CN110109211A - The optical laminate of belt surface protective film - Google Patents

The optical laminate of belt surface protective film Download PDF

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Publication number
CN110109211A
CN110109211A CN201910103207.4A CN201910103207A CN110109211A CN 110109211 A CN110109211 A CN 110109211A CN 201910103207 A CN201910103207 A CN 201910103207A CN 110109211 A CN110109211 A CN 110109211A
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CN
China
Prior art keywords
optical laminate
protective film
film
layer
resin
Prior art date
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Pending
Application number
CN201910103207.4A
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Chinese (zh)
Inventor
新美健二郎
中田美惠
森永总司
高山侃也
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Nitto Denko Corp
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Nitto Denko Corp
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Publication date
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Publication of CN110109211A publication Critical patent/CN110109211A/en
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Classifications

    • 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
    • B32B7/022—Mechanical 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
    • 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
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention provide a kind of surface protection film high-rate release property it is excellent and inhibit with can dramatically bubble, excellent appearance belt surface protective film optical laminate.The optical laminate of belt surface protective film of the invention has optical laminate and surface protection film.Surface protection film has substrate and adhesive phase and strippingly fits in optical laminate by adhesive phase.The adhesive phase of surface protection film with a thickness of 2 μm hereinafter, and adhesive phase surface roughness Sa1For 30nm or less.The surface roughness Sa in the face of optical laminate contacted with adhesive phase2For 30nm or less.

Description

The optical laminate of belt surface protective film
Technical field
The present invention relates to the optical laminates of belt surface protective film.
Background technique
For optical laminate (for example, polarizing film, include the laminated body of polarizing film), the light is applied in actual use It, can in order to protect the optical laminate (being finally image display device) during learning until the image display device of laminated body It is fitted with surface protection film to removing.In actual use, optical laminate/surface protection film laminated body is fitted in into display Unit and make image display device, by surface protection film stripping and removed at the subsequent appropriate moment.Representative surface is protected Cuticula has the resin film and adhesive phase as substrate.In recent years, according to purpose, the adhesive of surface protection film is sometimes required that The light separation and/or slimming of layer.When surface protection film with thin adhesive phase is fitted in optical laminate, exist sometimes Entire binding face generates bubble.In this case, even if being fitted with display unit of optical laminate itself, there is no problem, sometimes Also image display device can be caused to be judged as due to the bubble from surface protection film in the inspection before delivery bad.By This, has that efficiency of the image display device from manufacture to delivery reduces, strong it is expected improvement alternative or resolution policy.Separately Outside, as the fundamental characteristics of surface protection film, it is desirable that for continuing to improve from the fissility on optical laminate.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-088651 bulletin
Summary of the invention
Problems to be solved by the invention
The present invention is to complete in order to solve the above-mentioned existing problems, and main purpose is to provide a kind of surface protection film High-rate release property it is excellent and inhibit with can dramatically bubble, excellent appearance belt surface protective film optical laminate.
Solution to the problem
The optical laminate of the belt surface protective film of embodiments of the present invention has optical laminate and surface protection film； The surface protection film has substrate and adhesive phase, and strippingly fits in the optical laminate by the adhesive phase；It should The adhesive phase of surface protection film with a thickness of 2 μm hereinafter, and the adhesive phase surface roughness Sa1For 30nm or less；It should The surface roughness Sa in the face of optical laminate contacted with the adhesive phase2For 30nm or less.
In one embodiment, described adhesive layer with a thickness of 1 μm or less.
In one embodiment, the surface roughness Sa of described adhesive layer1For 10nm or less.
In one embodiment, the surface roughness in the face of the optical laminate contacted with described adhesive layer Sa2For 10nm or less.
In one embodiment, the high speed peeling force of the optical laminate of the belt surface protective film is 0.20N/25mm Below.
In one embodiment, the surface protection film with a thickness of 15 μm~60 μm.
In one embodiment, the surface protection film is further in the opposite with described adhesive layer of the substrate Side has antistatic layer.
In one embodiment, constitute described adhesive layer adhesive base resin be selected from organic silicon resin, Acrylic resin, urethane based resin and rubber resin.
In one embodiment, the optical laminate includes polarizer.
In one embodiment, the polarizer with a thickness of 3 μm~30 μm.
The effect of invention
According to the present invention, by the optical laminate of belt surface protective film to the thickness of the adhesive phase of surface protection film Degree and surface roughness Sa1With the surface roughness Sa of the optical laminate contacted with adhesive phase2It is optimized, Ke Yishi The high-rate release property of existing surface protection film inhibit excellent and significantly bubble, excellent appearance belt surface protective film optical layer Stack.
Detailed description of the invention
Fig. 1 is the constructed profile of the optical laminate of the belt surface protective film of an embodiment of the invention.
Symbol description
10 optical laminates
20 surface protection films
21 substrates
22 adhesive phases
The optical laminate of 100 belt surface protective films
Specific embodiment
Hereinafter, being illustrated to the preferred embodiment of the present invention, but the present invention is not limited to these embodiments.
