CN108864974A - Antistatic surface protective film - Google Patents

Antistatic surface protective film Download PDF

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Publication number
CN108864974A
CN108864974A CN201810778041.1A CN201810778041A CN108864974A CN 108864974 A CN108864974 A CN 108864974A CN 201810778041 A CN201810778041 A CN 201810778041A CN 108864974 A CN108864974 A CN 108864974A
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methyl
film
compound
antistatic
surface protective
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CN108864974B (en
Inventor
长仓毅
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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides the pollution to adherend less and without deterioration and with the Antistatic surface protective film of excellent antistripping antistatic property.It is successively to pass through：It is formed in the single side for the base material film (1) being made of transparent resin by the acrylic polymer containing copolymer, and then the process of the adhesive layer (2) of the adhesive composition composition also containing more than (D) two function isocyanate compound, (E) crosslinking accelerator and (F) ketone-enol tautomers compound；Stripping film (5) made of the peeling agent layer (4) containing antistatic agent will be laminated in the single side of resin film (3), it is made by the process that peeling agent layer (4) fits in adhesive layer (2) surface, peeling agent layer (4) is by containing making remover as main component with dimethyl polysiloxane, at 20 DEG C be that the polysiloxane-based compound of liquid and the resin combination of antistatic agent are formed, the removing electrostatic pressure of adhesive layer (2) is ± 0.6kV or less.

Description

Antistatic surface protective film
It is on February 02nd, 2015 that the present invention, which is application No. is the 201510053597.0, applying date, entitled " is resisted quiet The divisional application of ammeter surface protective film ", the application on May 15th, 2014 Japanese publication patent application JP2014- It is claimed priority based on No. 101328.
Technical field
The present invention relates to a kind of adhesive composition and surface protection films.Specifically, it is related to that there is antistatic property Antistatic surface protective film.More specifically, the present invention provide a kind of pair of adherend pollution it is few, and also without deterioration The manufacturing method and Antistatic surface protective film of Antistatic surface protective film with excellent antistripping antistatic property.
Background technique
Currently, when manufacture, carrying polarizer, phase plate, display lens coating, antireflection film, hard coat film, touch surface When the optical articles such as the optical film of plate transparent conductive film etc. and the display for having used them, by being used in the optics The surface coating surface protective film of film and prevent the surface contamination and scratch in subsequent handling.In order to save to surface protection film into After row removing the labour that is bonded again and time to improve operating efficiency, the visual examination to the optical film as product For, also directly implement in the state of being bonded surface protection film on optical film sometimes.
Back and forth, in order to prevent the attachment of scar and dirt in the manufacturing process of optical articles, it is generally used in base The single side of material film is provided with the surface protection film of adhesive layer.Surface protection film is bonded by the adhesive layer of micro- cohesive force In on optical film.The reason of adhesive layer is set as micro- cohesive force be, in order to will use the surface protection film finished from Optical film sur-face peeling and when removing, can easily be done removing, and binder adheres to and remains in work in order to prevent On optical film for the product of adherend (so-called prevent glue residue there is a phenomenon where).
In recent years, in the production process of liquid crystal display panel, due to the surface protection film that will be fitted on optical film The removing electrostatic pressure generated when removing and removing can destroy the electricity such as the driving IC of display picture for controlling liquid crystal display panel Circuit unit, there are also the orientations of liquid crystal molecule to damage, and is also occurring although the number of packages of these phenomenons generation is few.
In addition, the driving voltage of liquid crystal material tends to reduce in order to reduce the power consumption of liquid crystal display panel, IC is driven therewith Breakdown voltage also tend to reduce.Recently, it is desirable that by removing electrostatic pressure control in the range of+0.7kV~-0.7kV.
Therefore, because removing electrostatic pressure is high when surface protection film is removed from the optical film as adherend in order to prevent Caused defect, it is thus proposed that a kind of surface protection film, it uses containing for reducing the antistatic of removing electrostatic pressure The adhesive layer of agent.
For example, in patent document 1, a kind of use is disclosed by alkyl trimethyl ammonium salt, the acrylic polymer of hydroxyl Close the surface protection film of object, the binder that polyisocyanate forms.
In addition, in patent document 2, disclosing one kind by ionic liquid and acid value is 1.0 acroleic acid polymerizations below The adhesive composition of object composition and the bonding sheet class for having used the composition.
In addition, in patent document 3, disclose it is a kind of by acrylate copolymer, polyether polyols, by yin from The adhesive composition of the sub- processed alkali metal salt composition of adsorptivity compound and the surface protection for having used the composition Film.
In addition, in patent document 4, disclosing one kind by ionic liquid, alkali metal salt, glass transition temperature 0 The adhesive composition of polymer composition DEG C below and the surface protection film for having used the composition.
In addition, disclosing the modified poly- silicon oxygen of the admixtured polyether in the adhesive layer of surface protection film in patent document 5,6 The technology contents of alkane.
In above patent document 1~4, antistatic agent is added with inside adhesive layer, but the thickness of adhesive layer is thicker, And the mobile amount of the adherend that over time, antistatic agent is bonded from adhesive layer to surface protection film can be got over It is more.In addition, in the optical film of LR (Low Reflective) polarizer, AG (AntiGlare)-LR polarizer etc., due to Anti-pollution processing is applied with to optical film surface using polysiloxane compound or fluoride etc., therefore, when from as being glued When removing surface protection film used in the optical film on the optical film of attached body, removing electrostatic pressure is got higher.
In addition, as described in patent document 5,6, when being mixed with Siloxane-Oxyalkylene Copolymers in adhesive layer, it is difficult to right The cohesive force of surface protection film is finely adjusted.In addition, due to being mixed with polyether modified siloxane in adhesive layer, when When the condition for being coated and dried adhesive composition on base material film changes, the adhesive layer table that is formed on surface protection film The characteristic in face knifeedge changes.Also, from the viewpoint of protecting optical film surface, the thickness of adhesive layer can not be made It is set as very thin.Therefore, according to the thickness of adhesive layer, need to increase the Siloxane-Oxyalkylene Copolymers mixed in adhesive layer Additive amount, is as a result easy pollution adherend surface, cohesive force at any time and changes to the pollution of adherend.
In recent years, along with the universal of 3D display device (autostereoscopic display), there is the table in optical films such as polarizers Face paste closes the case where FPR (patterned retarder, Film Patterned Retarder) film.Removing is used in optics such as polarizers After the surface protection film that the surface of film is bonded, it is bonded FPR film.But when the optical film surface of polarizer etc. is protected by surface When binder that cuticula uses, antistatic agent are polluted, there are problems that being difficult to be bonded FPR film.Therefore, to being used in the purposes Surface protection film for, it is desirable that it is few to the pollution of adherend.
On the other hand, in some liquid crystal display panel manufacturers, as surface protection film to the pollution of adherend Evaluation method is with the following method：The surface protection film being bonded on the optical film of polarizer etc. is once removed, It has been mixed into the state of bubble and has been bonded again, the object after being bonded again is heated under prescribed conditions, then removes table Surface protective film and the surface for observing adherend.In this evaluation method, though the surface contamination of adherend be it is micro, If there are adherend surface contaminations between the part that the part for being mixed into bubble is in contact with the binder of surface protection film Difference can then be remained as bubble impression (sometimes referred to as " bubble stains ").Therefore, as the pollution to adherend surface The evaluation method of property, the evaluation method that can be strict.In recent years, even being determined with this stringent evaluation method Result, it is also desirable to the surface protection film that there is no problem in terms of the surface contamination of adherend.But current situation is, In the surface protection film for having used the adhesive layer containing antistatic agent proposed in the past, it is difficult to solve the project.
Therefore, it is necessary to one kind surface protection film used in optical film, it is considerably less to the pollution of adherend and There is no ongoing change (not changing as time goes by) to the pollution of adherend.Furthermore, it is desirable to will be from adherend The surface protection film that removing electrostatic pressure when upper removing inhibits low.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2005-131957 bulletin
Patent document 2：Japanese Unexamined Patent Publication 2005-330464 bulletin
Patent document 3：Japanese Unexamined Patent Publication 2005-314476 bulletin
Patent document 4：Japanese Unexamined Patent Publication 2006-152235 bulletin
Patent document 5：Japanese Unexamined Patent Publication 2009-275128 bulletin
Patent document 6：No. 4537450 bulletins of Japanese Patent Publication No.
Summary of the invention
Subject to be solved by the invention
In order to solve the project, the inventors of the present invention are studied intensively.
