, and n is positive integer).
Table 8
Measurement result according to table 8, it is known that following situations.
The Antistatic surface diaphragm of the embodiment of the present invention 1~6, with appropriate cohesive force, and to adherend surface Without pollution, and, stripping electrostatic when Antistatic surface diaphragm is peeled off from adherend is forced down.
On the other hand, for be with the addition of in adhesive layer polysiloxane compound and antistatic additive comparative example 1 it is anti- For electrostatic surface diaphragm, the surface resistivity of adhesive layer is low and good, but due to the big reason of cohesive force, peels off electrostatic Pressure is high, re-workability is poor.In addition, in comparative example 2, in spite of the cohesive force of appropriateness, but due to the sheet resistance of adhesive layer Rate reason high, stripping electrostatic pressure is high, re-workability is poor.
That is, it is mixed with a binder in the comparative example 1,2 of polysiloxane compound and antistatic additive, it is difficult to while meeting Peel off the reduction of electrostatic pressure and the improvement of the contaminative to adherend.On the other hand, poly- silica is with the addition of in peeling agent layer After hydride compounds and antistatic additive, make polysiloxane compound and antistatic additive be transferred to the embodiment 1 on adhesive layer surface~ 6, with the effect of few addition reduction stripping electrostatic pressure, therefore also can not polluted to adherend, obtain good Good Antistatic surface diaphragm.
Industrial applicibility
Antistatic surface diaphragm of the invention, for example, Polarizer, polarizer, display lens can be applied to In the optical film of film etc., additionally, in production process in various optical components etc. etc., can be in order to protect the optical component etc. Surface and use.Particularly, as the LR for having carried out anti-pollution treatment with polysiloxane compound, fluorine compounds etc. as surface In the case that the Antistatic surface diaphragm of the optical films such as Polarizer, AG-LR Polarizers carrys out use, can reduce from being attached The static content produced when being peeled off on body.
Pollution of the Antistatic surface diaphragm of the invention to adherend (is not pushed away over time less and without deterioration Move and deteriorate), with excellent antistripping antistatic property, therefore, it is possible to improve the yield rate of production process, industrially Value it is high.

Claims (13)

1. a kind of Antistatic surface diaphragm, it is to sequentially pass through following operations (1)~(2) and manufacture,
Operation (1)：Form what is be made up of adhesive composition on the one side of the base material film being made up of the resin with the transparency The operation of adhesive layer,
The adhesive composition includes：Make the carbon number of (A) alkyl in (methyl) acrylate monomer of C4~C18 The copolymerisable monomer of at least one and (B) hydroxyl and selected from as copolymerisable monomer group by (C) is carboxylic can Comonomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl monomer or At least one copolymerization in the copolymerisable monomer group that (methyl) alkyl acrylate monomer containing alkoxy is constituted is total to The acrylic polymer of polymers；Also contain isocyanate compound more than (F) two function, (G) crosslinking accelerator and (H) Ketone-enol tautomers compound；And do not contain antistatic additive,
Operation (2)：The stripping film of the peeling agent layer containing antistatic additive will be laminated on resin film one side, by the stripping Operation on the surface that oxidant layer fits in the adhesive layer,
The peeling agent layer is by being the poly- of liquid containing the remover using dimethyl polysiloxane as main component, at 20 DEG C The resin combination of siloxane compound and the antistatic additive is formed,
The described polysiloxane-based compound and the antistatic additive of the peeling agent layer are transferred to the surface of the adhesive layer,
The stripping electrostatic pressure of the adhesive layer is -0.6kV~+0.6kV.
2. Antistatic surface diaphragm as claimed in claim 1, wherein,
The copolymerisable monomer of (B) hydroxyl is selected from by (methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) acrylic acid 6- The own ester of hydroxyl, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates, N- hydroxyls (methyl) acrylamide, In the compound group that N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide are constituted it is at least one with On,
(C) the carboxylic copolymerisable monomer is selected from by (methyl) acrylic acid, (methyl) carboxy ethyl acrylate, (methyl) Carboxypentyl acrylate, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloxypropyl hexahydro Phthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloyl-oxyethyls butanedioic acid, 2- (methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloxy second It is more than at least one in the compound group that base tetrahydrophthalic acid is constituted.
