CN110121416A - Surface protective film - Google Patents

Surface protective film Download PDF

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Publication number
CN110121416A
CN110121416A CN201780081268.4A CN201780081268A CN110121416A CN 110121416 A CN110121416 A CN 110121416A CN 201780081268 A CN201780081268 A CN 201780081268A CN 110121416 A CN110121416 A CN 110121416A
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CN
China
Prior art keywords
methyl
slider
aforementioned
protective film
surface protective
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201780081268.4A
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Chinese (zh)
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CN110121416B (en
Inventor
渡部奈津子
三井数马
野中崇弘
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN110121416A publication Critical patent/CN110121416A/en
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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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The present invention provides a kind of optics surface protective film with slider; wherein; automatic laminating machine utilizing is being used to carry out position adjustment with surface protective film to the optics with slider and in the optical component surface protective film after optical component surfaces are bonded removing slider; position scalability based on slider is excellent, can paste optics surface protective film in optical component surfaces with accurate position.Optics surface protective film with slider of the invention is characterized in that; include the slider that there is at least single side in base film the optics surface protective film of adhesive phase and opposing face in the face of aforementioned substrates film contacted with adhesive phase to have; aforementioned slider has release layer and substrate, and the mist degree of aforementioned slider is 90% or more, total light transmittance is 50% or less.

Description

Surface protective film
Technical field
The present invention relates to the optics surface protective films with slider.It can will especially be used to protect optical component (such as polarizer used in liquid crystal display etc., wavelength plate, phase plate, optical compensating film, reflector plate, brightness enhancement film Deng) optics with slider on surface accurately carries out position tune relative to aforementioned optical component surface with surface protective film It is whole, also, after the adjustment of position, slider is removed, it is possible thereby to be bonded optics in optical component surfaces with accurate position It is useful with surface protective film.
Background technique
Surface protective film generally has the composition that adhesive phase is provided on the base film (supporter) of film-form. The surface protective film is bonded in the optical component as adherend by aforementioned adhesion oxidant layer, is consequently for protection optical component Damage, the pollution on surface whens when from processing, conveying, inspection etc..For example, the panel of liquid crystal display, which passes through, utilizes bonding Oxidant layer is bonded the optical components such as polarizer, wavelength plate on liquid crystal cell to be formed.The adhesive phase is for until practical viscous Dry etc. necessity is protecteded from until before being affixed on optical component, by being demoulded the protection such as slider handled and keeping (patent document 1).
Then, the adhesive layer surface of aforementioned surfaces protective film optical component is pasted in reality to come using rear, it should Surface protective film is stripped removal in the stage no longer needed.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2012-224811
Summary of the invention
Problems to be solved by the invention
In addition, when optical component surfaces are bonded the surface protective film with slider, in order to the progress of accurate position Fitting, in a manner of not cutting off slider, is only cut into desired size for surface protective film, opens in the outer rim of slider Hole senses its aperture segment with sensor, carries out position adjustment using automatic laminating machine utilizing, then, after slider is removed, patch It closes in optical component surfaces.
However, even if want using the usually used transparent surface protective film with slider it is accurate on optical component Ground carries out position adjustment, also can not accurately sense aperture segment, can generate deviation, by the surface protective film with slider Slider removing and when being pasted on optical component, it may occur that the rough sledding such as can not paste with accurate position, constitute problem.
Therefore, the inventors of the present invention have made intensive studies in view of the foregoing, as a result, its purpose is to provide a kind of band every In vitro optics surface protective film is carrying out the optics with slider with surface protective film using automatic laminating machine utilizing Position adjustment and when being fitted in optical component surfaces after removing slider, the position scalability based on slider is excellent, can be with It is pasted in optical component surfaces with accurate position.
The solution to the problem
That is, the optics surface protective film of the invention with slider is characterized in that, comprising: base film extremely Few single side has the optics surface protective film of adhesive phase and the face contacted with adhesive phase in the base film The slider that has of opposing face, aforementioned slider has release layer and a substrate, and the mist degree of aforementioned slider is 90% or more, total Light transmittance is 50% or less.
Optics with slider of the invention is preferably with surface protective film, and aforementioned substrates film is polyester film.
Optics with slider of the invention is preferably with surface protective film, and aforementioned adhesion oxidant layer is by containing selected from third At least one kind of adhesive composition in alkene acrylic binder, carbamates adhesive and silicone adhesive category is formed.
The effect of invention
By the present invention in that the following optics with slider can be obtained with the slider with specific optical characteristics With surface protective film: using automatic laminating machine utilizing relative to optical component table the surface protective film of the optics with slider Face carries out position adjustment and when being fitted in optical component surfaces after removing slider, and the position scalability based on slider is excellent It is different, it can be pasted in optical component surfaces with accurate position, be useful.
Detailed description of the invention
Fig. 1 is the schematic sectional for showing a configuration example of the optics surface protective film of the invention with slider Figure.
Fig. 2 is to show to carry out position tune with surface protective film to the optics of the invention with slider on optical component The schematic cross sectional views of a configuration example after whole.
Specific embodiment
Hereinafter, detailed description of embodiments of the present invention.
<overall structure of the optics surface protective film with slider>
Optics with slider disclosed herein is with surface protective film (hereinafter sometimes referred to simply as " surface protective film ".) The adhesive layer surface for being generally known as the forms such as adhesive tape, adhesive label, adhesive film is isolated made of body protection Film (such as is used as the panel of LCD constituent element such as polarizer, wavelength plate especially as in optical component Optical component) processing, inspection, conveying when protection optical component the surface protective film on surface be suitable.Aforementioned surfaces Adhesive phase in protective film is typically formed continuously, and is not limited to the form, can be created as example dotted, item The adhesive phase of the rule such as shape or irregular pattern.In addition, surface protective film disclosed herein can be web-like, it is also possible to Single sheet.
<base film>
Optics surface protective film with slider of the invention is characterized by having base film.Disclosed herein In technology, the resin material for constituting base film can be used without particular limitation, it is preferable to use such as transparency, machinery is strong The material of the excellents such as degree, thermal stability, water shielding, isotropism, flexibility, dimensional stability.Especially because substrate Film has flexibility, can coil into web-like by the coating adhesives composition such as roll-coater, be useful.
As aforementioned substrates film (supporter), it is preferable to use by using following compositions as principal resinous ingredients (tree Main component in rouge ingredient, the ingredient for typically accounting for 50 weight % or more) the plastic film conduct that constitutes of resin material Aforementioned substrates film, the ingredient be for example polyethylene terephthalate (PET), polyethylene naphthalate (PEN), The polyester polymers such as polybutylene terephthalate (PBT)；The cellulosic polymers such as cellulose diacetate, cellulose triacetate； Polycarbonate polymer；The acrylic polymers such as polymethyl methacrylate；Etc..As other of aforementioned resin material Example can be enumerated using materials described below as resin material: the styrene polymers such as polystyrene, acrylonitritrile-styrene resin Close object；Polyethylene, polypropylene, with polymerization of olefines such as cyclic annular or norbornene structure polyolefin, ethylene-propylene copolymers Object；Vinyl chloride polymer；The acylamide polymers such as nylon 6, nylon 6,6, aromatic polyamide；Etc..As aforementioned resin The other examples again of material, can enumerate: acid imide polymer, sulfone quasi polymer, polyether sulfone polymer, polyetheretherketone Polymer, polyphenylene sulfide quasi polymer, vinyl alcohol polymer, vinylidene chloride quasi polymer, vinyl butyral Type of Collective Object, aromatic ester quasi polymer, polyoxymethylene quasi polymer, epoxide polymer etc..It can be by two or more above-mentioned polymer The base film that blend is formed.
It, can be preferably using the plastic film formed by transparent thermoplastic resin material as aforementioned substrates film.Before It states in plastic film, the use of polyester film is preferred mode.Here, polyester film refers to poly terephthalic acid second two Alcohol ester (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT) etc. have the master based on ester bond Film of the polyester polymer material (polyester resin) of skeleton as principal resinous ingredients.The polyester film has optics special The preferred characteristic for the base film of surface protective film such as property, excellent in dimensional stability.