In order to reduce the ongoing change polluted and also reduce antistatic property to adherend, reduction is needed to be speculated It is the additive amount of antistatic agent the reason of polluting adherend.But when reduce antistatic agent additive amount when, will lead to from Removing electrostatic pressure when removing surface protection film in adherend is got higher.The inventors of the present invention, which have studied, to be added not increasing antistatic agent Lower inhibit the method for removing electrostatic pressure when removing surface protection film from adherend in the case where the absolute magnitude of dosage. Itself as a result, it has been found that, added not in adhesive composition and antistatic agent and mixed and form adhesive layer, but be coated with viscous Knot agent composition and be dried and after laminating adhesive layer, by adhesive layer surface assign suitable antistatic agent at Point, it can lower inhibit removing electrostatic pressure when removing surface protection film from the optical film as adherend, and base The present invention is completed in above-mentioned discovery.
The present invention is exactly to complete in view of the foregoing, project be to provide the pollution of a kind of pair of adherend less, And the Antistatic surface of the excellent antistripping antistatic property with no deterioration (not deteriorating as time goes by) is protected Cuticula.
The method to solve the problem
In order to solve the above problems, the technical idea of Antistatic surface protective film of the present invention is, in applied adhesive group Close object and be dried and after laminating adhesive layer, the surface of the adhesive layer is assigned be at suitable 20 DEG C liquid poly- silicon Oxygen alkane (silicone, silicone) class compound and antistatic agent, thereby, it is possible to lower inhibit the pollution to adherend, And can lower inhibit from the optical film as adherend remove when removing electrostatic pressure.
In order to solve the above problems, the present invention provides a kind of Antistatic surface protective film, is successively by following processes (1)~(2) are fabricated,
Process (1)：It is formed on by the single side for the base material film that there is the resin of the transparency to constitute by adhesive composition structure At adhesive layer process,
The adhesive composition includes：(A) carbon atom number of alkyl is in (methyl) acrylate monomer of C4~C18 It is at least one with selected from as not the including carboxylic copolymerisable monomer of copolymerisable monomer group and by (B) hydroxyl can Comonomer and (C) not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer institute group containing alkoxy At at least one of copolymerisable monomer group copolymer acrylic polymer；It further include the different of (D) two function or more Cyanate esters, (E) crosslinking accelerator and (F) ketone-enol tautomers compound,
Process (2)：Stripping film made of the peeling agent layer containing antistatic agent will be laminated on resin film single side, passes through institute The process that peeling agent layer fits on the surface of the adhesive layer is stated,
Aforementioned peeling agent layer is by containing making remover as main component with dimethyl polysiloxane, at 20 DEG C be liquid The resin combinations of polysiloxanes (silicone) the class compound of body and foregoing antistatic agents is formed, foregoing adhesives layer Removing electrostatic pressure is ± 0.6kV or less.
In addition, preferably further containing (G) polyalkylene glycol mono (methyl) acrylic acid as aforementioned copolymerisable monomer group Ester monomer.
Additionally, it is preferred that aforementioned (E) crosslinking accelerator is selected from being made of aluminium chelate compound, titanium chelate, iron chelate At least one of group more than.
Additionally, it is preferred that the copolymerisable monomer of aforementioned (B) hydroxyl be selected from by (methyl) acrylic acid 8- hydroxyl monooctyl ester, The own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxy methacrylate, N- hydroxyl (methyl) acrylamide, N- methylol (methyl) acrylamide, compound group composed by N- ethoxy (methyl) acrylamide At least one of more than.
Additionally, it is preferred that aforementioned (G) polyalkylene glycol mono (methyl) acrylate monomer is selected from polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl polyalkylene glycol (methyl) propylene It is more than at least one of acid esters.
In addition, for isocyanate compound more than aforementioned (D) two function, preferably as two functional isocyanates Closing object is non-ring type aliphatic isocyanates compound and diisocyanate cpd is made to react and generate with diol compound Compound, wherein as diisocyanate cpd be aliphatic diisocyanate, be selected from by tetramethylene diisocyanate Ester, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine two are different One of compound group composed by cyanate；It is selected from by 2- methyl 1,3- propylene glycol, 2,2- as diol compound Dimethyl -1,3- propylene glycol, 2- methyl-2-propyl -1,3- propylene glycol, 2- ethyl -2- butyl -1,3- propylene glycol, 3- methyl-1, 5- pentanediol, 2,2- dimethyl -1,3- propylene glycol monohydroxy pivalate, polyethylene glycol, compound composed by polypropylene glycol One of group, as trifunctional isocyanates compound, the preferably isocyanuric acid of hexamethylene diisocyanate compound Ester, the isocyanuric acid ester of isophorone diisocyanate compound, the addition product of hexamethylene diisocyanate compound, different Buddhist That addition product of ketone diisocyanate cpd, the biuret of hexamethylene diisocyanate compound, two isocyanide of isophorone The biuret of ester compound, the isocyanuric acid ester of tolunediisocyanate compound, xylylene diisocyanate compound Isocyanuric acid ester, the isocyanuric acid ester of hydrogenated xylylene diisocyanate compound, tolunediisocyanate compound Addition product, the addition product of xylylene diisocyanate compound, hydrogenated xylylene diisocyanate compound addition product.
In addition, preferably comprising (H) polyether modified siloxane chemical combination that HLB value is 7~15 in foregoing adhesives composition Object.
Additionally, it is preferred that the polysiloxane-based compound in aforementioned peeling agent layer is Siloxane-Oxyalkylene Copolymers.
Additionally, it is preferred that the foregoing antistatic agents in aforementioned peeling agent layer are alkali metal salt.
In addition, in order to solve the above problems, it is by with transparent that the present invention, which provides a kind of Antistatic surface protective film, Property the single side of base material film that constitutes of resin on form adhesive layer, will be in the list of resin film and on the surface of the adhesive layer Remover film made of the peeling agent layer containing antistatic agent is laminated on face, be bonded by the peeling agent layer,
The adhesive layer be by (A) alkyl carbon atom number be C4~C18 (methyl) acrylate monomer in extremely It is few a kind of and selected from as not the including carboxylic copolymerisable monomer of copolymerisable monomer group and by (B) hydroxyl can Comonomer and (C) not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer institute group containing alkoxy At at least one of copolymerisable monomer group the adhesive layer of acrylic polymer that constitutes of copolymer,
The peeling agent layer is by containing making remover as main component with dimethyl polysiloxane, at 20 DEG C be liquid The resin combination of the polysiloxane-based compound of body and antistatic agent is formed.
In addition, preferably further containing (G) polyalkylene glycol mono (methyl) acrylic acid as aforementioned copolymerisable monomer group Ester monomer.
Additionally, it is preferred that the polysiloxane-based compound in aforementioned peeling agent layer is Siloxane-Oxyalkylene Copolymers.
Additionally, it is preferred that the foregoing antistatic agents in aforementioned peeling agent layer are alkali metal salt.
In addition, the present invention provides a kind of optical film, it is bonded above-mentioned Antistatic surface protective film and forms.
In addition, the present invention provides a kind of optical component, it is bonded above-mentioned Antistatic surface protective film and forms.
Invention effect
Antistatic surface protective film of the invention is few to the pollution of adherend, and to the low pollution of adherend without warp Shi Bianhua (will not change) as time goes by.In addition, based on the present invention, even be capable of providing one kind LR polarizer, The adherend such as AG-LR polarizer surface was carried out the optical film of anti-pollution processing by polysiloxane compound, fluoride etc., Also the removing electrostatic pressure occurred when removing Antistatic surface protective film from adherend can lower be inhibited, and with no warp When deterioration and excellent antistripping antistatic property Antistatic surface protective film.
Based on Antistatic surface protective film of the invention, optical film surface can be reliably protected, therefore can be realized The raising of production efficiency and the raising of yield rate.
Detailed description of the invention
Fig. 1 is the constructed profile of Antistatic surface protective film of the invention.
Fig. 2 is the sectional view for indicating to peel the state of stripping film from Antistatic surface protective film of the invention.
Fig. 3 is the sectional view for indicating an embodiment of optical component of the invention.
The explanation of appended drawing 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 agent of liquid at 7 ... 20 DEG C；
8 ... adherend (optical component)；10 ... Antistatic surface protective films；
11 ... peel the Antistatic surface protective film after stripping film；
20 ... have been bonded the optical component of Antistatic surface protective film.
Specific embodiment
In the following, based on embodiment, the present invention will be described in detail.
Fig. 1 is the constructed profile of Antistatic surface protective film of the invention.The Antistatic surface protective film 10, is saturating The surface of the single side of bright base material film 1 is formed with adhesive layer 2.Stripping film 5 is fitted on 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 protective film 10 of the invention, using by there is the transparency and scratch Property resin constitute base material film.Thereby, it is possible to Antistatic surface protective film is being fitted in the optical section as adherend Implement the visual examination of optical component in the state of part.The film being made of the resin with the transparency as base material film 1, preferably Use polyethylene terephthalate, polyethylene naphthalate, polyethylene glycol isophthalate (polyethylene Isophthalate), the polyester films such as polybutylene terephthalate (PBT).As long as there is required intensity as the base material film and have The film being made of other resins also can be used in optics adaptability other than polyester film.Base material film 1 is not either draw Film is stretched, is also possible to be subjected to the film being stretched uniaxially or biaxially.Alternatively, it is also possible to by the stretching ratio of stretched film, stretch The orientation angles for being formed by axis direction along with crystallization of film are controlled in particular value.