A. the summary of the optical laminate of belt surface protective film
Fig. 1 is the constructed profile of the optical laminate of the belt surface protective film of an embodiment of the invention.This reality The optical laminate 100 for applying the belt surface protective film of mode has optical laminate 10 and surface protection film 20.Surface protection film 20 have substrate 21 and adhesive phase 22.Surface protection film 20 strippingly fits in optical laminate by adhesive phase 22 10.It is any suitable that the side opposite with adhesive phase 22 of substrate 21 in surface protection film 20 can according to need setting Process layer (not shown).In embodiments of the present invention, adhesive phase 22 with a thickness of 2 μm or less and surface roughness Sa1 For 30nm or less；The surface roughness Sa in the face of optical laminate 10 contacted with adhesive phase 222For 30nm or less.By such as The thickness of the adhesive phase of surface protection film is set as very thin, by surface roughness Sa by this place1Be set as given value or less, And by the surface roughness Sa in the face of optical laminate contacted with adhesive phase2It is set as given value hereinafter, may be implemented The high-rate release property of surface protection film is excellent and the optics of (inhibiting bubble significantly) belt surface protective film of excellent appearance Laminated body.In actual use, the optical laminate of belt surface protective film is fitted in into display unit, is shown to make image Device, when the subsequent appropriate moment removing surface protection film stripping, if the optical laminate of belt surface protective film exists Bubble, even if being then fitted with display unit of optical laminate of belt surface protective film itself, there is no problem, sometimes also can be because of band The bubble of the optical laminate of surface protection film and to cause image display device to be judged as in the inspection before delivery bad.By This, has that efficiency of the image display device from manufacture to delivery reduces.The belt surface of embodiments of the present invention is protected The optical laminate of film can eliminate such problems, therefore industrial value is very big.In addition, as described above, the present invention Embodiment belt surface protective film optical laminate it is excellent in terms of the high-rate release property of surface protection film, therefore, from It is from the perspective of treatability and operability and highly useful.
The high speed peeling force of the optical laminate of representative belt surface protective film is 0.20N/25mm or less.Institute as above It states, embodiment according to the present invention, such very excellent (i.e. very small, be easily peeled off) high speed may be implemented and remove Power.The high speed peeling force the low the more preferred.High speed peeling force be preferably 0.10N/25mm or less, more preferably 0.08N/25mm with Under, further preferably 0.05N/25mm or less.The lower limit of high speed peeling force can be such as 0.01N/25mm.It needs to illustrate It is that high speed peeling force refers to the peeling force under tensile speed 30m/ points, 180 ° of peel angle.
As optical laminate, the laminated body comprising the layer with any suitable optical function can be used.As light Learn laminated body specific example, can enumerate: polarizer, phase difference board, touch panel conductive film, Surface Treated Films, with And the laminated body comprising polarizing film and with appropriate configuration corresponding with purpose is (for example, antireflection circular polarizing disk, band touch surface The polarizing film of plate conductive layer, the polarizing film with phase separation layer, the one-piece type polarizing film of prismatic lens).
Hereinafter, having to the optical laminate of the belt surface protective film for having used polarizing film of an example as optical laminate It is illustrated to body, but those skilled in the art are it will be appreciated that present invention can be suitably applied to any suitable optics as described above Laminated body.
B. polarizing film
Representative polarizing film has polarizer and is configured at the protective layer of the one or both sides of polarizer.Protective layer only In the case where the side for being configured at polarizer, the outside that representative protective layer is configured in polarizer is (opposite with display unit Side).In embodiments of the present invention, as described above, the face of optical laminate (polarizing film) contacted with adhesive phase Surface roughness Sa2For 30nm or less.The face can substantially be arranged in the surface of the protective layer in the outside of polarizer.
Surface roughness Sa2Be as described above 30nm or less, preferably 15nm or less, more preferably 10nm or less, into one Step is preferably 5nm or less, particularly preferably 3nm or less, particularly preferably 1nm or less.Surface roughness Sa2Lower limit can be Such as 0.1nm.In surface roughness Sa2When for such range, can by the thickness of the adhesive phase of surface protection film with Surface roughness Sa1Synergy, realize the high-rate release property of excellent surface protection film, and gas can be inhibited significantly Bubble, realizes excellent appearance.It should be noted that surface roughness Sa2It can be according to ISO25178-6 (2010) or JIS B 0681-6:2014 is measured (about aftermentioned Sa1Also the same processing).
B-1. polarizer
As the polarizer of polarizing film, any suitable polarizer can be used.For example, the resin film for forming polarizer can be with It is the resin film of single layer, can also be formed by two layers or more of laminated body.
As the specific example for the polarizer being made of the resin film of single layer, can enumerate to polyvinyl alcohol (PVA) class film, The hydrophilic macromolecule films such as part formalizing PVA class film, the partly-hydrolysed film of vinyl-vinyl acetate copolymer class implement benefit The dehydration for dyeing film obtained from processing and stretch processing, PVA carried out with dichroic substances such as iodine, dichroic dyes Polyenoid based oriented film such as dehydrochlorinated products of object, polyvinyl chloride etc..Since optical characteristics is excellent, it is preferable to use with iodine pair PVA class film dye and polarizer obtained from simple tension.