In the resin material for constituting aforementioned substrates film, it can according to need and be compounded antioxidant, ultraviolet radiation absorption The various additives such as agent, plasticizer, colorant (pigment, dyestuff etc.).Such as Corona discharge Treatment, plasma can be implemented Processing, ultraviolet treatment with irradiation, sour processing, alkali process, silane coupling agent coating etc. known in or usual surface treatment.This surface Processing can be for example for improving the processing of the adaptation (anchoring of adhesive phase) of base film and adhesive phase.
As aforementioned substrates film, the plastic film through antistatic treatment also can be used.It is thin by using aforementioned substrates Film, can inhibit the electrification of the surface protective film itself when removing, therefore it is preferred that.In addition, by making base film plastic film And antistatic treatment is implemented to foregoing plastics film, the electrification of surface protective film itself can be reduced and is made to adherend Antistatic energy is excellent.It should be noted that being not particularly limited, can be used existing as the method for assigning anti-static function Well known method, such as can enumerate: it is coated with the antistatic property resin formed by antistatic agent and resin component, electric conductivity polymerize The method of object, electroconductive resin containing conductive material；The method of vapor deposition or plated conductive substance；There are also mixing resist it is quiet The method etc. of electric agent etc..
As the thickness of aforementioned substrates film, usually 5~200 μm, preferably 10~100 μm or so.If aforementioned base The thickness of material film is in aforementioned range, then excellent to the fitting workability of adherend and the fissility from adherend, workability, Therefore it is preferred that.
Surface protective film disclosed herein can also on the basis of base film, adhesive phase and slider also into One step includes that the mode of other layers is implemented.As other aforementioned layers, the anchoring for improving antistatic layer, adhesive phase can be enumerated Priming coat (anchor layer) etc..
<adhesive phase>
If adhesive phase used in the present invention is combined by the adhesive containing the binding property polymer with adhesiveness Object is formed, then can be used without particular limitation.As aforementioned adhesion agent composition, such as acrylic adhesive can be used Agent, carbamates adhesive, synthetic rubber class adhesive, natural rubber based binder, silicone adhesive category, polyesters Adhesive etc., in the middle, it is preferable to use (containing) is selected from by acrylic adhesives, carbamates adhesive and organosilicon At least one kind of adhesive composition in the group of class adhesive composition, particularly preferred use are employed as aforementioned adhesion polymerization The adhesive composition (acrylic adhesives) of (methyl) acrylic polymer of object.
In the case that aforementioned adhesion oxidant layer uses acrylic adhesives, for as composition foregoing acrylic adhesive Binding property polymer (methyl) acrylic polymer, as its starting monomer is constituted, can be used with carbon number 1~ (methyl) acrylic monomer of 14 alkyl is as principal monomer.As aforementioned (methyl) acrylic monomer, 1 can be used Kind or two or more.By using (methyl) acrylic monomer of the aforementioned alkyl for being 1~14 with carbon number, being easy to will be opposite It controls lower in the peeling force (bonding force) of adherend (by protective), the excellent table of light fissility, releasable can be obtained Face protective film.It should be noted that (methyl) acrylic polymer in the present invention refer to acrylic polymer and/or Metering system quasi polymer, in addition, (methyl) acrylate refers to acrylate and/or methacrylate.
The specific example of (methyl) acrylic monomer as the aforementioned alkyl with carbon number 1~14, such as can enumerate Out: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid 2- ethyl hexyl Ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, the positive nonyl ester of (methyl) acrylic acid, the different nonyl of (methyl) acrylic acid Ester, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) acrylic acid n-dodecane base ester, (methyl) propylene Sour n-tridecane base ester, (methyl) n-myristyl base ester etc..
Wherein, in surface protective film of the invention, (methyl) n-butyl acrylate, (methyl) acrylic acid can be enumerated Own ester, (methyl) 2-EHA, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) propylene Sour positive nonyl ester, the different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) propylene Sour n-dodecane base ester, (methyl) acrylic acid n-tridecane base ester, (methyl) n-myristyl base ester etc. have carbon number 4~ (methyl) acrylic monomer of 14 alkyl is as particularly suitable example.Especially by using with carbon number 4~14 (methyl) acrylic monomer of alkyl is easy to control lower by the peeling force (bonding force) to adherend, and releasable is excellent It is different.
Especially with respect to the 100 weight % of monomer component total amount for constituting aforementioned (methyl) acrylic polymer, have (methyl) acrylic monomer of the alkyl of carbon number 1~14 preferably comprises 65 weight % or more, more preferably 75 weight % or more, Further preferably 85~99.9 weight %, most preferably 90~99 weight %.If it is less than 65 weight %, then adhesive combines The wetability of appropriateness of object, the cohesive force of adhesive phase can be deteriorated, and be undesirable.
In addition, hydroxyl (methyl) acrylic monomer can be used as raw material in aforementioned (methyl) acrylic polymer Monomer.As aforementioned hydroxyl (methyl) acrylic monomer, can be used one kind or two or more.By using aforementioned hydroxyl (methyl) acrylic monomer, the crosslinking etc. of easily controllable adhesive composition, and then the easily controllable wetability based on flowing Improvement and removing in peeling force (bonding force) reduce between balance.
As aforementioned hydroxyl (methyl) acrylic monomer, such as can enumerate: (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) acrylic acid 2- hydroxypropyl acrylate, (methyl) acrylic acid 4- hydroxy butyl ester, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 8- Hydroxyl monooctyl ester, (methyl) acrylic acid 10- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid 12- hydroxylauric ester, acrylic acid (4- hydroxymethylcyclohexyl) Methyl esters, N- methylol (methyl) acrylamide etc..
Relative to the 100 weight % of monomer component total amount for constituting aforementioned (methyl) acrylic polymer, aforementioned hydroxyl (methyl) acrylic monomer preferably comprise 25 weight % hereinafter, more preferably 15 weight % hereinafter, further preferably 0.1~ 10 weight %.If in aforementioned range, the wetability of easily controllable adhesive composition and the cohesion of gained adhesive phase Balance between power, therefore it is preferred that.
It, can be not the reasons why for the balance for being easily obtained bond properties in addition, as other polymerizable monomer ingredients It damages in the range of effect of the invention and adjusts (methyl) propylene using for making 0 DEG C of Tg or less (usually -100 DEG C or more) Glass transition temperature, polymerizable monomer of fissility of acids polymers etc..
In addition, aforementioned (methyl) acrylic polymer can be used containing carboxyl (methyl) acrylic monomer as raw material Monomer.Contain carboxyl (methyl) acrylic monomer by using aforementioned, is able to suppress the viscous of adhesive phase (surface protective film) Resultant force rises at any time, and releasable prevents that bonding force is ascending and workability is excellent.In addition, the cohesive force of adhesive phase and Shearing force is also excellent, is preferred.
Contain carboxyl (methyl) acrylic monomer as aforementioned, such as can enumerate: (methyl) acrylic acid, (methyl) propylene Sour carboxylic ethyl ester, (methyl) carboxypentyl acrylate etc..
It is aforementioned to contain carboxyl relative to the monomer component total amount 100 weight % for constituting aforementioned (methyl) acrylic polymer (methyl) acrylic monomer is preferably 10 weight % hereinafter, more preferably 0~8 weight %, further preferably 0~6 weight Measure %.If in aforementioned range, the cohesive force of the wetability of easily controllable adhesive composition and gained adhesive phase it Between balance, therefore it is preferred that.
In turn, aforementioned (methyl) acrylic polymer can be without special in the range of not damaging characteristic of the invention It limits ground and uses other polymerizable monomers in addition to aforementioned raw material monomer.It, can be with for example, as other aforementioned polymerizable monomers The appropriate ingredient that cohesive force, heat resistance are improved using cyano-containing monomer, vinyl ester monomers, aromatic vinyl monomer etc., is contained Amide groups monomer, monomer containing imide, emulsion stability, containing epoxy based monomers, N- acryloyl morpholine, vinyl ether monomers etc. Improve peeling force (bonding force), the ingredient with the functional group worked as Cross-linked basic point.In the middle, it is preferable to use cyano-containing The nitrogen containing monomers such as monomer, amide-containing monomer, monomer containing imide, emulsion stability and N- acryloyl morpholine.By using Nitrogen containing monomer, it can be ensured that the peeling force (bonding force) for the appropriateness do not float, remove etc., and then it is excellent to obtain shearing force Different surface protective film, therefore be useful.These polymerizable monomers can be used one kind or two or more.