For the thickness of the base material film 1 used in the Antistatic surface protective film 10 of the invention, there is no special limits It is fixed, for example, it is preferable to be 12~100 μm or so of thickness；It is then easily operated therefore more excellent if 20~50 μm or so of thickness Choosing.
In addition, as needed, can be arranged in the opposite sides in face that the formation of base material film 1 has adhesive layer 2 for preventing The only stain-proofing layer, antistatic layer of surface contamination, the hard conating for preventing scratch etc..In addition, on the surface of base material film 1, it can also be real The easily bondingizations such as the modified, smearing of silane coupling agent in the surface carried out based on corona discharge are applied to handle.
In addition, for adhesive layer 2 used in Antistatic surface protective film 10 of the invention, as long as in adherend Surface on be bonded, can simply be peeled after use and be difficult to pollute the adhesive layer of adherend, and It is not particularly limited, but in view of the durability etc. after being bonded on optical film, generalling use keeps (methyl) acrylate total Acrylic adhesive layer made of polymers crosslinking.
In particular it is preferred that (methyl) third that the host agent of acrylic adhesive is C4~C18 by the carbon atom number of (A) alkyl At least one of olefin(e) acid ester monomer with selected from as not the including carboxylic copolymerisable monomer of copolymerisable monomer group and by (B) copolymerisable monomer of hydroxyl and (C) not hydroxyl and nitrogenous vinyl monomer or (methyl) acrylic acid containing alkoxy The bonding that the acrylic polymer of the copolymer of at least one of copolymerisable monomer group composed by alkyl ester monomer is constituted Oxidant layer.
As aforementioned copolymerisable monomer group, it can further contain (G) polyalkylene glycol mono (methyl) acrylate monomer.
Isocyanates chemical combination more preferably by also containing (D) two function or more other than foregoing acrylic polymer The adhesive layer that the adhesive composition of object, (E) crosslinking accelerator and (F) ketone-enol tautomers compound is constituted.
(methyl) acrylate monomer that carbon atom number as (A) alkyl is C4~C18, can enumerate：(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 setting the total amount of acrylic polymer of copolymer as 100 parts by weight, the preferred carbon atom of (A) alkyl The content of (methyl) acrylate monomer that number is C4~C18 is 50~95 parts by weight.
As the copolymerisable monomer of (B) hydroxyl, can enumerate：(methyl) acrylic acid 8- hydroxyl monooctyl ester, (methyl) propylene (methyl) dihydroxypropyls such as the own ester of sour 6- hydroxyl, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxy methacrylate Alkyl esters；N- hydroxyl (methyl) acrylamide, N- methylol (methyl) acrylamide, N- ethoxy (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- hydroxyl monooctyl ester, (methyl) propylene The own ester of sour 6- hydroxyl, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxy methacrylate, N- hydroxyl (methyl) acryloyl At least one of amine, N- methylol (methyl) acrylamide, compound group composed by N- ethoxy (methyl) acrylamide More than.
When setting the total amount of acrylic polymer of copolymer as 100 parts by weight, preferably aforementioned (B) hydroxyl The content of copolymerisable monomer is 0.1~10 parts by weight.
It is preferred that foregoing acrylic polymer contains (C) not hydroxyl and nitrogenous ethylene as aforementioned copolymerisable monomer group It is more than at least one of base monomer or (methyl) alkyl acrylate monomer containing alkoxy.
In (C), the vinyl monomer nitrogenous as (C-1) can be enumerated：Vinyl monomer containing amido bond contains Vinyl monomer, vinyl monomer with nitrogen-containing heterocycle structure for having amino etc..More specifically, it can enumerate：N- ethylene Base -2-Pyrrolidone, n-vinyl pyrrolidone, methyl ethylene pyrrolidones, N- vinylpyridine, N- vinylpiperidine Ketone, N- vinyl pyrimidine, N- vinyl piperazine, N- vinylpyrazine, N- vinyl pyrrole, N- vinyl imidazole, N- vinyl Replacing with N- vinyl for oxazole, N- polyvinyl morpholinone, N- caprolactam, N- vinyl lauric lactam etc. is miscellaneous The cyclic annular nitrogen vinyl compound of ring structure；N- (methyl) acryloyl morpholine, N- (methyl) acryloylpiperazines, N- (methyl) Propylene acyl group aziridine, N- (methyl) acryloyl group azetidine, N- (methyl) acryloyl group pyrrolidines, N- (methyl) acryloyl group Piperidines, N- (methyl) acryloyl group azepan, N- (methyl) acryloyl group Azacyclooctane etc. have N- (methyl) third The cyclic annular nitrogen vinyl compound for the heterocycle structure that enoyl- replaces；N- N-cyclohexylmaleimide, N-phenylmaleimide Deng the cyclic annular nitrogen vinyl compound with the heterocycle structure containing nitrogen-atoms and vinyl-based unsaturated bond in ring；(methyl) Acrylamide, N- methyl (methyl) acrylamide, N- isopropyl (methyl) acrylamide, N- tert-butyl (methyl) acrylamide etc. (methyl) acrylamide that unsubstituted or monoalkyl replaces；N, N- dimethyl (methyl) acrylamide, N, N- diethyl (first Base) acrylamide, N, N- dipropyl acrylamide, N, N- diisopropyl (methyl) acrylamide, N, N- dibutyl (methyl) third Acrylamide, N- ethyl-N-methyl (methyl) acrylamide, N- Methyl-N-propyl (methyl) acrylamide, N- methyl-N-isopropyl 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- dimethylaminopropyl (methyl) acrylate, N, N- dimethyl Amino isopropyl (methyl) acrylate, N, N- dimethrlaminobutyl (methyl) acrylate, N, N- diethylamino methyl (methyl) acrylate, N, N- diethylamino ethyl (methyl) acrylate, N- ethyl-N-methylamino ethyl (methyl) third Olefin(e) acid ester, N- methyl-N-propylamino ethyl (methyl) acrylate, N- methyl-N-isoproylamino ethyl (methyl) propylene Acid esters, N, the dialkyl aminos such as N- Dibutylaminoethyl (methyl) acrylate, t-butylamino ethyl (methyl) acrylate Base (methyl) acrylate；N, N- dimethylaminopropyl (methyl) acrylamide, N, N- diethyl amino propyl (methyl) third Acrylamide, N, N- dipropylamino propyl (methyl) acrylamide, N, N- diisopropylaminoethyl propyl (methyl) acrylamide, N- Ethyl-N-methylamino propyl (methyl) acrylamide, N- methyl-N-propylamino propyl (methyl) acrylamide, N- methyl- The N of N- isopropylaminopropyl (methyl) acrylamide etc., N- dialkyl group substituted-amino propyl (methyl) acrylamide；N- ethylene The N- vinylcarboxylic acid amide types such as base formamide, N- vinyl acetamide, N- vinyl-N-methylacetaniide；N- methoxy methyl Base (methyl) acrylamide, N- ethoxyethyl group (methyl) acrylamide, N- butoxymethyl (methyl) acrylamide, diacetone Acrylamide, N, (methyl) acrylic amide such as N- di-2-ethylhexylphosphine oxide (methyl) acrylamide；The unsaturation carboxylic such as (methyl) acrylonitrile Sour nitrile；Deng.
The vinyl monomer nitrogenous as (C-1), preferably not hydroxyl, more preferably not hydroxyl and carboxyl.As this Monomer, the monomer being preferably illustrated above, such as：Containing N, N- dialkyl group substituted-amino, N, N- dialkyl group substituted amido Acrylic monomer；The N- vinyl such as n-vinyl-2-pyrrolidone, N- caprolactam, 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 (C), (methyl) alkyl acrylate monomer as (C-2) containing alkoxy can be enumerated：(methyl) propylene Sour 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 2- propoxy ethyl, (methyl) acrylic acid 2- isopropoxyethyl cyanoacrylate, (methyl) acrylic acid 2- butoxyethyl, (methyl) acrylic acid 2- methoxyl group propyl ester, (methyl) acrylic acid 2- ethyoxyl propyl ester, (methyl) acrylic acid 2- propoxyl group propyl ester, (methyl) acrylic acid 2- isopropoxy propyl ester, (methyl) acrylic acid 2- butoxy propyl ester, (methyl) acrylic acid 3- methoxyl group propyl ester, (methyl) acrylic acid 3- ethyoxyl propyl ester, (methyl) acrylic acid 3- Propoxyl group propyl ester, (methyl) acrylic acid 3- isopropoxy propyl ester, (methyl) acrylic acid 3- butoxy propyl ester, (methyl) acrylic acid 4- Methoxybutyl, (methyl) acrylic acid 4- Ethoxybutyl, (methyl) acrylic acid 4- propoxyl group butyl ester, (methyl) acrylic acid 4- are different Propoxyl group butyl ester, (methyl) acrylic acid 4- butoxy butyl ester etc..