The above-mentioned dyeing using iodine is for example by carrying out PVA class film immersion in iodine aqueous solution.Above-mentioned simple tension Stretching ratio is preferably 3~7 times.Stretching can carry out after dyeing processing, can also be carried out on one side with an Edge Coloring.In addition, It can dye after the stretch.It can according to need and swelling treatment, crosslinking Treatment, cleaning treatment, drying process are implemented to PVA class film Deng.For example, can not only clean the dirt of PVA class film surface by washing PVA class film immersion in water before dyeing Dirt, antiblocking agent, and PVA class membrane swelling can be made, it prevents from dyeing unequal.
It as the specific example for the polarizer for using laminated body to obtain, can enumerate: using resin base material and be laminated in this It the laminated body of the PVA resinoid layer (PVA resin film) of resin base material or is applied using resin base material on the resin base material Polarizer obtained from the laminated body for the PVA resinoid layer that cloth is formed.Shape is coated with using resin base material and on the resin base material At PVA resinoid layer laminated body obtained from polarizer can make in the following manner: for example, PVA resinoid is molten Liquid is coated on resin base material, makes it dry, and forms PVA resinoid layer on resin base material, obtains resin base material and PVA resinoid The laminated body of layer；The laminated body is stretched and dyed, polarizer is made in PVA resinoid layer.In the present embodiment, generation The stretching of table includes being impregnated in laminated body in boric acid aqueous solution and stretching.In addition, stretching can according to need into one Step includes carrying out laminated body under high temperature (for example, 95 DEG C or more) to draw in atmosphere before stretching in boric acid aqueous solution It stretches.Obtained resin base material/polarizer laminated body can be used directly (i.e., it is possible to using resin base material as the guarantor of polarizer Sheath), resin base material can also be removed from resin base material/polarizer laminated body and stacking and mesh in the release surface Corresponding any suitable protective layer and use.The details of the manufacturing method of such polarizer is recorded in for example Japanese Special open 2012-73580 bulletin.Whole record of the bulletin is quoted into this specification in reference form.
Representative polarizer with a thickness of 3 μm~30 μm.In one embodiment, the thickness of polarizer is preferably 15 μm or less, more preferably 1 μm~12 μm, further preferably 3 μm~12 μm, particularly preferably 3 μm~8 μm.In another reality It applies in mode, the thickness of polarizer is preferably greater than 15 μm and 25 μm or less.
B-2. protective layer
Protective layer is formed by any suitable film that can be used as the protective layer of polarizer.Formation material as resin film Material, can enumerate for example: the cellulosic resins such as (methyl) acrylic resin, cellulose diacetate, cellulose triacetate, drop The esters such as the olefine kind resins such as the cyclenes such as borneol vinyl resin hydrocarbon resins, polypropylene, polyethylene terephthalate resinoid Resinoid, polyamide-based resin, polycarbonate resin, their copolymer resin etc..Preferably (methyl) acrylic compounds tree Rouge.It should be noted that " (methyl) acrylic resin " refers to acrylic resin and/or methacrylic resin.
In one embodiment, as above-mentioned (methyl) acrylic resin, can be used has glutarimide structure (methyl) acrylic resin.(methyl) acrylic resin (hereinafter also referred to glutaryl with glutarimide structure Imide resin) it is recorded in for example: Japanese Unexamined Patent Publication 2006-309033 bulletin, Japanese Unexamined Patent Publication 2006-317560 bulletin, Japan Special open 2006-328329 bulletin, Japanese Unexamined Patent Publication 2006-328334 bulletin, Japanese Unexamined Patent Publication 2006-337491 bulletin, day This special open 2006-337492 bulletin, Japanese Unexamined Patent Publication 2006-337493 bulletin, Japanese Unexamined Patent Publication 2006-337569 bulletin, Japanese Unexamined Patent Publication 2007-009182 bulletin, Japanese Unexamined Patent Publication 2009-161744 bulletin, Japanese Unexamined Patent Publication 2010-284840 public affairs Report.These records are quoted into this specification in reference form.
The protective layer for being set to the side of coating surface protective film can preferably carry out surface treatment for reducing contact angle. As the typical example of such surface treatment, sided corona treatment can be enumerated.The condition of sided corona treatment can be suitably set, so as to for Above-mentioned desired contact angle can be obtained in aforesaid liquid.
In the case where polarizing film is configured at the visible side of image display device, can according to need to being configured at polarizing film The protective layer of visible side implement hard coating, antireflection process, the surface treatment such as anti-adhesion process.Further/or can be with The processing for implementing to improve visibility to the protective layer as needed (is typically imparting (ellipse) circular polarization function, assigns Superelevation phase difference), the visibility is the visibility carried out in the case where visuognosis across polarized sunglasses.