As aforementioned cyano-containing monomer, such as acrylonitrile, methacrylonitrile can be enumerated.
It as aforementioned amide-containing monomer, such as can enumerate: acrylamide, Methacrylamide, diethyl acryloyl Amine, n-vinyl pyrrolidone, N, N- dimethylacrylamide, N, N- dimethylmethacryl amide, N, N- diethyl propylene Amide, N, N- diethyhnethacrylamide, N, N '-methylene-bisacrylamide, N, N- dimethylamino propyl acrylamide, N, N- dimethylamino-propyl Methacrylamide, diacetone acrylamide etc..
It as aforementioned monomer containing imide, such as can enumerate: N-cyclohexylmaleimide, isopropyl maleimide Amine, N- N-cyclohexylmaleimide, clothing health acid imide etc..
It as aforementioned emulsion stability, such as can enumerate: (methyl) acrylate, (methyl) acrylic acid N, N- Dimethylaminoethyl, (methyl) acrylic acid N, N- dimethylamino propyl ester etc..
It as aforementioned vinyl ester monomers, such as can enumerate: vinylacetate, vinyl propionate, vinyl laurate Deng.
It as aforementioned fragrance race vinyl monomer, such as can enumerate: styrene, chlorostyrene, 1-chloro-4-methyl-benzene, α- Methyl styrene, other substituted phenylethylenes etc..
Contain epoxy based monomers as aforementioned, such as can enumerate: (methyl) glycidyl acrylate, (methyl) acrylic acid Methylglycidyl esters, allyl glycidyl ether etc..
It as aforementioned vinyl ether monomers, such as can enumerate: methyl vinyl ether, ethyl vinyl ether, isobutyl group second Alkene ether etc..
In the present invention, the 100 weight % of monomer component total amount relative to aforementioned (methyl) acrylic polymer of composition, Other aforementioned polymerizable monomers are preferably 0~30 weight %, more preferably 0~10 weight %.Other aforementioned polymerizable monomers can Suitably to be adjusted to obtain desired characteristic.
Aforementioned (methyl) acrylic polymer can further contain (the alkylene oxide of alkyl containing alkylene oxide Group) reactive monomer is as monomer component.
In addition, the average addition molal quantity of the oxygen alkylidene unit as the aforementioned reactive monomer of alkyl containing alkylene oxide, from From the perspective of the compatibility of oxygen-containing alkylidene compound, preferably 1~40, more preferably 3~40, further preferably 4 ~35, particularly preferably 5~30.In the case that aforementioned average addition molal quantity is 1 or more, exists and efficiently obtain adherend (quilt Protective) pollution reduce effect tendency.In addition, in the case that aforementioned average addition molal quantity is greater than 40, with oxygen-containing alkylene The interaction of based compound increases, and rises there are the viscosity of adhesive composition and is difficult to the tendency coated, it is not preferable.It needs It is noted that the end of oxyalkylene chain can remain hydroxyl, can also be replaced by other functional groups etc..
The aforementioned reactive monomer of alkyl containing alkylene oxide may be used alone, can also be 2 or more kinds in combination, as whole The content of body, in the monomer component total amount of aforementioned (methyl) acrylic polymer, preferably 0~20 weight %, more preferably For 0~10 weight %.If the content of the reactive monomer of alkyl containing alkylene oxide is more than 20 weight %, to the pollution of adherend It is deteriorated, it is not preferable.
As the oxygen alkylidene unit of the aforementioned reactive monomer of alkyl containing alkylene oxide, the alkylene with carbon number 1~6 can be enumerated The unit of base, such as Oxymethylene, oxygen ethylidene, oxygen propylidene, oxygen butylidene can be enumerated etc..The alkyl of oxyalkylene chain can To be straight chain, there can also be branch.
In addition, the aforementioned reactive monomer of alkyl containing alkylene oxide is more preferably the reactive monomer with Oxyranyle.It is logical It crosses and uses (methyl) acrylic polymer comprising the reactive monomer with Oxyranyle as basic polymer, basis The compatibility of polymer and oxygen-containing alkylidene compound improves, and can suitably inhibit the exudation to adherend, low pollution can be obtained The adhesive composition of property.
It as the aforementioned reactive monomer of alkyl containing alkylene oxide, such as can enumerate: the alkane addition of (methyl) acrylic acid epoxy Object has acryloyl group, methylacryloyl, reactive surfactant of allyl isoreactivity substituent group etc. in molecule.
It as the specific example of aforementioned (methyl) acrylic acid epoxy alkane addition product, such as can enumerate: polyethylene glycol (first Base) acrylate, polypropylene glycol (methyl) acrylate, polyethylene glycol propylene glycol (methyl) acrylate, polyethylene glycol- Polytetramethylene glycol (methyl) acrylate, polypropylene glycol-polytetramethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) third Olefin(e) acid ester, ethyoxyl polyethylene glycol (methyl) acrylate, butoxy polyethylene glycol (methyl) acrylate, the poly- second two of octyloxy Alcohol (methyl) acrylate, laurel oxygroup polyethylene glycol (methyl) acrylate, stearic oxygroup polyethylene glycol (methyl) acrylic acid Ester, phenoxy group polyethylene glycol (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, octyloxy polyethylene glycol- Polypropylene glycol (methyl) acrylate etc..
In addition, the specific example as previous reaction surfactant, such as can enumerate: there is (methyl) acryloyl The anionic reactive surfactant of base or allyl, non-ionic reactive surfactant, cation type reactive Surfactant etc..
The weight average molecular weight (Mw) of aforementioned (methyl) acrylic polymer is preferably 100,000~5,000,000, more preferably 20 Ten thousand~4,000,000, further preferably 300,000~3,000,000, most preferably 300,000~1,200,000.Feelings of the weight average molecular weight less than 100,000 Under condition, there is the tendency that residue glue occurs because the cohesive force of adhesive phase reduces.And weight average molecular weight the case where being more than 5,000,000 Under, the mobility of polymer reduces, exist it is insufficient to the wetting of adherend (such as polarizer), be formed in adherend and surface The tendency for the reason of heaving is generated between the adhesive phase of protective film.It should be noted that weight average molecular weight, which refers to, passes through GPC Molecular weight obtained by (gel permeation chromatography) measurement.
In addition, the glass transition temperature (Tg) of aforementioned (methyl) acrylic polymer is preferably 0 DEG C hereinafter, more preferably For -10 DEG C or less (usually -100 DEG C or more).In the case that glass transition temperature is higher than 0 DEG C, polymer is difficult to flow, and deposits In the bonding for for example wetting of the polarizer as optical component being become inadequate, being formed in polarizer and surface protective film The tendency for the reason of heaving is generated between oxidant layer.Especially by preferably make -40 DEG C of glass transition temperature or less, it is more preferable For -70 DEG C hereinafter, the readily available adhesive phase excellent to the wetability of polarizer and light fissility.It should be noted that (first Base) glass transition temperature of acrylic polymer can adjust by suitably changing used monomer component, ratio of components It is whole in aforementioned range.
The polymerization of aforementioned (methyl) acrylic polymer is not particularly limited, and can pass through polymerisation in solution, cream Method well known to liquid polymerization, bulk polymerization, suspension polymerisation etc. is polymerize, especially from the angle of workability, to adherend (quilt Protective) the characteristics such as low pollution in terms of from the point of view of, polymerisation in solution is preferred mode.In addition, resulting polymers can be Any one of random copolymer, block copolymer, alternate copolymer, graft copolymer etc..
In the case that aforementioned adhesion oxidant layer uses carbamates adhesive, any appropriate carbamic acid can be used Ester adhesive.As this carbamates adhesive, it is preferably listed out by as being esterified polyalcohol and polyisocyanic acid Close the adhesive that the carbamate quasi polymer of binding property polymer obtained by object reaction is formed.As polyalcohol, such as can It enumerates: polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol etc..It is esterified as polyisocyanic acid Object is closed, such as can be enumerated: methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), hexamethylene diisocyanate etc..
In the case that aforementioned adhesion oxidant layer uses silicone adhesive category, it can be bonded using any appropriate organic silicon Agent.It, can be preferably using by making the silicone-based polymers as binding property polymer as this silicone adhesive category Adhesive obtained by being blended or assembling.