These (methyl) alkyl acrylate monomers containing alkoxy, with the alkyl in (methyl) alkyl acrylate The structure that atom is replaced by alkoxy.
When setting the total amount of acrylic polymer of copolymer as 100 parts by weight, preferably (C-1) not hydroxyl and The content of (methyl) alkyl acrylate monomer of nitrogenous vinyl monomer or (C-2) containing alkoxy is 0~20 parts by weight. For (C-1) not hydroxyl and nitrogenous vinyl monomer and (methyl) alkyl acrylate monomer of (C-2) containing alkoxy, Both it using one kind or can be used together two or more respectively.It can not also in the adhesive composition of adhesive layer of the invention Include (C) not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxy.
As isocyanate compound more than (D) two function, as long as at least having two or more in a molecule At least one of polyisocyanate compounds of isocyanates (NCO) base or two or more.Polyisocyanate chemical combination Object includes aliphatic category isocyanates, aromatic isocyanates, non-ring type kind isocyanate, ester ring type kind isocyanate equal part Class, the present invention can be any kind therein.As the specific example of polyisocyanate compounds, can enumerate：Six methylenes The rouge such as group diisocyanate (HDI), isophorone diisocyanate (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 isocyanate compound.
As isocyanate compound more than trifunctional, can enumerate：Two functional isocyanate compounds are (in a molecule Middle tool there are two NCO base compound) biuret modified body or isocyanurate-modified body, with trimethylolpropane (TMP) Or the addition product of polyalcohols (at least having the compound there are three the above OH base in a molecule) more than the trivalents such as glycerol is (polynary Alcohol modified body) etc..
As isocyanate compound more than (D) two function, can only with (D-1) trifunctional isocyanates compound, Or only with (D-2) two functional isocyanate compound.Alternatively, it is also possible to and with (D-1) trifunctional isocyanates compound (D-2) two functional isocyanate compound.
Also, (D-1) trifunctional isocyanates compound used in the present invention is preferably included selected from (D-1-1) At least one of first aliphatic category isocyanate compound group is above and is selected from (D-1-2) second aromatic isocyanates More than at least one of compound group, wherein (D-1-1) first aliphatic category isocyanate compound group is by six Asias The isocyanuric acid ester of methyl diisocyanate compound, the isocyanuric acid ester of isophorone diisocyanate compound, six methylenes The addition product of group diisocyanate compound, the addition product of isophorone diisocyanate compound, hexa-methylene diisocyanate The biuret of ester compounds, the biuret of isophorone diisocyanate compound are formed；(D-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 object, the isocyanuric acid ester of hydrogenated xylylene diisocyanate compound, tolunediisocyanate compound Addition product, xylylene diisocyanate compound addition product, hydrogenated xylylene diisocyanate compound addition Object is formed.(D-1-1) the first aliphatic category isocyanate compound group and (D-1-2) second aromatic isocyanide is preferably used in combination Ester compound group.In the present invention, as (D-1) trifunctional isocyanates compound, by and be selected from (D-1-1) first At least one of aliphatic category isocyanate compound group is above and is selected from (D-1-2) second aromatic isocyanates chemical combination More than at least one of object group, it can further improve the balance of low speed stripping area and the cohesive force in high speed stripping area Property.
Additionally, it is preferred that (D-1) trifunctional isocyanates compound contains selected from aforementioned (D-1-1) the first aliphatic category isocyanide At least one of ester compound group is above and in aforementioned (D-1-2) second aromatic isocyanate compound group More than at least one, total amount is 0.5~5.0 parts by weight relative to the aforementioned copolymer of 100 parts by weight.In addition, as choosing From more than at least one of (D-1-1) first aliphatic category isocyanate compound group and selected from (D-1-2) second aromatic series Blending ratio more than at least one of kind isocyanate compound group, being calculated with weight ratio is preferably (D-1-1):(D-1- 2) 10%:90%~90%:In the range of 10%.
Also, (D-2) the two functional isocyanate compound used as the present invention, preferably non-ring type aliphatic isocyanide Ester compound and it is diisocyanate cpd and diol compound reacts and the compound that generates.
For example, when indicating diisocyanate chemical combination with general formula " O=C=N-X-N=C=O " (wherein, X is divalent group) Object, when indicating diol compound with general formula " HO-Y-OH " (wherein, Y is divalent group), as diisocyanate cpd and two Alcoholic compound reacts compound generated, for example, the compound of the following general formula Z expression can be enumerated.
[general formula Z]
O=C=N-X- (NH-CO-O-Y-O-CO-NH-X)n- N=C=O
Here, the integer that n is 0 or more.When n is 0, general formula Z is expressed as " O=C=N-X-N=C=O ".As two officials Can non-ring type aliphatic isocyanates compound also may include n is 0 in general formula Z compound (not relative to diol compound The diisocyanate cpd of reaction), preferably as must composition contain n be 1 or more integer compound.Two functions are acyclic Formula aliphatic isocyanates compound is also possible to the mixture as composed by the n different multiple compounds in general formula Z.
The diisocyanate cpd that general formula " O=C=N-X-N=C=O " indicates, is aliphatic diisocyanate.It is preferred that X is the aliphatic divalent group of non-ring type.As aforementioned aliphatic diisocyanate, it is preferably chosen from by two isocyanide of tetramethylene Acid esters, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine two One or more of compound group composed by isocyanates.
Diol compound shown in general 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, it is preferably selected from by 2- methyl 1,3-PD, 2,2-dimethyl-1,3-propanediol, 2- Methyl-2-propyl -1,3- propylene glycol, 2- ethyl -2- butyl -1,3- propylene glycol, 3- methyl-1,5- pentanediol, 2,2- dimethyl - One or more of 1,3- propylene glycol monohydroxy pivalate, polyethylene glycol, compound group composed by polypropylene glycol.
It is preferred that the weight ratio of aforementioned (D-1) trifunctional isocyanates compound and (D-2) two functional isocyanate compound It (D-1/D-2) is 1~90.It is more than preferably aforementioned (D) two function different relative to 100 parts by weight foregoing acrylic polymer Cyanate esters are 0.1~10 parts by weight.
Using polyisocyanate compounds as crosslinking agent, (E) as long as crosslinking accelerator as catalyst And to the substance that the reaction of aforementioned copolymer and crosslinking agent (cross-linking reaction) functions, it can enumerate：The amine of tertiary amine etc. Organo-metallic compounds such as class compound, metallo-chelate, organo-tin compound, organo-lead compound, organic zinc compound etc.. In the present invention, metallo-chelate, organo-tin compound are preferably used as crosslinking accelerator.
It is that more than one multidentate ligand L is bonded to compound made of central metal atom M as metallo-chelate.Gold Category chelate, which both can have, can also not have the more than one monodentate ligand X being bonded on metallic atom M.For example, working as The general formula for the metallo-chelate that metallic atom M is one is with M (L) m (X)nWhen expression, m >=1, n >=0.When m is 2 or more, m L either identical ligand is also possible to different ligand.When n is 2 or more, n X are either identical ligand It is also possible to different ligand.
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- pentanedione), 2, The beta-diketon of 4- acetyl butyryl, benzoyl acetone etc..They are ketone-enol tautomers compounds, can also in multidentate ligand L To be that enol carries out enolate (for example, acetylacetonate) made of deprotonation.
As monodentate ligand X, the halogen atoms such as chlorine atom, bromine atom, valeryl, caproyl, 2- ethyl hexanoyl can be enumerated The acyloxy such as base, caprylyl, pelargonyl group, capryl, Lauroyl, stearyl, methoxyl group, ethyoxyl, positive propoxy, isopropyl Alkoxies such as oxygroup, butoxy etc..
As the specific example of metallo-chelate, can enumerate：Three (2,4- pentanedione) 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), bis- (2,4- acetyl butyryl) zinc, three (2,4- acetyl butyryl) titaniums, three (2,4- acetyl butyryl) aluminium, four (2,4- acetyl butyryls) Zirconium etc..
As organo-tin compound, can enumerate：Dialkyl tin oxide, the fatty acid salt of dialkyl tin, stannous rouge 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 especially tributyl tin contained in dibutyltin compound (TBT) is also to make us carrying on a shoulder pole as endocrine disruptors The heart.It sets 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 Object, but in view of the trend for requiring the higher substance of safety in utilization in the future, it is preferable to use highly-safe Al, Ti, Fe in Sn Deng metallo-chelate.