The protective layer (inside protective layer) for being configured at the display unit side of polarizer is preferably optical isotropy.This explanation " optical isotropy " refers in book, and phase difference Re (550) is 0nm~10nm, the phase difference Rth (550) of thickness direction in face For -10nm~+10nm.As long as inside protective layer optical isotropy, so that it may be made of any suitable material.The material It can suitably be selected from above-mentioned material.
Representative protective layer with a thickness of 5mm or less, preferably 1mm or less, more preferably 1 μm~500 μm, further Preferably 5 μm~150 μm.It should be noted that in the case where implementing surface treatment, the thickness of protective layer be include surface The thickness of process layer thickness.
B-3. process layer
Can any suitable process layer preferably be formed in the side of the coating surface protective film of polarizing film.Process layer is preferred Has the function of contact angle reduction.As the specific example of process layer, antistatic layer, hydrophilic layer, hard conating can be enumerated.
Representative antistatic layer includes conductive material and adhesive resin.As conductive material, can be used any Conductive material appropriate preferably uses electric conductive polymer.As electric conductive polymer, it can be mentioned, for example: polythiophene class Polymer, polyacetylene quasi polymer, polybutadiene acetylenic polymer, carbene hydrocarbon polymer, polyphenylene quasi polymer, poly- naphthalenes Polymer, poly- anthracene quasi polymer, poly- pyrene quasi polymer, gathers at polyfluorene quasi polymerQuasi polymer, is gathered multi-metal polypyrrole polymer Furans quasi polymer, polyisothianaphthene quasi polymer, is gathered at polyselenophenes quasi polymerDiazole quasi polymer, polyaniline compound polymerization Object, polysulfur nitride (polythiazyl) quasi polymer, polyphenylene vinylene (polyphenylenevinylene) quasi polymer, Polythiophene ethylene (polythienylenevinylene) quasi polymer, polyacene (polyacene) quasi polymer, poly- phenanthrene are birdsed of the same feather flock together Close object, poly- perinaphthene (polyperinaphthalene) quasi polymer etc..These electric conductive polymers can be used alone, or Two or more is applied in combination.As adhesive resin, it is preferable to use polyurethane based resin.It, can be with by using polyurethane based resin The antistatic layer for having both flexibility and the excellent adaptation to polarizing film (being essentially protective layer) is set.
For hydrophilic layer and hard conating, composition as known in the art can be used, therefore omit detailed description.
C. surface protection film
C-1. substrate
The substrate 21 of surface protection film 20 can be made of any suitable resin film.It, can as the forming material of resin film It enumerates: the cyclenes hydrocarbon resins, polypropylene such as the esters resins such as polyethylene terephthalate resinoid, norbornene resin Equal olefine kind resins, polyamide-based resin, polycarbonate resin, their copolymer resin etc..Preferably esters resin is (special It is not polyethylene terephthalate resinoid).In the case where such material, elasticity modulus is sufficiently high, even if having Apply the advantages of tension is also not susceptible to deformation in transport and/or fitting.
Representative substrate with a thickness of 10 μm~100 μm, preferably 20 μm~50 μm.In such thickness, have The advantages of being not susceptible to deformation applying tension even if in transport and/or fitting.In embodiments of the present invention, adhesive The thickness of layer is very thin, accordingly, with respect to the thickness of surface protection film, substrate with a thickness of leading.In one embodiment, table The thickness of surface protective film can be such as 15 μm~60 μm.
The elasticity modulus of substrate can be measured typically according to JIS K 7127:1999.The elasticity modulus of substrate is preferred It is lower for 100MPa~350MPa at tensile speed 100mm/ points.When the elasticity modulus of substrate is such range, even if having Apply the advantages of tension is also not susceptible to deformation in transport and/or fitting.
C-2. adhesive phase
The thickness of adhesive phase is 2 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less as described above.Pass through The thickness of adhesive phase is set as very thin in this wise, can use the surface roughness Sa of adhesive phase1It is laminated with optics The surface roughness Sa of body2Synergy realize the high-rate release property of excellent surface protection film, and can significantly Inhibit bubble, realizes excellent appearance.The lower limit of thickness is such as 0.1 μm.When thickness is lower than lower limit, generates for example exist sometimes The problem of end tilts is easy to happen in the shock of the processing, conveying that fit in after being attached to object (optical laminate).
The surface roughness Sa of adhesive phase1It is as described above 30nm or less, preferably 15nm or less, more preferably 10nm It below, is more preferably 5nm or less.Surface roughness Sa1Lower limit can be such as 0.1nm.Surface roughness Sa1For this When the range of sample, the thickness of adhesive phase and the surface roughness Sa of optical laminate can use2Synergy realize The high-rate release property of excellent surface protection film, and bubble can be inhibited significantly, realize excellent appearance.Such surface Roughness can be realized for example, by the surface roughness of combination adjustment substrate and the thickness of adhesive phase.
The storage modulus of adhesive phase is preferably 1.0 × 104Pa~1.0 × 107Pa, more preferably 2.0 × 104Pa~5.0 ×106Pa.When the storage modulus of adhesive phase is such range, it can further inhibit bubble significantly.It needs to illustrate It is that storage modulus can be found out for example, by the Measurement of Dynamic Viscoelasticity at 23 DEG C of temperature and angular speed 0.1rad/s.