In addition, addition reaction curing type silicone class adhesive, peroxide can be enumerated as aforementioned organic silicon class adhesive Compound curing type silicone class adhesive.In these silicone adhesive categories, due to not using peroxide (benzoyl peroxide first Acyl etc.), do not generate decomposition product and it is preferred that addition reaction curing type silicone class adhesive.
As the curing reaction of aforementioned addition reaction curing type silicone class adhesive, such as obtain poly- alkyl organic class In the case where adhesive, can generally enumerate makes the cured method of polyalkylhydrogensiloxanes composition using platinum catalyst.
<oxygen-containing alkylidene compound>
Adhesive composition used in the present invention can also contain oxygen-containing alkylidene compound.By containing oxygen-containing alkylene Based compound can further show light fissility.As oxygen-containing alkylidene compound, can enumerate with oxyalkylene chain Organopolysiloxane, the oxygen-containing alkylidene compound without organopolysiloxane.
As the specific example of the aforementioned organopolysiloxane with oxyalkylene chain, there is oxyalkylene as in main chain The specific example of the organopolysiloxane of chain, such as commercially available product, can enumerate trade name X-22-4952, X-22-4272, X-22-6266, KF-6004, KF-889 (the above are Shin-Etsu Chemial Co., Ltd's manufactures), BY16-201, SF8427 (more than For the manufacture of Dong Li Dow Corning Corporation), IM22 (manufacture of WACKER ASAHIKASEI SILICONE Co., Ltd.) etc..In addition, making To have the organosiloxane of oxyalkylene chain in side chain, such as commercially available product, trade name KF-351A, KF- can be enumerated 352A、KF-353、KF-354L、KF-355A、KF-615A、KF-945、KF-640、KF-642、KF-643、KF-6022、X-22- 6191, (the above are SHIN-ETSU HANTOTAI's chemical industry strains by X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, X-22-2516 The manufacture of formula commercial firm), SF8428, FZ-2162, SH3749, FZ-77, L-7001, FZ-2104, FZ-2110, L-7002, FZ- 2122, (the above are Dong Li Dow Corning Corporations by FZ-2164, FZ-2203, FZ-7001, SH8400, SH8700, SF8410, SF8422 Manufacture), TSF-4440, TSF-4441, TSF-4445, TSF-4450, TSF-4446, TSF-4452, TSF-4460 (Momentive Performance Materials Inc. manufacture), BYK-333, BYK-307, BYK-377, BYK- UV3500, BYK-UV3570 (BYK Japan KK manufacture) etc..These compounds can be used alone, can also be by two or more It is used in mixed way.
It as the specific example of the aforementioned oxygen-containing alkylidene compound without organopolysiloxane, such as can enumerate: poly- Oxyalkylene alkylamine, polyoxy alkylene diamine, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan acid anhydride aliphatic ester, Polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether, polyoxyalkylene alkyl phenyl The nonionic surfactants such as allyl ether；Polyoxyalkylene alkyl ether sulfuric acid, polyoxyalkylene alkyl ether phosphate ester salt, The Anionic surfactants such as polyoxyalkylene alkyl phenyl ether sulfuric acid, polyoxyalkylene alkyl phenyl ether phosphate salt Agent；In addition there are cationic surfactants, amphoteric ion surface with polyoxy alkylidene chain (polyalkylene oxide hydrocarbon chain) Activating agent, the polyether compound (further including its derivative) with polyoxy alkylidene chain, the propylene with polyoxy alkylidene chain Acid compounds (further including its derivative) etc..Furthermore, it is possible to which polyoxy alkylidene chain monomer will be contained as chain containing polyoxy alkylidene Compound compounding.This, which contains polyoxy alkylidene chain compound, may be used alone, or two or more kinds may be used in combination.
As the specific example of the aforementioned polyether compound (polyether components) with polyoxy alkylidene chain, can enumerate: Polypropylene glycol (the PPG)-block copolymer of polyethylene glycol (PEG), the block copolymer of PPG-PEG-PPG, PEG-PPG-PEG Block copolymer etc..As the derivative of the aforementioned polyether compound with polyoxy alkylidene chain, end can be enumerated by ether The oxygen-containing propylidene compound (PPG monoalky lether, PEG-PPG monoalky lether etc.) changed, end is by acetylating oxygen-containing sub- third Based compound (terminal acetyl group PPG etc.) etc..
In addition, the specific example as the aforementioned acrylic compounds with polyoxy alkylidene chain, can enumerate with oxygen (methyl) acrylate polymer of alkylidene.As aforementioned oxyalkylene, the addition molal quantity of oxygen alkylidene unit is preferably 1 ~50, more preferably 2~30, further preferably 2~20.In addition, the end of aforementioned oxyalkylene chain can remain hydroxyl, It can also be replaced by alkyl, phenyl etc..
Aforementioned (methyl) acrylate polymer with oxyalkylene preferably contains (methyl) acrylic acid alkylene oxide Polymer of the compound as monomer component, as the specific example of aforementioned (methyl) acrylic acid alkylene oxide, as containing second Glycol-based (methyl) acrylate, such as can enumerate: methoxyl group-diethylene glycol (methyl) acrylate ,-three second two of methoxyl group Alcohol (methyl) acrylate etc. methoxypolyethylene glycols (methyl) acrylic ester type, ethyoxyl-diethylene glycol (methyl) acrylic acid Ethyoxyls-polyethylene glycol (methyl) acrylic ester types such as ester, ethyoxyl-triethylene glycol (methyl) acrylate, butoxy-diethyl Butoxy-polyethylene glycol (methyl) acrylic acid such as glycol (methyl) acrylate, butoxy-triethylene glycol (methyl) acrylate Ester type, the poly- second of phenoxy groups-such as phenoxy group-diethylene glycol (methyl) acrylate, phenoxy group-triethylene glycol (methyl) acrylate Glycol (methyl) acrylic ester type, 2- ethylhexyl-polyethylene glycol (methyl) acrylate, nonyl phenol-polyethylene glycol (first Base) acrylic ester type, methoxyl group-dipropylene glycol (methyl) acrylate etc. methoxyl groups-polypropylene glycol (methyl) acrylic ester type Deng.
In addition, also can be used in addition to aforementioned (methyl) acrylic acid alkylene oxide as aforementioned monomer component Other monomers ingredient.It as the specific example of other monomers ingredient, can enumerate: (methyl) methyl acrylate, (methyl) propylene Acetoacetic ester, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid Isobutyl ester, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) propylene The different monooctyl ester of acid, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) propylene Sour isodecyl ester, (methyl) acrylic acid n-dodecane base ester, (methyl) acrylic acid n-tridecane base ester, (methyl) acrylic acid positive 14 Arrcostab etc. has the acrylate and/or methacrylate of the alkyl of carbon number 1~14.
It in turn, can also be appropriate as the aforementioned other monomers ingredient in addition to (methyl) acrylic acid alkylene oxide Using containing carboxyl (methyl) acrylate, phosphorous acidic group (methyl) acrylate, cyano-containing (methyl) acrylate, vinyl esters Class, contains anhydride group (methyl) acrylate, hydroxyl (methyl) acrylate, amide-containing (first at aromatic ethenyl compound Base) acrylate, containing amino (methyl) acrylate, contain epoxy group (methyl) acrylate, N- acryloyl morpholine, vinyl ethers Class etc..
A scheme more preferably, the aforementioned chain compound containing polyoxy alkylidene without organopolysiloxane are extremely Few a part has the compound of (poly-) oxygen ethylidene chain.By being compounded the aforementioned ethylidene chain compound containing (poly-) oxygen, so that with The compatibility of base polymer improves, and can suitably inhibit the exudation to adherend, and the adhesive combination of low pollution can be obtained Object.In the middle, the excellent bonding of low pollution especially can be obtained using the block copolymer of PPG-PEG-PPG Agent.As aforementioned chain compound containing polyoxyethylene, (poly-) oxygen ethylidene chain contains polyoxy without organopolysiloxane aforementioned Shared weight is preferably 5~90 weight % in alkylidene chain compound entirety, more preferably 5~85 weight %, further excellent It is selected as 5~80 weight %, most preferably 5~75 weight %.