As (E) crosslinking accelerator in adhesive composition of the invention, it is preferably selected from by aluminium chelate compound, titanium chela Close at least one of group composed by object, iron chelate or more.
Relative to 100 parts by weight copolymers, the preferably content of (E) crosslinking accelerator is 0.001~0.5 parts by weight.
As (F) 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 butyryl, benzoyl acetone etc..They are in the binder combination using polyisocyanate compounds as crosslinking agent In object, by closing isocyanate group possessed by crosslinking agent, it is able to suppress adhesive composition after cooperation crosslinking agent The phenomenon that excessive rising or gelation of viscosity, it is able to extend the storage period of adhesive composition.
Relative to the copolymer of 100 parts by weight, preferably the content of (F) ketone-enol tautomers compound be 0.1~ 200 parts by weight.
(F) ketone-enol tautomers compound has the effect of the inhibition crosslinking opposite with (E) crosslinking accelerator, because This, preferably suitably sets ratio of (F) the ketone-enol tautomers compound relative to (E) crosslinking accelerator.It is viscous in order to extend The storage period of agent composition is tied, and improves storage stability, preferably (E):(F) weight ratio is 1:1~1:500 range, more Preferably 1:30~1:500, most preferably 1:80~1:500.
For foregoing acrylic polymer, as aforementioned copolymerisable monomer group, it can arbitrarily contain (G) polyalkylene two Alcohol list (methyl) acrylate monomer.As (G) polyalkylene glycol mono (methyl) acrylate monomer, as long as polyalkylene A hydroxyl in multiple hydroxyls possessed by glycol is esterified as the compound of (methyl) acrylate.Due to (methyl) Acrylate-based is polymerism base, therefore can be copolymerized with host agent polymer.Other hydroxyls can both keep the shape of OH State can also become the alkyl ether of methyl ether, ether etc., or can become saturated carboxylic acids esters such as acetate etc..
As alkylidene possessed by polyalkylene glycol, ethylidene, propylidene, butylidene etc. can be enumerated, but not It is defined in these.Polyalkylene glycol is also possible to the two or more poly- alkylenes in polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc. The copolymer of base glycol.As the copolymer of polyalkylene glycol, polyethylene glycol propylene glycol, polyethylene glycol can be enumerated Butanediol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol propylene glycol-polytetramethylene glycol etc., which can be block copolymerization Object, random copolymer.
It is preferred that constituting the alkylene oxide of polyalkylene glycol chain in (G) 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 (G) polyalkylene Alkylene oxide unit weight in " polyalkylene glycol chain " part contained in the molecular structure of glycol list (methyl) acrylate monomer Multiple average.
As (G) polyalkylene glycol mono (methyl) acrylate monomer, it is preferably selected from polyalkylene glycol mono (first Base) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl polyalkylene glycol (methyl) acrylate At least one of more than.
More specifically, it can enumerate：Mono- (methyl) acrylate of polyethylene glycol-, mono- (methyl) acrylic acid of polypropylene glycol- Mono- (methyl) acrylate of ester, polytetramethylene glycol-, polyethylene glycol propylene glycol-mono- (methyl) acrylate, polyethylene glycol fourth Mono- (methyl) acrylate of glycol-, mono- (methyl) acrylate of polypropylene glycol-polytetramethylene glycol-, polyethylene glycol propylene glycol-are poly- Mono- (methyl) acrylate of butanediol-；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, the poly- second of ethyoxyl- Glycol-polypropylene glycol-(methyl) acrylate, ethyoxyl-polyethylene glycol butanediol-(methyl) acrylate, ethyoxyl- Polypropylene glycol-polytetramethylene glycol-(methyl) acrylate, ethyoxyl-polyethylene glycol propylene glycol-polytetramethylene glycol-(methyl) propylene Acid esters etc..
When setting the total amount of acrylic polymer of copolymer as 100 parts by weight, preferably aforementioned (G) polyalkylene The content of glycol list (methyl) acrylate monomer is 0~50 parts by weight.Adhesive composition in adhesive layer of the invention (G) polyalkylene glycol mono (methyl) acrylate monomer can also not included.
Adhesive composition can arbitrarily contain (H) polyether modified siloxane compound.(H) polyether-modified silicone compound Object is the silicone compounds with polyether-based, in addition to common siloxane unit (- SiR1 2- O-) except, also have comprising poly- The siloxane unit (- SiR of ether1(R2O(R3O)nR4)-O-).Here, R1Indicate one or more kinds of alkyl or aryls, R2And R3Indicate one or more kinds of alkylidenes, R4Indicate (terminal groups) such as one or more kinds of alkyl, acyl groups.Make It can be enumerated for polyether-based：Polyethylene oxide base ((C2H4O)n) or polypropylene oxide base ((C3H6O)n) etc. polyoxyalkylenes.
It is preferred that (H) polyether modified siloxane compound is the polyether modified siloxane compound that HLB value is 7~15.In addition, Relative to the copolymer of 100 parts by weight, preferably the content of (H) polyether modified siloxane compound is 0.01~1.0 parts by weight, more Preferably 0.1~0.5 parts by weight.
HLB refer to such as JIS K3211 (surfactant term) as defined in hydrophile-lipophile balance (hydrophily and oleophylic The ratio of property).
(H) 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 It obtains.Specifically, can enumerate：Dimethyl siloxane-methyl (polyethylene glycol oxide) silicone copolymers, dimethyl silica Alkane-methyl (polyethylene glycol oxide) siloxane-methyl (polypropylene oxide) silicone copolymers, dimethyl siloxane-methyl (polyoxy Change propylene) silicone copolymers etc..
By the way that (H) polyether modified siloxane compound is matched with adhesive composition, the bonding of binder 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 ingredients, 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 promotion Additive well known to agent, plasticizer, filler, curing inhibitors, processing aid, age resister, antioxidant etc..These both may be used To be used alone, can also be used in combination of two or more.
It, can be by by the carbon atom number of (A) alkyl as the copolymer of host agent used in adhesive composition of the invention At least one of (methyl) acrylate monomer for C4~C18, with selected from as copolymerisable monomer group by (B) containing hydroxyl The copolymerisable monomer of base, (C) not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate list containing alkoxy At least one of copolymerisable monomer group composed by body is copolymerized to synthesize.It, can also be into as aforementioned copolymerisable monomer group One step contains (G) polyalkylene glycol mono (methyl) acrylate monomer.To the polymerization of copolymer, there is no particular limitation, The polymerization appropriate such as polymerisation in solution, emulsion polymerization can be used.
Adhesive composition of the invention can pass through the isocyanates in above-mentioned copolymer more than cooperation (D) two function Compound, (E) crosslinking accelerator, (F) ketone-enol tautomers compound, there are also any additives appropriate to be matched System.
It is preferred that aforementioned copolymer is acrylic polymer, (methyl) acrylate of 50~100 weight % is preferably comprised The acrylic monomers such as monomer or (methyl) acrylic acid, (methyl) acrylic amide.
Since foregoing acrylic polymer does not include carboxylic copolymerisable monomer as copolymerisable monomer group, to crosslinking The raising of speed and the stabilisation of cohesive force are effective.As be used as crosslinking agent (D) two function more than isocyanates chemical combination Monomer that object reacts, it is preferable to use (B) hydroxyl copolymerisable monomer.As the preferred monomer composition of aforementioned copolymer, Can enumerate in aforementioned (A) and aforementioned (B) it is each more than one, in aforementioned (A) and aforementioned (B) and aforementioned (C) it is each it is a kind of with In upper, aforementioned (A) and aforementioned (B) and aforementioned (G) it is each more than one, in aforementioned (A) and aforementioned (B) and aforementioned (C) and (G) Respectively more than one etc..
It is preferred that bonding of the adhesive layer at low peeling rate 0.3m/min made of being crosslinked foregoing adhesives composition Power is 0.05~0.1N/25mm, and the cohesive force at high peeling rate 30m/min is 1.0N/25mm or less.Thereby, it is possible to obtain The cohesive force performance small with the variation of peeling rate is obtained, even can also remove rapidly in the case where high speed is removed.Also, Even if temporarily remove surface protection film to re-paste, without excessive strength, it is easy to remove from adherend.
It is preferred that the surface resistivity of adhesive layer made of being crosslinked foregoing adhesives composition is 5.0 × 10+12Ω/□ Hereinafter, removing electrostatic pressure is " ± 0.6kV or less ".In addition, in the present invention, so-called " ± 0.6kV's or less " is meant that " 0 ~-0.6kV " and " 0~+0.6kV ", i.e. " -0.6~+0.6kV ".If surface resistivity is big, produced when to removing because of electrification The performance that raw electrostatic is discharged is poor, therefore, by keeping surface resistivity sufficiently small, can reduce and shells with from adherend Electrostatic pressure is removed caused by the electrostatic occurred when from adhesive layer, is able to suppress the shadow to the electric control circuit of adherend etc. It rings.