As the adhesive for forming adhesive phase, any suitable adhesive can be used.As the base resin of adhesive, It can be mentioned, for example: acrylic resin, styrene resin, organic silicon resin, urethane based resin, rubber tree Rouge.Such base resin is recorded in such as Japanese Unexamined Patent Publication 2015-120337 bulletin or Japanese Unexamined Patent Publication 2011-201983 public affairs Report.The record of these bulletins is quoted into this specification in reference form.From chemical resistance, for prevent dipping when from Manage adaptation that liquid penetrates into, to freedom degree for being attached to object etc. from the perspective of, preferably acrylic resin.As can be viscous The crosslinking agent for including in mixture, it can be mentioned, for example: isocyanate compound, epoxide, aziridine cpd.Adhesive Such as silane coupling agent can be contained.The compounding recipe of adhesive can be suitably set according to purpose.
C-3. process layer
As set forth above, it is possible to which any suitable processing is arranged in the side opposite with adhesive phase of substrate as needed Layer.As the specific example of process layer, antistatic layer, hydrophilic layer, hard conating can be enumerated.In antistatic layer such as above-mentioned B-3 item It is described.
Embodiment
Hereinafter, the present invention is concretely demonstrated by embodiment, but the present invention is not limited to these embodiments.Implement The measuring method of each characteristic in example is as described below.It should be noted that in case of no particular description, in embodiment " part " and " % " is weight basis.
(1) thickness
It for the thickness of adhesive phase, is determined as described below: cutting out the section for being formed with the film of adhesive phase, The section is observed with scanning electron microscope (SEM), determines the thickness of layer.
It for the thickness of antistatic layer, is determined as described below: using RuO4The surface of antistatic layer is contaminated Color is embedded in epoxy resin.Then, RuO is used4It is dyed to being sliced made of ultrathin sectioning, uses TEM (strain H-7650, the acceleration voltage 100V of Hitachi, formula commercial firm new and high technology manufacture) coating layer cross section is determined.
(2) surface roughness Sa1And Sa2
It is determined according to JIS B 0681-6:2014 standard.As sensing equipment, three-dimensional non-planar contact surfaces have been used Roughometer (Zygo company manufacture, ProductName: NewView7300), 50 times of object lens, measurement area 0.14mm × Arithmetic average roughness is determined under conditions of 0.11mm.
(3) high speed peeling force
For the optical laminate (polarizing film) of belt surface protective film obtained in Examples and Comparative Examples, determine table Peeling force when surface protective film is removed from polarizing film.Remove 23 DEG C of temperature, humidity 50%RH atmosphere under, use is omnipotent Cupping machine (manufacture of Minebea company, ProductName: TCM-1kNB) is carried out with 180 ° of peel angle, tensile speed 30m/ points.
(4) appearance
For the polarizing film of belt surface protective film obtained in Examples and Comparative Examples, the gas of entire surface is observed by the naked eye The generation state of bubble, is evaluated according to benchmark below.
Zero: not confirming bubble
△: major diameter 10mm bubble below is confirmed
×: confirm the bubble of major diameter 10mm or more.
<reference example 1-1>polarizing film
The production of 1-1-1. methacrylic resin film
With monomethyl amine to MS resin (MS-200；The copolymer of methyl methacrylate/styrene (molar ratio)=80/20, Nippon Steel Chemical Co., Ltd's manufacture) carry out imidizate (acid imide rate: 5%).MS resin after obtained imidizate With general formula (1) indicate glutarimide unit (in formula, R1And R3For methyl, R2For hydrogen atom), general formula (2) indicate (first Base) acrylic ester unit (R4For hydrogen atom, R5For methyl) and styrene units, acid value 0.5mmol/g.It needs to illustrate It is in above-mentioned imidizate, to have used the engagement type rotating Vortex formula double screw extruder of aperture 15mm.By each of extruder The set temperature in temperature adjustment region be set as 230 DEG C, screw speed be set as 150rpm, with 2.0kg/ hours supply MS resins, monomethyl amine Supply amount relative to 100 parts by weight of MS resin be 2 parts by weight.MS resin is put into from hopper, resin melting is made by kneading block And after being full of, monomethyl amine is filled with from nozzle.It is put into sealing ring in the end of conversion zone, is full of resin.By exhaust outlet Pressure is to -0.08MPa, to make by-product and excessive methylamine devolatilization after reaction.From being set to outlet of extruder The resin that die head is discharged in the form of strand is cooled down in the sink, is then granulated with granulator.Above-mentioned acyl is sub- MS resin after amination carries out melting extrusion and forms a film.At this point, supplying ultraviolet absorbing agent relative to 100 parts by weight of MS resin (manufacture of ADEKA company, " T-712 ") 0.66 parts by weight.Then, biaxial tension has been made to vertical 2 times, horizontal 2 times transparency protected Film (40 μm of thickness, Re=2nm, Rth=2nm).