In addition, the commercially available product as the aforementioned chain compound containing polyoxy alkylidene without organopolysiloxane, such as can arrange It enumerates: Adeka Pluronic 17R-4, Adeka Pluronic 25R-2 (being above Asahi Denka Co., Ltd.'s manufacture), LATEMUL PD-420, LATEMUL PD-420, LATEMUL PD-450,120 EMULGEN (Kao Corp's manufacture), (the above are the first industry systems by Aquaron HS-10, KH-10, NOIGEN EA-87, EA-137, EA-157, EA-167, EA-177 The manufacture of medicine Co., Ltd.) etc..
As the content of aforementioned oxygen-containing alkylidene compound, relative to the adhesiveness polymerization for constituting aforementioned adhesion agent composition Object (for host polymer, such as (methyl) acrylic polymer, carbamate quasi polymer, silicone-based polymers etc.) 100 parts by weight, preferably 0.01~5 parts by weight, more preferably 0.02~2 parts by weight, further preferably 0.03~1.6 weight Part, most preferably 0.1~0.8 parts by weight.If being easy to show adhesive phase used in the present invention in aforementioned range The light fissility (releasable) of (surface protective film), is preferred.
<crosslinking agent>
The preferred aforementioned adhesion agent composition of surface protective film of the invention contains crosslinking agent.In addition, in the present invention, it can To use aforementioned adhesion agent composition that adhesive phase is made.Such as aforementioned adhesion agent composition be contain aforementioned (methyl) propylene In the case where the acrylic adhesives of acids polymers, by the composition for suitably adjusting aforementioned (methyl) acrylic polymer Unit, component ratio, the selection of crosslinking agent and addition ratio etc. are crosslinked, the available superior adhesive phase of heat resistance (surface protective film).
Isocyanate compound, epoxide, melamine class can be used in crosslinking agent used in the present invention Resin, aziridine derivative and metal chelate compound etc. are preferred especially with isocyanate compound, epoxide Mode.In addition, these compounds may be used alone, can also be 2 or more kinds in combination.
It as aforementioned isocyanates compound, such as can enumerate: trimethylene diisocyanate, butylidene diisocyanate Aliphatic polyisocyantes class, the cyclopentylenes two such as ester, hexamethylene diisocyanate (HDI), dimer acid diisocyanate are different Bis- (isocyanatomethyl) hexamethylenes of cyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI), 1,3- The alicyclic isocyanates class such as alkane, 2,4- toluene di-isocyanate(TDI)s, 4,4 '-methyl diphenylene diisocyanates, xyxylene two The aromatic isocyanates classes such as isocyanates (XDI) pass through allophanic acid ester bond, biuret linkage, isocyanurate-bond, urea diketone Key, urea bond, carbodiimide key, uretonimine key, three ketonic bond of oxadiazines etc. are modified aforementioned isocyanates compound and obtain Modified polyisocyanate body.For example, can be enumerated as commercially available product: trade name TAKENATE 300S, 500 TAKENATE, TAKENATE 600, TAKENATE D165N, TAKENATE D178N (the above are Takede Chemical Industries Ltd's manufactures), (the above are Sumika Bayer Urethane Co., Ltd. systems by SUMIDUR T80, SUMIDUR L, Desmodur N3400 Make), (it is poly- that the above are Japan by MILLONATE MR, MILLONATE MT, CORONATE L, CORONATE HL, CORONATE HX The manufacture of urethane Industrial Co., Ltd) etc..These isocyanate compounds can be used alone, two or more mixing can also be made With the isocyanate compound of the isocyanate compound and 3 functions of 2 functions or more can also be applied in combination.Made by combination With crosslinking agent, adhesiveness and resistance to resilience (to the cementability of curved surface) can be further taken into account, available bonding reliability is more Excellent adhesive phase (surface protective film).
As aforementioned epoxy compound, such as N, N, N can be enumerated ', N '-four glycidyl group-m-xylene diamine (quotient Name of an article TETRAD-X, Mitsubishi Gas Chemical Co., Ltd's manufacture), 1,3- bis- (N, N- diglycidyl amino methyl) hexamethylenes (trade name TETRAD-C, Mitsubishi Gas Chemical Co., Ltd's manufacture) etc..
As aforementioned melamine resinoid, hexamethylolmelamine etc. can be enumerated.As aziridine derivative, such as Trade name HDU, TAZM, TAZO (the above are the manufactures of mutual Yao Gong Co., Ltd.) etc. as commercially available product can be enumerated.
Aluminium, iron, tin, titanium, nickel etc. can be enumerated, as chelating as metal component for aforementioned metal chelate compound Ingredient can enumerate acetylene, methyl acetoacetate, ethyl lactate etc..
For the content of crosslinking agent used in the present invention, such as relative to aforementioned (methyl) acrylic polymer 100 Parts by weight, preferably 0.01~20 parts by weight, more preferably 0.1~15 parts by weight, further preferably 0.5~10 parts by weight, Most preferably 1~8 parts by weight.In the case that aforementioned content is less than 0.01 parts by weight, being cross-linked to form based on crosslinking agent becomes not Sufficiently, the reason of cohesive force of gained adhesive phase reduces, and can not obtain enough heat resistances sometimes, and there is also composition residue glues Tendency.And in the case that content is more than 20 parts by weight, the cohesive force of polymer increases, and mobility reduces, (such as partially to adherend Tabula rasa) wetting become inadequate, exist to be formed in generate between adherend and adhesive phase (adhesive composition layer) and heave The reason of tendency.In addition, these crosslinking agents can be used alone, two or more can also be used in mixed way.
<crosslinking catalyst>
It, can be further containing for carrying out any of the above-described cross-linking reaction more effectively in aforementioned adhesion agent composition Crosslinking catalyst.As the crosslinking catalyst, it can be used for example: dibutyl tin dilaurate, tin dilaurate dioctyl tin etc. Tin series catalysts, tri acetylacetonato iron, three (hexane -2,4- diketone) iron, three (heptane -2,4- diketone) iron, three (heptane -3, 5- diketone) iron, three (5- methyl hexane -2,4- diketone) iron, three (octane -2,4- diketone) iron, three (6- methyl heptane -2,4- two Ketone) iron, three (2,6- dimethyl heptane -3,5- diketone) iron, three (nonane -2,4- diketone) iron, three (nonane -4,6- diketone) iron, Three (2,2,6,6- tetramethyl base heptane -3,5- diketone) iron, three (tridecane -6,8- diketone) iron, three (1- phenyl butane -1,3- two Ketone) iron, three (hexafluoroacetylacetone) iron, three (ethyl acetoacetate) iron, three (acetoacetate n-propyl) iron, three (acetoacetates Isopropyl ester) iron, three (acetoacetate N-butyl) iron, three (the secondary butyl ester of acetoacetate) iron, three (tert-butyl acetoacetate) iron, three (propionyl methyl acetate) iron, three (Propionylacetic acid ethyl ester) iron, three (propionyl n-propyl acetate) iron, three (propionyl isopropyl acetates) Iron, three (propionyl n-butyl acetate) iron, three (propionyl sec-butyl acetate) iron, three (propionyl tert-butyl acetate) iron, three (acetoacetates Benzyl ester) iron, three (dimethyl malenate) iron, three (diethyl malonate) iron, trimethoxy iron, triethoxy iron, three isopropyl oxygen The Fe-series catalysts such as base iron, iron chloride.These crosslinking catalysts can be a kind, two or more can also be applied in combination.
The content of aforementioned crosslinking catalyst is not particularly limited, such as relative to aforementioned (methyl) acrylic polymer 100 parts by weight, preferably from about 0.0001~1 parts by weight, more preferably 0.001~0.5 parts by weight.If in aforementioned range, Then fast in the speed for forming adhesive phase post-crosslinking reaction, the service life of adhesive composition also increases, and is preferred mode.
In turn, in aforementioned adhesion agent composition, other well known additives can be contained, it can be according to used use It is properly added the powder such as lubricant, colorant, pigment, plasticizer, tackifier, low-molecular weight polymer, surface profit on the way It is lubrication prescription, levelling agent, antioxidant, anticorrosive, light stabilizer, ultraviolet absorbing agent, polymerization inhibitor, silane coupling agent, antistatic Agent, inorganic or organic filler, metal powder, granular substance, foil-like object etc..