It is preferred that the gel point of adhesive layer (binder after crosslinking) made of being crosslinked adhesive composition of the invention Number is 95~100%.Since gel fraction is so high, cohesive force will not become excessive in the case where low peeling rate, reduce The phenomenon that unconverted monomer or oligomer are dissolved out from copolymer, it is so as to improve resistance under re-workability, high temperature/high humidity Long property, and inhibit 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 of the invention is crosslinked.In addition, surface protection film of the invention is the single side formation bonding in resin film Oxidant layer forms, and the adhesive layer is to be crosslinked adhesive composition of the invention.In adhesive composition of the invention In, due to being combined with each ingredient of above-mentioned (A)~(F) with good balance, so there is excellent antistatic property, low The balance of peeling rate and the cohesive force under high peeling rate is excellent, and endurance quality and cycling processability (use ball After pen is described on surface protection film across adhesive layer, do not transfer the pollution to adherend) it is also excellent.Therefore, may be used Preferably as polarizer surface protection film purposes be subject to using.
To the thickness of adhesive layer 2 used in Antistatic surface protective film 10 of the invention, it 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 for Antistatic surface protective film It is 0.03~0.3N/25mm or so, binder with micro- cohesive force to the peel strength (cohesive force) on adherend surface When layer 2, operability when removing Antistatic surface protective film from adherend is excellent, therefore preferably.In addition, based on quiet from resisting Ammeter surface protective film 10 peels operational excellent viewpoint when stripping film 5, and preferably stripping film 5 is peeled from adhesive layer 2 Peeling force is 0.2N/50mm or less.
In addition, being the list in resin film 3 for the stripping film 5 used in the Antistatic surface protective film 10 of the invention It forms peeling agent layer 4 on face to form, which is using containing with dimethyl polysiloxane making removing as main component Agent is that the polysiloxane-based compound of liquid and the resin combination of antistatic agent are formed at 20 DEG C.
As resin film 3, polyester film, PA membrane, polyethylene film, polypropylene screen, polyimide film etc. can be enumerated, from From the perspective of excellent transparency and less expensive, particularly preferably polyester film.Resin film either unstretching film, It 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 Change the orientation angles control for being formed by axis direction in particular value.
The thickness of 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, also can according to need the surface modification for implementing to carry out based on corona discharge, bottom on the surface of resin film 3 The easily bondingization processing such as smearing of paint.
As constitute peeling agent layer 4, remover as main component made with dimethyl polysiloxane, addition can be enumerated The well known polysiloxane-based remover of response type, condensation reaction type, cationic polymerization type, radical polymerization mould assembly etc..As adding At the commercially available product of the polysiloxane-based remover of response type, for example, can enumerate：KS-776A,KS-847T,KS-779H,KS- 837, 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..As the commercially available product of cationic polymerization type, for example, TPR- can be enumerated 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 polysiloxane-based compound that constitute peeling agent layer 4, at 20 DEG C to be liquid, can enumerate polyether-modified poly- Siloxanes, alkyl-modified polysiloxanes, methanol high-grade aliphatic ester modified polyorganosiloxane etc..In the present invention, viscous in order to improve The antistatic property for tying oxidant layer surface, using in the state for making to mix in peeling agent layer as main component with dimethyl polysiloxane 20 DEG C at be liquid polysiloxane-based compound.For purposes of the invention, preferably modified polyorganosiloxane compound In Siloxane-Oxyalkylene Copolymers.Polyether chain in Siloxane-Oxyalkylene Copolymers is by ethylene oxide (ethylene oxide), oxidation third Alkene (propylene oxide) etc. is constituted, for example, can be adjusted and poly- silicon by the molecular weight of polyethylene glycol oxide used in selection side chain 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- 353, 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 (it is high-new to step figure Materials Co., Ltd (Momentive Performance Materials Inc.) manufacture)；BYK-300,BYK-306,BYK-307, BYK-320, BYK-325, BYK-330 (manufacture of BYK-Chemie company) etc..
It is that the polysiloxane-based compound of liquid makees stripping as main component relative to dimethyl polysiloxane at 20 DEG C Additive amount from agent, be according to the type of polysiloxane compound, from the difference of the intermiscibility degree of remover and it is different, as long as Required removing electrostatic pressure when in view of removing Antistatic surface protective film from adherend, to the pollution of adherend, Bonding characteristic etc. and set.
As the antistatic agent for constituting peeling agent layer 4, make stripping as main component preferably for dimethyl polysiloxane Favorable dispersibility from agent solution, and do not hinder to make the cured anti-of remover as main component with dimethyl polysiloxane Electrostatic agent.As such antistatic agent, preferred as alkali salt.
As alkali metal salt, can enumerate：Comprising lithium, sodium, potassium metal salt, specifically, for example, it is preferable to using passing through Include Li+、Na+、K+Deng cation with include Cl-、Br-、I-、BF4 -、PF6 -、SCN-、ClO4 -、CF3SO3 -、(CF3SO2)2N-、 (C2F5SO2)2N-、(CF3SO2)3C-Deng the metal salt that is constituted of anion.Wherein, particularly preferably using LiBr, LiI, LiBF4、LiPF6、LiSCN、LiClO4、LiCF3SO3、Li(CF3SO2)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.It, can also be with for the stabilisation of ionic substance Add the compound containing polyoxyalkyl based structures.
Antistatic agent is quiet according to resisting relative to the additive amount for making remover as main component with dimethyl polysiloxane The type of electric agent, from the difference of the degree of the compatibility of remover and it is different, but in view of removed from adherend it is antistatic Required removing electrostatic pressure when surface protection film sets pollution, bonding characteristic of adherend etc..
For making remover and Siloxane-Oxyalkylene Copolymers and antistatic agent as main component with dimethyl polysiloxane Mixed method for, be not particularly limited.It can be using any method in following mixed method：With dimethyl Polysiloxanes is made in remover as main component, and addition after Siloxane-Oxyalkylene Copolymers and antistatic agent mixed is added Remover solidification catalyst and mixed method；Use organic solvent diluting using dimethyl polysiloxane as master in advance After the remover for wanting ingredient, adds Siloxane-Oxyalkylene Copolymers and antistatic agent and remover solidification catalyst and mixed The method of conjunction；In advance use organic solvent diluting to make remover as main component with polysiloxanes after, addition catalyst and into Then row mixing adds Siloxane-Oxyalkylene Copolymers and antistatic agent and mixed method etc..In addition, as needed, The material of the auxiliary antistatic effect of the adhesion promotors such as silane coupling agent, compound containing polyoxyalkylene etc. can be added Material.
For making remover and Siloxane-Oxyalkylene Copolymers and antistatic agent as main component with dimethyl polysiloxane Blending ratio for, be not particularly limited, but make remover as main component relative to dimethyl polysiloxane Solid component 100, preferred, polyethers modified polyorganosiloxane and antistatic agent are calculated as 5~100 or so ratio with solid component.Phase For making the solid component 100 of remover as main component with dimethyl polysiloxane, if Siloxane-Oxyalkylene Copolymers and anti- Ratio of the additive amount less than 5 of electrostatic agent to be converted with solid component, then transfer amount of the antistatic agent to adhesive layer surface It tails off, it is difficult to adhesive layer be made to play antistatic function.In addition, as main component relative to being made with dimethyl polysiloxane The solid component 100 of remover, if the additive amount with solid component conversion of Siloxane-Oxyalkylene Copolymers and antistatic agent is more than 100 ratio then causes together with Siloxane-Oxyalkylene Copolymers and antistatic agent using dimethyl polysiloxane as main component Remover can also be transferred to adhesive layer surface, accordingly, it is possible to which the bonding characteristic of adhesive layer can be reduced.
The method and fitting stripping of adhesive layer 2 are formed in the present invention on the base material film 1 of Antistatic surface protective film 10 Well known method can be used to carry out in method from film 5, and there is no particular limitation.Specifically, can enumerate：(1) it will use It in the resin combination for forming adhesive layer 2, is coated on the single side of base material film 1 and is dried, pasted after forming adhesive layer The method for closing stripping film 5；(2) resin combination for being used to form adhesive layer 2 is coated on 5 surface of stripping film and is done It is dry, after forming adhesive layer, it is bonded the method etc. of base material film 1.Any method therein can be used.
In addition, well known method can be used to carry out when adhesive layer 2 is formed in 1 surface of base material film.It is specific and Speech is able to use and coating, comma scraper coating, intaglio plate coating, slit extrusion coated, wheat is reversed to strangle stick (Mayer bar) and apply Coating method well known to cloth, airblade coating etc..
In addition, similarly, when peeling agent layer 4 is formed in resin film 3, can be carried out using well known method.Tool For body, coating method well known to stick coating, airblade coating etc. can be strangled using intaglio plate coating, wheat.