[chemical formula 1]
[chemical formula 2]
1-1-2. the production of polarizing film
As resin base material, strip is used and water absorption rate 0.75%, Tg75 DEG C of amorphous M-phthalic acid is total Poly- polyethylene terephthalate (IPA is copolymerized PET) film (thickness: 100 μm).Sided corona treatment is implemented to the one side of substrate, and Being coated at 25 DEG C to the sided corona treatment face with the ratio of 9:1 includes that (degree of polymerization 4200, saponification degree 99.2 rub polyvinyl alcohol Your %) and acetoacetyl modified PVA (99.0 moles of degree of polymerization 1200, acetoacetyl modified degree 4.6%, saponification degree % with Upper, the Nippon Synthetic Chemical Industry Co., Ltd's manufacture, trade name " GOHSEFIMER Z200 ") aqueous solution and be dried, shape At 11 μm of thickness of PVA resinoid layer, laminated body has been made.
By obtained laminated body, (length direction) is free along longitudinal direction between the different roller of peripheral speed in 120 DEG C of baking oven Hold simple tension to 2.0 times (assisting tension in atmosphere).
Then, the insoluble bath by laminated body at 30 DEG C of fluid temperature (cooperates 4 weight of boric acid relative to 100 parts by weight of water Part obtained from boric acid aqueous solution) in impregnated of 30 seconds (insoluble processing).
Then, in 30 DEG C of fluid temperature of dye bath, it is dense in a manner of making polarizing film reach given transmissivity to adjust iodine Degree, dip time, while being impregnated.In the present embodiment, cooperates 0.2 parts by weight of iodine relative to 100 parts by weight of water and cooperate 1.5 parts by weight of potassium iodide and obtain iodine aqueous solution, impregnated of 60 seconds (dyeing processing) in the iodine aqueous solution.
Then, the crosslinking bath at 30 DEG C of fluid temperature (cooperates 3 parts by weight of potassium iodide relative to 100 parts by weight of water and cooperates Boric acid aqueous solution obtained from 3 parts by weight of boric acid) in impregnated of 30 seconds (crosslinking Treatment).
Then, the boric acid aqueous solution that laminated body is impregnated in 70 DEG C of fluid temperature (is cooperated into boric acid relative to 100 parts by weight of water 4 parts by weight simultaneously cooperate aqueous solution obtained from 5 parts by weight of potassium iodide) in, and along longitudinal direction between the different roller of peripheral speed (length direction) has carried out simple tension, so that total stretching ratio reaches 5.5 times (stretching in aqueous solution).
Then, the cleaner bath that laminated body is impregnated in 30 DEG C of fluid temperature (is cooperated into potassium iodide 4 relative to 100 parts by weight of water Aqueous solution obtained from parts by weight) in (cleaning treatment).
Next, in PVA resinoid layer (polarizer) surface coating ultraviolet curing type bonding agent of laminated body, so that solid For adhesive layer after change with a thickness of 1.0 μm, fitting constitutes the above-mentioned methacrylic resin film (thickness: 40 μm) of protective layer, from The methacrylic resin film side is heated to 50 DEG C using IR heater, irradiates ultraviolet light, solidifies bonding agent.As a result, The polarizing film 1-1 with resin base material (protective layer)/polarizer/protective layer structure is arrived.It should be noted that polarizer With a thickness of 5 μm, monomer transmissivity is 42.3%.In addition, protective layer (the methacrylic acid tree for the side being bonded with surface protection film Adipose membrane) surface roughness Sa2For 0.9nm.
<reference example 1-2>polarizing film
It, will be as friendship when adding ultraviolet absorbing agent in " production of methacrylic resin film " of reference example 1-1-1 The core-shell-type elastomer of connection elastomer adds together, has made surface roughness Sa2For the methacrylic resin film of 4.9nm. It has used the film as the protective layer for the side being bonded with surface protection film, in addition to this, has made similarly to Example 1 partially Shake piece 1-2.It should be noted that core-shell-type elastomer the production method is as follows described.
(core-shell-type elastomer)
Glass system reactor is added in the mixture of following compositions, is warming up to 80 DEG C while stirring in nitrogen stream, It then will be by 25 parts of methyl methacrylate, 1 part of the allyl methacrylate monomer mixture and tert-butyl hydroperoxide constituted 25% in mixed liquor that 0.1 part of hydrogen is added together, has carried out polymerization in 45 minutes.
Next, being continuously added to the residue 75% of the mixed liquor with 1 hour.After addition, at the same temperature It is kept for 2 hours, terminates polymerization.In addition, having added 0.2 part of N- sodium lauroyl sarcosine during this period.Obtained innermost layer is handed over The polymerisation conversion (polymerization production quantity/monomer additive amount) for joining methacrylic polymer latex is 98%.