<the optics surface protective film with slider>
Optics with slider of the invention with surface protective film (surface protective film) be base film at least Single side is formed made of aforementioned adhesion oxidant layer, at this point, the crosslinking of adhesive composition is generally after the coating of adhesive composition It carries out, the adhesive phase formed by the adhesive composition after being crosslinked can also be transferred to base film etc..
In addition, the method for forming adhesive phase on base film is unlimited, such as by the way that aforementioned adhesion agent composition is (molten Liquid) it is coated on base film, dry removal polymer solvent etc. and forms adhesive phase on base film to make.Then, may be used Adjustment with the adjustment, cross-linking reaction shifted for the ingredient of adhesive phase etc. and cured.In addition, being combined by adhesive Object is coated on base film come when making surface protective film, in order to be equably coated on base film, Ke Yi More than one solvents in addition to polymer solvent are newly added in aforementioned adhesion agent composition.
In addition, the forming method as adhesive phase when manufacturing surface protective film of the invention, can be used adhesive tape Well known method used in the manufacture of class.Specifically, can for example enumerate: print roll coating method, heliogravure rubbing method, inverse Turn rubbing method, roller brush method, spraying coating method, air knife coating method, extrusion coating methods based on mould coating machine etc. etc..
Surface protective film of the invention is usually with aforementioned adhesive phase with a thickness of 3~100 μm, preferably 5~50 μm The mode of left and right makes.If the thickness of adhesive phase in aforementioned range, be easy to get appropriate releasable with it is bonding Balance between property, therefore it is preferred that.
In addition, the overall thickness of surface protective film of the invention is preferably 8~300 μm, more preferably 10~200 μm, most Preferably 20~100 μm.If in aforementioned range, adhesion characteristic (releasable, cementability etc.), workability, appearance characteristics It is excellent, it is preferred mode.It should be noted that aforementioned overall thickness refer to including base film, adhesive phase, slider and its The summation of thickness including all layers such as his layer.
<slider>
Surface protective film of the invention is characterized in that thering is adhesive phase in at least single side of base film, The opposing face in the face of aforementioned substrates film contacted with adhesive phase has slider, and aforementioned slider has release layer and base Material, the mist degree of aforementioned slider is 90% or more, total light transmittance is 50% or less.Aforementioned slider is in order to protect adhesive phase Adhesive surface and adhesive layer surface fitting slider, especially by make slider have specific mist degree, total light transmittance This optical characteristics can accurately carry out position tune with surface protective film to the optics with slider on optical component It is whole, also, after the adjustment of position, the optics for having removed slider surface protective film is pasted into (stacking) in optical component table Face is preferred mode.
The mist degree of aforementioned slider is 90% or more, total light transmittance is 50% or less (0~50%), and preferably mist degree is 92% Above, total light transmittance is 5~50%, and more preferable mist degree is 94% or more, total light transmittance is 8~48%, further preferred mist degree It is 10~45% for 96% or more, total light transmittance.By 90% or more the mist degree, the total light transmittance 50% that make aforementioned slider Hereinafter, make the position scalability relative to optical component surfaces of the optics surface protective film with slider excellent, After the adjustment of position, by removing slider, optical component surfaces can be fitted in accurate position, therefore be preferred mode. It is 50% or less (0~50%) especially as total light transmittance, preferably 48% hereinafter, more preferably 45% hereinafter, further Preferably 40% hereinafter, particularly preferably 30% or less.By keeping total light transmittance lower, make it easy to carry out the light with slider Surface protective film is adjusted relative to the position of optical component surfaces, and position scalability, workability are excellent, are preferred.
<substrate>
It is suitable for using paper, plastic film as aforementioned substrates.As the film, as long as aforementioned adhesion oxidant layer can be protected Film be not particularly limited, such as can enumerate: polyethylene film, polypropylene film, polybutene film, polybutadiene are thin Film, poly-methyl pentene film, polyvinyl chloride film, vinyl chloride copolymer film, pet film, poly- naphthalene Naphthalate film, polybutylene terephthalate (PBT) film, polyurethane film, ethylene-vinyl acetate copolymer Film etc., especially with polyethylene terephthalate (PET) film as polyester film, poly- naphthalenedicarboxylic acid second two Alcohol ester film, polybutylene terephthalate (PBT) film etc. are preferred modes.
It is prepared into 90% or more mist degree, 50% the following method of total light transmittance as by aforementioned slider, it can be without spy Not Xian Zhi ground use well known method, can for example, by constitute slider substrate in setting cavity, addition coloured material, It is prepared by roughening of substrate surface etc..Specifically, the method etc. of Japanese Unexamined Patent Publication 9-12759 record can be enumerated.
The thickness of aforementioned substrates is usually 5~200 μm, and preferably 10~100 μm or so.If in aforementioned range, It is excellent relative to the fissility of adhesive phase, workability to the fitting workability of adhesive phase, slider, therefore it is preferred that.
For aforementioned substrates, it can according to need and the various surface treatments such as Corona discharge Treatment are implemented to its surface, or Implement the various surface processing such as embossing processing.Furthermore, it is possible to be compounded filler (inorganic filler, organic filling as needed Agent etc.), anti-aging agent, antioxidant, ultraviolet absorbing agent, antistatic agent, lubricant, plasticizer, colorant (pigment, dyestuff etc.) Etc. various additives.
As the commercially available product of aforementioned substrates, such as can enumerate: (the above are three by DIAFOIL W100, DIAFOIL W400 The manufacture of water chestnut resin Co., Ltd.), Lumirror#50-EA3S (Dongli Ltd.'s manufacture), CQ952 (manufacture of KOLON company) Deng.
<release layer>
Aforementioned release layer has adaptation to aforementioned substrates, and has fissility, Ke Yiyou relative to aforementioned adhesion oxidant layer Mold release compositions are formed.As aforementioned mold release compositions, be not particularly limited, can be used such as dimethyl siloxane, The organo-silicon compound such as diphenyl siloxane, chain alkyls class compound such as organic siliconresin, fluororesin, ASHIO RESIN etc..
In turn, can be containing additive well known to other in aforementioned mold release compositions, it can be according to used use It is properly added the powder such as antistatic agent, colorant, pigment, surfactant, plasticizer, tackifier, low molecular weight on the way Polymer, surface lubricant, levelling agent, antioxidant, anticorrosive, light stabilizer, ultraviolet absorbing agent, polymerization inhibitor, silane Coupling agent, inorganic or organic filler, metal powder, granular substance etc..
<production of slider>
Aforementioned slider is to be formed in aforementioned substrates using aforementioned mold release compositions.
On substrate formed release layer method it is unlimited, such as by by the solution coating of aforementioned mold release compositions in base Material, drying remove polymer solvent etc. and form release layer on substrate to make.It is then possible to which the ingredient for release layer shifts Adjustment etc. and cured.In addition, when mold release compositions are coated on substrate to make release layer, in order to It is equably coated on substrate, more than one solvents in addition to polymer solvent can be newly added in aforementioned mold release compositions.
In addition, the forming method as aforementioned release layer, can be used well known method used in the manufacture of release layer.Tool For body, such as can enumerate: print roll coating method, reverses rubbing method, roller brush method, spraying coating method, gas at heliogravure rubbing method Knife rubbing method, extrusion coating methods based on mould coating machine etc. etc..
The thickness of aforementioned release layer is typically 1~200nm, preferably 5~100nm, more preferably 10~50nm.If The thickness of release layer is too small, then becomes difficult to removing slider, and therefore, the operation of fitting optics surface protective film is possible to It can become difficult.And if blocked up, the pollution of the adhesive phase of optics surface protective film is had an impact sometimes.
It as the commercially available product of aforementioned slider, such as can enumerate: Crisper K7211-50 μm, Crisper K7211- 38 μm (the above are Japan spin Co., Ltd. manufacture), PET50 (K2411) PAT1 8LK, PET50 (K2411) PAT1 9K (more than For Lindeke Co., Ltd's manufacture) etc..
< optics surface protective film is bonded (production of the optics surface protective film with slider) with slider >
Optics with slider of the invention is by the adhesive phase of optics surface protective film with surface protective film Form made of being bonded with the release layer of slider.Fitting uses well known method, such as can enumerate using laminating machine (strain formula meeting Society MCK manufacture, MRK-600) mode that is bonded optics surface protective film with slider.