3. Antistatic surface diaphragm as claimed in claim 1 or 2, wherein, (D) polyalkylene glycol mono (methyl) third Olefin(e) acid ester monomer is selected from polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylic acid It is more than at least one in ester, ethyoxyl PAG (methyl) acrylate.
4. Antistatic surface diaphragm as claimed in claim 1 or 2, wherein, the acrylic polymer as it is described can Comonomer group contains (E) not hydroxyl and nitrogenous vinyl monomer or (methyl) acrylic acid alkyl containing alkoxy It is more than at least one in ester monomer.
5. Antistatic surface diaphragm as claimed in claim 1 or 2, wherein,
For isocyanate compound more than (F) two function,
As two functional isocyanate compounds it is non-ring type aliphatic isocyanates compound and is diisocyanate cpd The compound for being reacted with diol compound and being generated,
The diisocyanate cpd is aliphatic diisocyanate, is selected from by tetramethylene diisocyanate, five Asias Methyl diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, LDI institute One kind in the compound group of composition,
The diol compound is selected from by 2- methyl 1,3- propane diols, 2,2- dimethyl -1,3- propane diols, 2- methyl -2- Propyl group -1,3- propane diols, 2- ethyl -2- butyl -1,3- propane diols, 3- methyl isophthalic acids, 5- pentanediols, 2,2- dimethyl -1,3- third One kind in the compound group that glycol monohydroxy pivalate, polyethylene glycol, polypropylene glycol are constituted,
It is isocyanuric acid ester, the isophorone two of hexamethylene diisocyanate compound as trifunctional isocyanates compound The isocyanuric acid ester of isocyanate compound, the addition product of hexamethylene diisocyanate compound, isophorone diisocyanate The addition product of ester compounds, the biuret of hexamethylene diisocyanate compound, IPDI compound Biuret, the isocyanuric acid ester of tolunediisocyanate compound, the isocyanuric acid ester of xylylene diisocyanate compound, The isocyanuric acid ester of hydrogenated xylylene diisocyanate cpd, the addition product of tolunediisocyanate compound, benzene diformazan The addition product of group diisocyanate compound, the addition product of hydrogenated xylylene diisocyanate cpd.
6. Antistatic surface diaphragm as claimed in claim 1 or 2, wherein,
In the adhesive composition, contain the polyether modified siloxane compound that (I) HLB value is 7~15.
7. Antistatic surface diaphragm as claimed in claim 1 or 2, wherein,
Polysiloxane-based compound in the peeling agent layer is Siloxane-Oxyalkylene Copolymers.
8. Antistatic surface diaphragm as claimed in claim 1 or 2, wherein,
The antistatic additive in the peeling agent layer is alkali metal salt.
9. a kind of Antistatic surface diaphragm, it is by adhesive layer and remover film so that the adhesive layer and the stripping The mode that oxidant layer is in contact is stacked gradually and formed in by the one side of the base material film constituted with transparent resin,
The adhesive layer by the carbon number of (A) alkyl for (methyl) acrylate monomer of C4~C18 in it is at least one, With the copolymerisable monomer of (B) hydroxyl and selected from as copolymerisable monomer group by (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl monomer or containing alkoxy The copolymerisable monomer group that is constituted of (methyl) alkyl acrylate monomer at least one copolymerization copolymer third Alkene acids polymers are constituted, also containing isocyanate compound more than (F) two function, (G) crosslinking accelerator and (H) ketone- Enol tautomer compound, and antistatic additive is not contained,
The stripping film is to be laminated the peeling agent layer containing antistatic additive on the one side of resin film to form,
It by containing the remover using dimethyl polysiloxane as main component, at 20 DEG C is liquid that the peeling agent layer is The resin combination of polysiloxane-based compound and antistatic additive is formed,
The described polysiloxane-based compound and the antistatic additive of the peeling agent layer are transferred to the surface of the adhesive layer,
The stripping electrostatic pressure of the adhesive layer is -0.6kV~+0.6kV.
10. Antistatic surface diaphragm as claimed in claim 9, wherein,
Polysiloxane-based compound in the peeling agent layer is Siloxane-Oxyalkylene Copolymers.
The 11. Antistatic surface diaphragm as described in claim 9 or 10, wherein,
The antistatic additive in the peeling agent layer is alkali metal salt.
A kind of 12. optical films, it is fitted with the Antistatic surface diaphragm any one of claim 1~11.
A kind of 13. optical components, it is fitted with the Antistatic surface diaphragm any one of claim 1~11.
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