Obtained innermost layer polymer emulsion is remained 80 DEG C in nitrogen stream, and is added to 0.1 part of potassium peroxydisulfate, so It was continuously added to afterwards by 1 part of 41 parts of n-butyl acrylate, 9 parts of styrene, allyl methacrylate monomer constituted with 5 hours Mixture.It is divided into 3 times during this period and is added to 0.1 part of potassium oleate.After the addition of monomer mixture, in order to make polymerization eventually Only, further 0.05 part of potassium peroxydisulfate of addition, and kept for 2 hours, obtain rubber particles.The polymerization of obtained rubber particles turns Rate is 99%, partial size 225nm.Obtained rubber particles latex is remained 80 DEG C, and is added to 0.02 part of potassium peroxydisulfate, Then the monomer mixture of 14 parts of methyl methacrylate, 1 part of n-butyl acrylate was continuously added to 1 hour.It is mixed in monomer It is kept for 1 hour after the addition for closing object, has obtained graft copolymer latex.Polymerisation conversion is 99%.The grafting that will be obtained Copolymer emulsion remains 80 DEG C, and the list of 5 parts of methyl methacrylate, 5 parts of n-butyl acrylate was continuously added to 0.5 hour Body mixture.After the addition of monomer mixture, is kept for 1 hour, obtained the graft copolymer latex containing rubber.It is poly- Closing conversion ratio is 99%.The obtained graft copolymer latex containing rubber saltout solidification, heat treatment, dry with calcium chloride It is dry, obtain the cross-linked elastomer of white powder.
<reference example 1-3>polarizing film
Antiglare layer is formd on the surface of methacrylic resin film, in addition to this, is made in the same manner as reference example 1-1 Polarizing film 1-3.Here, antiglare layer becomes the side being bonded with surface protection film.The surface roughness Sa of antiglare layer2For 50nm.
<reference example 2-1>surface protection film
2-1-1. antistatic layer forms the preparation for using composition (coating fluid)
Having prepared the aqueous dispersions comprising the saturation copolymer polyester resin 25% as adhesive, (Co. Ltd. system is spun by Japan Make, trade name " VYLONAL MD-1480 ") (bonding agent dispersing liquid).Further, the Brazil wax as lubricant has been prepared The aqueous dispersions (lubrication agent dispersing liquid) of (wax ester).In addition, having prepared comprising poly- (3, the 4- ethylenes two as electric conductive polymer Oxygen thiophene) (PEDOT) 0.5% and poly styrene sulfonate (number-average molecular weight 150,000) (PSS) 0.8% aqueous solution (trade name " Baytron P ", H.C.Stark Products) (electric conductive polymer aqueous solution).It is added in the in the mixed solvent of water and ethyl alcohol 100 parts of above-mentioned bonding agent dispersing liquid (solid component), above-mentioned lubrication agent dispersing liquid 30 parts (solid components) and above-mentioned conductive poly 50 parts of object aqueous solution (solid component) and melamine class crosslinking agents are closed, stir about 20 minutes, have been sufficiently carried out mixing. It is prepared for the antistatic layer formation coating fluid of NV about 0.15% as a result,.
2-1-2. the formation of antistatic layer
Transparent polyethylene terephthalate (PET) film (three of 50 μm of thickness, width 30cm, length 40cm are prepared The trade name " Diafoil T600 " of water chestnut Chemical Co., Ltd. manufacture).Sided corona treatment is implemented on one side to the PET film.Use stick Above-mentioned coating liquid in the sided corona treatment face of the PET film, is heated 2 minutes at 130 DEG C and is made it dry by painting machine.It makes as a result, Antistatic layer (10nm)/PET film laminated body is made.
2-1-3. the preparation of adhesive
(acrylic polymer)
Acrylic acid 2- ethyl hexyl is added in the 4 neck flasks for having stirring blade, thermometer, nitrogen ingress pipe, cooler 100 parts of ester (2EHA), 10 parts of acrylic acid 4- hydroxybutyl (4HBA), 0.02 part of acrylic acid (AA), as the 2 of polymerization initiator, 2 ' -0.2 part of azodiisobutyronitriles, 157 parts of ethyl acetate, import nitrogen while being slowly stirred, by the liquid temperature in flask Degree remains 65 DEG C or so, carries out 6 hours polymerization reactions, is prepared for acrylic polymer (I) solution (40%).Above-mentioned third The weight average molecular weight of olefin(e) acid quasi polymer (I) is 540,000, and glass transition temperature (Tg) is -67 DEG C.
(acrylic compounds oligomer)
Toluene is put into the 4 neck flasks for having stirring blade, thermometer, nitrogen ingress pipe, cooler, dropping funel 100 parts, two ring pentyl ester (DCPMA) of methacrylic acid (trade name: FA-513M, Hitachi Chemical Co., Ltd.'s manufacture) 60 parts, 40 parts of methyl methacrylate (MMA) and as 3.5 parts of methyl thioglycolate of chain-transferring agent.Then, in 70 DEG C, nitrogen atmosphere After lower stirring stirring in 1 hour, 0.2 part of 2, the 2 '-azodiisobutyronitrile as polymerization initiator is put into, it is small that 2 are reacted at 70 DEG C When, it is then reacted at 80 DEG C 4 hours, is then reacted 1 hour at 90 DEG C, obtained acrylic acid oligomer solution (51%). The weight average molecular weight of above-mentioned acrylic acid oligomer is 4000, and glass transition temperature (Tg) is 144 DEG C.