<optical component>
In the present invention, it can will be shelled from the surface of the adhesive phase of the optics surface protective film of aforementioned strip slider Optics from aforementioned slider is pasted on optical component with surface protective film to protect optical component.Aforementioned slider due to Resiliency is excellent, therefore is not likely to produce impression, in addition, aforementioned optical surface protective film is excellent due to exterior quality (aesthetic appearance) It is different, therefore the surface protection purposes (surface protective film) when being processed to, convey, shipping etc., thus for protection before It is useful for stating the surface of optical component (polarizer etc.).
Embodiment
Hereinafter, being illustrated several embodiments related to the present invention, but it is not intended to limit the invention to these Scheme shown in concrete example.It should be noted that " part " and " % " in following explanation is in the case where no special declaration Weight basis.In addition, giving the compounding amount (additive amount) in table.
In addition, each characteristic in following explanation is measured or evaluates as follows respectively.
<measurement of mist degree>
The measurement of mist degree (haze value) is according to specified in JIS K7136 " the seeking method of plastics-transparent material haze value " Method is carried out using mist degree instrument (manufacture of color technical research institute, HM-150 type in village).
<measurement of total light transmittance>
The measurement of total light transmittance is according to regulation in JIS K7361 " test method of plastics-transparent material total light transmittance " Method carried out using mist degree instrument (in village color technical research institute manufacture, HM-150 type).
<measurement of the glass transition temperature (Tg) of (methyl) acrylic polymer>
Glass transition temperature (Tg) (DEG C) uses following literature values as the glass of the homopolymer formed by each monomer Change transition temperature Tgn (DEG C), is found out according to following formula.
Formula: 1/ (Tg+273)=Σ [Wn/ (Tgn+273)]
(in formula, Tg (DEG C) indicates that the glass transition temperature of copolymer, Wn (-) indicate the weight fraction of each monomer, Tgn (DEG C) indicates that the glass transition temperature of the homopolymer formed by each monomer, n indicate the type of each monomer.)
Literature value:
2-EHA (2EHA): -70 DEG C
Butyl acrylate (BA): -55 DEG C
Acrylic acid 2- hydroxyl ethyl ester (HEA): -15 DEG C
Acrylic acid (AA): 106 DEG C
It should be noted that having references to " compounding design and new application of acrylic resin are developed " as literature value (" ア Network リ Le resins synthesis designs と new application Kai development ", central Management and exploitation center publishing department (Zhong Yang Longitude Operating Kai development セ ン タ ー publishing department) distribution).
<measurement of the weight average molecular weight (Mw) of (methyl) acrylic polymer>
The weight average molecular weight (Mw) of used (methyl) acrylic polymer is manufactured using TOSOH Co., Ltd GPC device (HLC-8220GPC) is measured.Determination condition is as follows.
Sample concentration: 0.2 weight % (THF solution)
Sample injection rate: 10 μ l
Eluent: THF
Flow velocity: 0.6ml/min
Measuring temperature: 40 DEG C
Chromatographic column:
Sample chromatogram column；TSKguardcolumn SuperHZ-H (1)+TSKgel SuperHZM-H (2)
Reference chromatogram column；TSKgel SuperH-RC (1)
Detector: differential refractometer (RI)
It should be noted that weight average molecular weight is found out with polystyrene scaled value.In addition, measurement number-average molecular weight (Mn) When, also equally it is measured with weight average molecular weight (Mw).
<can automatic attaching>
Only surface protective film is cut in a manner of the slider of surface protective film by not cutting off the optics with slider At 100mm × 110mm.Then, it is opened on slider in a manner of being contacted respectively with the 4 of the surface protective film being cut into angle The hole of diameter 5mm out.
Adsorption plate in the side of accurate monolithic make-up machine (Climb Products. manufacture, SE650naa) (is denoted as below Adsorption plate 1) on be arranged in a manner of side is isolated upward and protected by the optics with slider that the above method has opened hole with surface Film is protected, the glass of 100mm × 110mm is set on the adsorption plate (being denoted as adsorption plate 2 below) of the other side.Revolve adsorption plate 1 Turn and Chong Die with adsorption plate 2, the position of adsorption plate 2 is adjusted by the subsidiary CCD camera of accurate monolithic make-up machine, so that band The hole of the optics of slider surface protective film is not be overlapped with glass.Behind adjustment position (referring to fig. 2), temporarily by adsorption plate 1 It is lifted from adsorption plate 2, removes slider, adsorption plate 1 is moved on adsorption plate 2 again, with roller pressure 8kgf/cm2, roller speed Optics was fitted in glass surface with surface protective film in 5mm/ seconds.
Can automatic attaching (evaluation) be position tune automatically and accurately to be carried out with surface protective film to optics Whole and the case where being bonded, is denoted as zero, will fail the case where automatically and accurately carrying out position adjustment with surface protective film to optics Be denoted as ×.
<preparation of (methyl) acrylic polymer (A)>
Into the four-hole boiling flask for having stirring blade, thermometer, nitrogen ingress pipe, condenser, acrylic acid 2- ethyl is added Own 100 parts by weight of ester (2EHA), 4 parts by weight of acrylic acid 2- hydroxyl ethyl ester (HEA), as polymerization initiator 2,2 '-azos two it is different 0.2 parts by weight of butyronitrile (AIBN), 205 parts by weight of ethyl acetate, nitrogen is passed through when being slowly stirred, and the liquid temperature in flask is kept The polymerization reaction that about 4 hours are nearby carried out at 63 DEG C, is made (methyl) acrylic polymer (A) solution (about 35 weight %). The weight average molecular weight (Mw) of aforementioned (methyl) acrylic polymer (A) is 650,000, and glass transition temperature (Tg) is -68 DEG C.
<preparation of (methyl) acrylic polymer (B)>
Into the four-hole boiling flask for having stirring blade, thermometer, nitrogen ingress pipe, condenser, butyl acrylate is added (BA) 95 parts by weight, 5 parts by weight of acrylic acid (AA), as 2,2 '-azodiisobutyronitrile, 0.1 parts by weight of polymerization initiator, vinegar 234 parts by weight of acetoacetic ester, nitrogen is passed through when being slowly stirred, and the liquid temperature in flask is maintained at 65 DEG C and is nearby carried out 6 hours (methyl) acrylic polymer (B) solution (30 weight %) is made in polymerization reaction.Aforementioned (methyl) acrylic polymer (B) weight average molecular weight (Mw) is 1,100,000, and glass transition temperature (Tg) is -47 DEG C.
[preparation of acrylic adhesives (1) solution]
Above-mentioned (methyl) acrylic polymer (A) solution (35 weight %) is diluted to 29 weight % with ethyl acetate, In 500 parts by weight of solution (100 parts by weight of solid component), it is added as crosslinking agent and belongs to 3 functional isocyanate chemical combination The isocyanuric acid ester body (CORONATE HX:C/HX, the manufacture of Japanese polyurethane Co., Ltd.) of the hexamethylene diisocyanate of object 4 parts by weight (4 parts by weight of solid component), dibutyl tin dilaurate (" Sn ", 1 weight % in table 2 as crosslinking catalyst Ethyl acetate solution) 1.5 parts by weight (0.015 parts by weight of solid component), it is maintained at the mixing that 25 DEG C nearby carry out about 1 minute and stirs It mixes, acrylic adhesives (1) solution is made.
[preparation of acrylic adhesives (2) solution]
Above-mentioned (methyl) acrylic polymer (A) solution (35 weight %) is diluted to 29 weight % with ethyl acetate, In 500 parts by weight of solution (100 parts by weight of solid component), isocyanates crosslinking agent (six Asias as crosslinking agent are added The isocyanuric acid ester body (trade name " CORONATE HX ": C/HX, the manufacture of Japanese polyurethane Co., Ltd.) of methyl diisocyanate 5 parts by weight (5 parts by weight of solid component), as the dibutyl tin dilaurate of crosslinking catalyst, (1 weight % ethyl acetate is molten Liquid) 3 parts by weight (0.03 parts by weight of solid component), as the chain containing polyoxy alkylidene without organopolysiloxane of additive Object (Aquaron HS-10, Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture) 0.3 parts by weight (0.3 parts by weight of solid component) are closed, are carried out It is mixed, acrylic adhesives (2) solution is made.