Fig. 2 is the sectional view for indicating to peel the state after stripping film from Antistatic surface protective film of the invention.
By the way that stripping film 5 is peeled from Antistatic surface protective film 10 shown in FIG. 1,4 institute of peeling agent layer of stripping film 5 It is the polysiloxane-based compound of liquid and a part of antistatic agent (appended drawing reference 7) at 20 DEG C contained, is transferred (attachment) To the surface of the adhesive layer 2 of Antistatic surface protective film 10.Therefore, in Fig. 2, schematically with the spot of appended drawing reference 7 Show polysiloxane-based chemical combination being transferred to 2 surface of adhesive layer of Antistatic surface protective film, at 20 DEG C being liquid Object and antistatic agent.
For Antistatic surface protective film of the invention, when by resisting for the state shown in Fig. 2 for having peeled stripping film it is quiet When ammeter surface protective film 11 is fitted in adherend, poly- silicon being transferred to 2 surface of adhesive layer, at 20 DEG C being liquid Oxygen alkyl compound and antistatic agent are contacted with adherend surface.Thereby, it is possible to lower inhibit again from being attached Removing electrostatic pressure when Antistatic surface protective film is peeled on body.
Fig. 3 is the sectional view for indicating the embodiment of optical component of the invention.
Stripping film 5 is being peeled from Antistatic surface protective film 10 of the invention to the exposed state of adhesive layer 2 Under, it is fitted on the optical component 8 as adherend by the adhesive layer 2.
That is, the optical component 20 for being fitted with Antistatic surface protective film 10 of the present invention is shown in FIG. 3.As optical section Part can enumerate polarizer, phase plate, lens coating, the polarizer for being also used as phase plate, the polarizer for being also used as lens coating Equal optical films.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 set etc..In addition, as optical component, antireflection film, hard coat film, touch panel can also be enumerated with transparent The optical films such as conductive film.In particular, can be preferably used as fitting in surface polysiloxane compound, fluorine compounds etc. into Going low reflection processing polarizer (LR polarizer) of anti-pollution processing, anti-dazzle low reflection handles polarizer (AG-LR polarizer) Antistatic surface protective film on the face for being applied with anti-pollution processing of equal optical films.
Based on optical component of the invention, when by Antistatic surface protective film 10 from the optical component as adherend When removing removal on (optical film), fully removing electrostatic pressure can be inhibited in low-level, therefore, can be destroyed without worrying The circuit block for driving IC, TFT element, gate line drive circuit etc. can be improved in the processes such as manufacture liquid crystal display panel Production efficiency, it is ensured that the reliability of production process.
Embodiment
In the following, further illustrating the present invention by embodiment.
<The manufacture of adhesive composition>
[embodiment 1]
Nitrogen is imported into the reaction unit equipped with blender, thermometer, reflux condenser and nitrogen ingress pipe, to use nitrogen Gas has replaced the air in reaction unit.Then, joined into reaction unit 100 parts by weight 2-EHA, The acrylic acid 8- hydroxyl monooctyl ester of 5.0 parts by weight, and joined the solvent (ethyl acetate) of 60 parts by weight simultaneously.Then, small by 2 When 0.1 parts by weight of azodiisobutyronitrile dripped as polymerization initiator, reacted 6 hours at a temperature of 65 DEG C, it is equal to obtain weight The acrylic acid copolymer soln of the embodiment 1 of molecular weight 500,000.To the acrylic acid copolymer soln, 8.5 parts by weight acetyl are added Acetone and after being stirred, is added 2.0 parts by weight Coronate HX (U ロ ネ ー ト HX, hexamethylene diisocyanate chemical combination The isocyanuric acid ester of object), 0.1 parts by weight praseodynium titanium and be stirred, obtain the binder combination of embodiment 1 Object.
[embodiment 2~6 and comparative example 1~3]
Other than each composition in addition to as described in Tables 1 and 2 having adjusted the adhesive composition of embodiment 1, with embodiment 1 It is carried out similarly operation, has obtained the adhesive composition of embodiment 2~6 and comparative example 1~3.In Tables 1 and 2, acrylic acid It is (A), (B), (C), (G) and " carboxylic monomer " that monomer (is copolymerized) contained in copolymer.
Table 1
Table 2
(E) (F) (G) (H) Antistatic agent
Embodiment 1 Titanium chelate (0.1) AA(8.5) - - -
Embodiment 2 Iron chelate (0.05) AA(4.0) G-1(5) H-1(0.1) -
Embodiment 3 Titanium chelate (0.03) AA(3.0) G-2(10) - -
Embodiment 4 Titanium chelate (0.03) AA(2.5) G-3(5) H-2(0.1) -
Embodiment 5 Iron chelate (0.03) AA(5.0) G-5(10) H-3(0.05) -
Embodiment 6 Iron chelate (0.04) EtAcAc(20) G-4(5) H-4(0.1) -
Comparative example 1 - - - - Li(CF3SO2)2N(0.3)
Comparative example 2 Iron chelate (1.5) AA(1.0) G-6(10) H-5(0.05) LiCF3SO3(0.1)
Comparative example 3 DOTL(0.1) AA(2.5) - - -
Tables 1 and 2 is the table that the whole table for indicating each components matching ratio is divided into two parts, the equal table of numerical value in bracket Show the numerical value for each Parts by Ingredients that the total amount organized with (A) is set as 100 parts by weight and finds out.In addition, will in Tables 1 and 2 The corresponding compound name of the abbreviation of each ingredient used is shown in table 3 and table 4.In addition, Coronate (U ロ ネ ー ト, registration Trade mark) HX, Coronate HL and Coronate L be Nippon Polyurethane Industry Co., Ltd. (Nippon Polyurethane Industry Co., Ltd.) product name, Takenate (タ ケ ネ ー ト, registered trademark) D-140N, D-127N, D-110N It is the product name of Mitsui Chemicals, Inc.
Table 3
Table 4
The synthesis > of bis- functional isocyanate compound of <
Two functional isocyanate compounds of synthesis example 1,2 are synthesized using following methods.That is, as shown in table 5 and table 6, it will Diisocyanate and diol compound are mixed with the ratio of molar ratio NCO/OH=16, are reacted 3 hours at 120 DEG C, then, are adopted It removes unreacted diisocyanate under reduced pressure with thin film evaporation unit, obtains desired two functional isocyanates chemical combination Object.
Table 5
Synthesis example 1D-1 Synthesis example 2D-2
Diisocyanate cpd HDI HDI
Diol compound K-1 K-2
Table 6
<The manufacture of Antistatic surface protective film>
[embodiment 1]
By addition reaction-type polysiloxanes (name of product SRX-345, the Dow Corning Toray Co., Ltd of 5 parts by weight (Dow Corning Toray Co., Ltd.) manufacture), (name of product is for the Siloxane-Oxyalkylene Copolymers of 0.15 parts by weight SH8400, Dow Corning Toray Co., Ltd (Dow Corning Toray Co., Ltd.) manufacture), the perchloric acid of 5 parts by weight The toluene and ethyl acetate of ethyl acetate solution, 95 parts by weight that lithium is 10% are 1:1 mixed solvent and 0.05 parts by weight Platinum catalyst (name of product be SRX-212 Catalyst (catalyst), Dow Corning Toray Co., Ltd manufacture) be blended in It together and is stirred, has prepared the coating for forming the peeling agent layer of embodiment 1.Stick is strangled using wheat, embodiment 1 will be formed Peeling agent layer coating, by make it is dry after thickness become 0.2 μm in a manner of, be coated on the poly- terephthaldehyde with a thickness of 38 μm The surface of sour glycol ester film, and it is 1 minute dry in 120 DEG C of heated air circulation type baker, obtain the removing of embodiment 1 Film.
The adhesive composition of embodiment 1 is coated in a manner of making the thickness after drying become 20 μm with a thickness of 38 μm polyethylene terephthalate film surface after, dry 2 minutes in 100 DEG C of heated air circulation type baker, 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 has been bonded it (polysiloxanes process face).Obtained adhesive film is kept the temperature 5 days in the environment of 40 DEG C, so that binder solidifies, is obtained The Antistatic surface protective film of embodiment 1.
[embodiment 2~6]
Other than each adhesive composition of embodiment 1 is respectively set as the adhesive composition of embodiment 2~6, It is operated similarly to Example 1, obtains the Antistatic surface protective film of embodiment 2~6.