[preparation of acrylic adhesives (3) solution]
Above-mentioned (methyl) acrylic polymer (B) solution (30 weight %) is diluted to 29 weight % with ethyl acetate, In 500 parts by weight of solution (100 parts by weight of solid component), be added as crosslinking agent epoxy crosslinking agent (it is 1,3- bis- (N, N- diglycidyl amino methyl) hexamethylene, epoxide equivalent: 110, functional group number: 4, trade name " TETRAD-C ": T/C, three The manufacture of water chestnut gas Chemical Co., Ltd.) 6 parts by weight (6 parts by weight of solid component), it is mixed, acrylic adhesive is made Agent (3) solution.
[preparation of carbamates adhesive (4) solution]
It is compounded Preminol S3011 (the Asahi Glass strain formula meeting for belonging to the polyalcohol with 3 hydroxyls as polyalcohol Society manufacture, Mn=10000) 85 parts by weight, belong to the polyalcohol with 3 hydroxyls SANNIX GP3000 (Sanyo be melted into strain formula Commercial firm manufacture, Mn=3000) 13 parts by weight, belong to the polyalcohol with 3 hydroxyls SANNIX GP1000 (Sanyo be melted into strain Formula commercial firm manufacture, Mn=1000) 2 parts by weight, as crosslinking agent the hexa-methylene two for belonging to 3 functional isocyanate compounds it is different Isocyanuric acid ester body (CORONATE HX:C/HX, Japanese polyurethane Co., Ltd. manufacture) 18 parts by weight of cyanate, as urging The pentanedione iron (III) (" Fe ", Tokyo Chemical Industry Co., Ltd's manufacture in tri acetylacetonato iron, table 3) of agent 0.04 parts by weight, the isopropyl myristate (EXCEPARL IPM, Kao Corp's manufacture) 30 as wetability modifier Parts by weight, as Irganox1010 (BASF AG's manufacture) 0.5 parts by weight of antioxidant, as the acetic acid second of retarder thinner 210 parts by weight of ester obtain carbamates adhesive (4) solution.
[preparation of silicone adhesive category (5) solution]
It is compounded " X-40-3229 " (60 weight % of solid component, SHIN-ETSU HANTOTAI's chemical industry strain formula as silicone adhesive category Commercial firm's manufacture) based on solid component 100 parts by weight, " CAT-PL-50T " (SHIN-ETSU HANTOTAI's chemical industry strain formula meeting as platinum catalyst Society's manufacture) 0.5 parts by weight, 100 parts by weight of toluene as solvent, obtain silicone adhesive category (5) solution.
[slider I, II and VII]
As shown in table 5, use the substrate with release layer to be provided with release layer in substrate (PET film) as isolation The commercially available product of body.
[production of slider III]
It is solid that silicone release (Shin-Etsu Chemial Co., Ltd's manufacture, KS-847H) 100 parts by weight, organosilicon is added Change catalyst (Shin-Etsu Chemial Co., Ltd's manufacture, CAT-PL-50T) 3.3 parts by weight, with toluene (light petrochemistry system out Make), hexane (Maruzen Petrochemical Co., Ltd. manufacture, n-hexane), methyl ethyl ketone (Idemitsu Kosen Co., Ltd.'s manufacture, MEK) press Solvent made of the weight ratio of 1:2:1 is diluted to 0.3 weight %, obtains mold release compositions.The mold release compositions are coated with In 50 μm of thickness of the PET film (Mitsubishi Plastics Inc's manufacture, DIAFOIL W100) as substrate, done at 130 DEG C Dry 1 minute, slider III is made.After the drying of release layer with a thickness of 20nm.
[production of slider IV~VI and VIII]
As shown in table 5, instead of PET film used in slider III, using the PET film for the trade name that table 5 is recorded, In addition to this it is made by method same as the production of slider III.
<embodiment 1>
[production of antistatic treatment film]
Antistatic agent (SOLVEX INC. manufacture, MICRO-SOLVER RMd-142, is made with tin oxide and polyester resin For main component) the mixed solvent dilution formed by 30 parts by weight of water and 70 parts by weight of methanol of 10 parts by weight, it is thus made anti- Electrostatic agent solution.
Use Meyer wire rod that gained antistatic agent solution is coated on to the poly terephthalic acid second two as base film On alcohol ester (PET) film (thickness: 38 μm), solvent is removed by drying 1 minute at 130 DEG C, it is (thick to form antistatic layer Degree: 0.2 μm), antistatic treatment film is made.
[production of the optics surface protective film with slider]
By above-mentioned acrylic adhesives (1) solution coating in above-mentioned antistatic treatment film and antistatic treatment face phase Anti- face is heated 2 minutes at 130 DEG C, forms 15 μm of thickness of adhesive phase.Then, it is pasted on the surface of above-mentioned adhesive phase For the pet film of slider that implements organosilicon processing to single side, (Co., Ltd. is spun by Japan for cooperation Manufacture, trade name: Crisper K7211-38 μm, mist degree: 99.3%, total light transmittance: 13.6%, 50 μm of thickness) organosilicon The optics surface protective film with slider is made in process face.
<embodiment 2 and 3>
As shown in table 2, acrylic adhesive is used instead of acrylic adhesives used in embodiment 1 (1) solution In addition to this agent (2) solution or acrylic adhesives (3) solution are made by method similarly to Example 1 with slider Optics surface protective film.
<embodiment 4 and 5>
As shown in Table 3 and Table 4, carbamic acid is used instead of acrylic adhesives used in embodiment 1 (1) solution Ester adhesive (4) solution or silicone adhesive category (5) solution, in addition to this by obtained pair of method similarly to Example 1 Heating condition etc., gained adhesive phase thickness into adjustment optics surface protective film with slider.
<embodiment 6~10, comparative example 1 and 2>
As shown in table 6, instead of slider I used in embodiment 1, using slider II~VIII, in addition to this by with The optics surface protective film with slider is made in the same method of embodiment 1.
For the optics surface protective film with slider of embodiment and comparative example, above-mentioned compounding content, each is carried out Kind measurement and evaluation, as a result shown in table 1~table 6.It should be noted that the compounding amount in table indicates effective component.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
Note) composition slider in table 5 all PET films of substrate.
[table 6]
It is confirmed by above-mentioned table 6, in all embodiments, automatic attaching can be carried out with accurate position.Comparative example 1 It is confirmed in comparative example 2, it, can not be opposite since the mist degree and total light transmittance of slider do not fall within desired range Position adjustment is carried out with surface protective film to the optics with slider automatically in optical component surfaces, after removing slider, nothing Method pastes optics surface protective film in optical component surfaces with accurate position.
Industrial availability
Optics with slider disclosed herein use surface protective film be suitable for as panel of LCD, etc. The manufacture for the optical component that the constituent element of gas ions display pannel (PDP), organic electroluminescent (EL) display etc. uses When, when conveying etc. for protecting the surface protective film of the optical component.It is used especially as panel of LCD is applied to Polarizer (polarizing film), wavelength plate, phase plate, optical compensating film, brightness enhancement film, light diffusing sheet, the light such as reflector plate The optics of component is useful with surface protective film.
Description of symbols
1: slider
2: optics surface protective film
3: the optics surface protective film with slider
10: optical component
11: substrate
12: release layer
21: adhesive phase
22: base film

Claims (3)

1. a kind of optics surface protective film with slider is comprising: at least single side in base film has There are the optics of adhesive phase surface protective film and the opposing face in the face of the base film contacted with adhesive phase The slider having,
The slider has release layer and substrate,
The mist degree of the slider is 90% or more, total light transmittance is 50% or less.
2. the optics surface protective film according to claim 1 with slider, which is characterized in that the base film For polyester film.
3. the optics surface protective film according to claim 1 or 2 with slider, which is characterized in that the bonding Oxidant layer is by containing at least one kind of in acrylic adhesives, carbamates adhesive and silicone adhesive category Adhesive composition is formed.
CN201780081268.4A 2016-12-28 2017-12-18 Surface protective film Active CN110121416B (en)

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US20040197533A1 (en) * 2001-11-02 2004-10-07 Koji Kamiyama Image covering laminate film and image projection sheet
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JP2013095913A (en) * 2011-11-07 2013-05-20 Lintec Corp Method for manufacturing adhesive sheet, and display device and portable device provided with adhesive sheet manufactured by the method
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JPWO2018123688A1 (en) 2019-10-31

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