[comparative example 1]
By addition reaction-type polysiloxanes (name of product SRX-345, the Dow Corning Toray Co., Ltd of 5 parts by weight Manufacture), the toluene of 95 parts by weight and ethyl acetate be 1:Platinum catalyst (the ProductName of 1 mixed solvent and 0.05 parts by weight Referred to as SRX-212 Catalyst, Dow Corning Toray Co., Ltd's manufacture) it mixes and is stirred, it prepares It is used to form the coating of the peeling agent layer of comparative example 1.Stick is strangled using wheat, the coating of the peeling agent layer of comparative example 1 will be used to form, In a manner of making the thickness after drying become 0.2 μm, it is coated on a thickness of the table of 38 μm of polyethylene terephthalate film Face, and it is 1 minute dry in 120 DEG C of heated air circulation type baker, obtain the stripping film of comparative example 1.
The adhesive composition of comparative example 1 is coated in a manner of making the thickness after drying become 20 μm with a thickness of 38 μm polyethylene terephthalate film surface after, dry 2 minutes in 100 DEG C of heated air circulation type baker, formed Adhesive layer.Then, on the surface of the adhesive layer, the remover of the stripping film of above-mentioned manufactured comparative example 1 has been bonded it Layer (polysiloxanes process face).Obtained adhesive film is kept the temperature 5 days in the environment of 40 DEG C, so that binder solidifies, is obtained The Antistatic surface protective film of comparative example 1.
[comparative example 2]
Other than the adhesive composition of comparative example 1 to be replaced with to the adhesive composition of comparative example 2, with comparative example 1 It is carried out similarly operation, obtains the Antistatic surface protective film of comparative example 2.
[comparative example 3]
Other than the adhesive composition of embodiment 1 to be replaced with to the adhesive composition of comparative example 3, with embodiment 1 It is carried out similarly operation, obtains the Antistatic surface protective film of comparative example 3.
The composition of peeling agent layer in the Antistatic surface protective film of Examples 1 to 6 and comparative example 1~3 and thickness are shown In table 7.
Table 7
<Test method and evaluation>
In the environment of 23 DEG C, 50%RH, after surface protection film aging 7 days of Examples 1 to 6 and comparative example 1~3, Stripping film (PET film for being coated with silicone (polysiloxanes) resin) is peeled off, to keep adhesive layer exposed, and as measurement surface electricity The sample of resistance rate.
In turn, 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 under 50 DEG C, 5 atmospheric pressure carry out pressure cooker handle 20 minutes, further at room temperature Sample after placing 12 hours, as measurement cohesive force, removing electrostatic pressure and re-workability.
<Cohesive force>
Using cupping machine, with low peeling rate (0.3m/min) and high peeling rate (30m/min), to 180 ° of directions Above-mentioned obtained measurement sample (surface protection film of 25mm wide is fitted in into sample made of polarisation plate surface) is removed, is measured Peel strength, and using the peel strength as cohesive force.
<Surface resistivity>
After weathering, it fits in front of polarizer, peels stripping film (PET film for being coated with silicone resin) off and make adhesive layer It is exposed, using resistivity meter HirestaUP-HT450 (Ha イ レ ス タ UP-HT450, Mitsubishi of Co., Ltd. chemical analysis technology (Mitsubishi Chemical Analytech Co., Ltd.) manufacture), determine the surface resistivity of adhesive layer.
<Remove electrostatic pressure>
Using high-precision electrostatic transducer SK-035, SK-200 (Co., Ltd.'s Keyemce (Keyence Corporation) Manufacture), determine the polarizer band when carrying out 180 ° of removings to above-mentioned obtained measurement sample with the tensile speed of 30m/min Electric and generation voltage (electrostatic pressure), using the maximum value of measured value as removing electrostatic pressure.
<Re-workability>
Described (load 500g, back and forth 3 on the surface protection film of measurement sample obtained above with ball pen It is secondary) after, surface protection film is removed from polarizer, the surface of polarizer is observed, is confirmed whether to transfer the pollution to polarizer.Evaluate mesh Mark benchmark："○" is evaluated as when not transferring the pollution to polarizer；When the track that confirmation is described along ball pen is at least to office Portion is evaluated as " △ " when displaced pollution；When confirmation along the track that ball pen is described has pollution transportation and from adhesive surface Also "×" is evaluated as when confirmation has the disengaging of binder.
It shows the results of the evaluation in table 8.In addition, indicating " m × 10 by " mE+n " in surface resistivity+n" (its In, m is arbitrary real number, and n is positive integer).
Table 8
According to measurement result shown in table 8, it is known that following situations.
The Antistatic surface protective film of the embodiment of the present invention 1~6 has cohesive force appropriate, and to adherend surface It does not pollute, moreover, removing electrostatic when removing Antistatic surface protective film from adherend forces down.
On the other hand, for be added in adhesive layer polysiloxane compound and antistatic agent comparative example 1 it is anti- For electrostatic surface protective film, the surface resistivity of adhesive layer is low and good, but the reason big due to cohesive force, removes electrostatic Pressure is high, re-workability is poor.In addition, in comparative example 2, it may be possible to due to crosslinking accelerator additive amount more than reason, binder hair Raw gelation, can not be coated.In addition, due to including carboxylic monomer, cohesive force is big, adds again in comparative example 3 Work is slightly worse.
That is, being mixed in the Comparative Examples 1 and 2 of polysiloxane compound and antistatic agent in a binder, it is difficult to meet simultaneously Remove the reduction of electrostatic pressure and the improvement of the pollution to adherend.On the other hand, poly- silicon oxygen is added in peeling agent layer After hydride compounds and antistatic agent, make polysiloxane compound and antistatic agent be transferred to the embodiment 1 on adhesive layer surface~ 6, have the effect of that removing electrostatic pressure can be reduced with few additive amount, therefore also do not pollute adherend, obtain good Good Antistatic surface protective film.
Industrial applicibility
Antistatic surface protective film of the invention, for example, can be applied to polarizer, phase plate, display lens It, can be in order to protect the optical component etc. in addition, in production process of various optical components etc. etc. in the optical film of film etc. Surface and use.In particular, as the LR for having carried out anti-pollution processing with polysiloxane compound, fluorine compounds etc. as surface In the case that the Antistatic surface protective film of the optical films such as polarizer, AG-LR polarizer carrys out use, it can reduce from being attached The static content generated when being removed on body.
Antistatic surface protective film of the invention is to the pollution of adherend less and without deterioration (not as the time pushes away Move and deteriorate) and there is excellent antistripping antistatic property, therefore can be improved the yield rate of production process, industrially Utility value it is high.

Claims (5)

1. antistatic agent can be transferred in the resin by having the transparency by a kind of Antistatic surface protective film stripping film On surface that be formed with the Antistatic surface protective film of adhesive layer on the single side of the base material film of composition, the adhesive layer, It is characterized in that,
The Antistatic surface protective film stripping film on the single side of resin film by being laminated the remover containing antistatic agent Layer forms, and the peeling agent layer is formed by resin combination, and the resin combination contains using dimethyl polysiloxane as master Want the remover of ingredient, as the Siloxane-Oxyalkylene Copolymers for the polysiloxane-based compound at 20 DEG C being liquid and as institute The alkali metal salt of antistatic agent is stated,
The adhesive layer is formed and crosslinking by making the adhesive composition containing acrylic polymer and crosslinking agent,
The acrylic polymer is to be copolymerized following monomer without containing carboxylic copolymerisable monomer Copolymer acrylic polymer：(A) carbon atom number of alkyl be C4~C18 (methyl) acrylate monomer in extremely At least one of few a kind of, (B) hydroxyl copolymerisable monomer and (C) not hydroxyl and in nitrogenous vinyl monomer At least one,
(C) hydroxyl and nitrogenous vinyl monomer are not selected from being replaced by cyclic annular nitrogen vinyl compound, dialkyl group (methyl) acrylamide contains N, (methyl) acrylate monomer, the dialkyl group substituted-amino alkyl of N- dialkyl group substituted-amino It is more than at least one of compound group composed by (methyl) acrylamide,
The institute contained when being bonded the Antistatic surface protective film stripping film by the peeling agent layer, in the peeling agent layer It states Siloxane-Oxyalkylene Copolymers and the alkali metal salt is transferred on the surface of the adhesive layer.
2. Antistatic surface protective film stripping film as described in claim 1, wherein the acrylic polymer also contains (G) polyalkylene glycol mono (methyl) acrylate monomer.
3. Antistatic surface protective film stripping film as claimed in claim 1 or 2, wherein (B) hydroxyl it is copolymerizable Monomer is selected from by (methyl) acrylic acid 8- hydroxyl monooctyl ester, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 4- hydroxyl Base butyl ester, (methyl) acrylic acid 2- hydroxy methacrylate, N- hydroxyl (methyl) acrylamide, N- methylol (methyl) acrylamide, N- It is more than at least one of compound group composed by ethoxy (methyl) acrylamide.
4. a kind of Antistatic surface protective film is fitted with Antistatic surface protective film removing of any of claims 1 or 2 Film.
5. a kind of optical component is fitted with Antistatic surface protective film as claimed in claim 4.
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