(acrylic adhesives A)
Above-mentioned acrylic polymer (I) solution (40%) is diluted to 4% with ethyl acetate, at 2500 parts of the solution Above-mentioned 0.59 part of the acrylic compounds oligomer solution (0.3 part of solid component) of addition in (100 parts of solid component), is added as crosslinking The chlorinated isocyanurates body (Nippon Polyurethane Industry Co., Ltd.'s manufacture, CORONATE HX) of the hexamethylene diisocyanate of agent 1.0 parts (1.0 parts of solid component), as crosslinking catalyst 3 parts of dibutyl tin dilaurate (1% ethyl acetate solution) (Gu 0.03 part of body ingredient), organopolysiloxane (KF-353, Shin-Etsu Chemial Co., Ltd manufacture) is diluted to ethyl acetate 2 parts of solution obtained from 10% (0.2 part of solid component) uses ethyl acetate will be as bis- (the three of the alkali metal salt of antistatic agent Fluorine methylsulfonyl) imine lithium (LiN (CF3SO2)2: LiTFSI, Tokyo Chemical Industry Co., Ltd's manufacture) it is diluted to obtained from 1% 15 parts of solution (0.15 part of solid component), is mixed, is prepared for acrylic adhesives solution A.
2-1-4. the production of surface protection film
Adhesive A obtained above is coated on to the PET film surface of above-mentioned laminated body using wheat Le stick (Meyer bar), So that after dry with a thickness of 0.3 μm, it is then, 1 minute dry with 130 DEG C in heated air circulation type baking oven, obtained surface guarantor Cuticula 2-1.
<reference example 2-2>surface protection film
Following adhesive M has been used, in addition to this, has got similarly surface protection film 2-2 with reference example 2-1.
(carbamates adhesive M)
Cooperation as polyalcohol with 3 hydroxyls polyalcohol PREMINOL S3011 (Asahi Glass Co., Ltd manufactures, Mn=10000) 85 parts, polyalcohol SANNIX GP3000 (Sanyo Chemical Industries Co., Ltd.'s manufacture, Mn=with 3 hydroxyls 3000) 13 parts, 2 parts of polyalcohol SANNIX GP1000 with 3 hydroxyls (Sanyo Chemical Industries Co., Ltd.'s manufacture, Mn=1000), As 10 parts of the isocyanate compound CORONATE HX (manufacture of Japanese polyurethane Co., Ltd.) of crosslinking agent, as catalyst 0.04 part of ferric acetyl acetonade (III) (Tokyo Chemical Industry Co., Ltd's manufacture), as the ethyl acetate 1000 of retarder thinner Part, obtain carbamates binder solution M.It should be noted that the original as carbamates binder solution Material, is the raw material of concentration 100% in addition to solvents.
<reference example 2-3>surface protection film
It has used following adhesive Cs, and the adhesive after coating has been dried 2 minutes at 150 DEG C, in addition to this, Surface protection film 2-3 has been got similarly with reference example 2-1.
(silicone adhesive category C)
Cooperate " X-40-3229 " (solid component 60%, SHIN-ETSU HANTOTAI's chemistry as silicone adhesive category using in terms of solid component Industrial Co., Ltd's manufacture) 100 parts, and cooperate " CAT-PL-50T " (Shin-Etsu Chemial Co., Ltd as platinum catalyst Manufacture) 0.3 part, as 1200 parts of toluene of solvent, obtained silicone adhesive category solution C.
<reference example 2-4>surface protection film
Following adhesive D has been used, in addition to this, has got similarly surface protection film 2-4 with reference example 2-1.
(rubber adhesive D)
Styreneisobutylene-styrene block copolymer (manufacture of KANEKA company, SIBSTAR072T) is dissolved in first Benzene is prepared for rubber adhesive solution D.
<reference example 2-5>surface protection film
The thickness of adhesive phase is set as 1.0 μm, in addition to this, has got similarly surface protection film with reference example 2-1 2-5。
<reference example 2-6>surface protection film
The thickness of adhesive phase is set as 5.0 μm, in addition to this, has got similarly surface protection film with reference example 2-1 2-6。
<reference example 2-7>surface protection film
PET film is changed to the trade name " Diafoil T100 " of 50 μm of thickness of Mitsubishi chemical Co., Ltd's manufacture, and The thickness of adhesive phase is set as 15 μm, in addition to this, has got similarly surface protection film 2-7 with reference example 2-1.
<reference example 2-8>surface protection film
PET film is changed to the T100 of Mitsubishi chemical Co., Ltd's manufacture, in addition to this, in the same manner as reference example 2-1 Surface protection film 2-8 is arrived.
<reference example 2-9>surface protection film
The thickness of adhesive phase is set as 0.15 μm, in addition to this, has got similarly surface protection film with reference example 2-8 2-9。
<reference example 2-10>surface protection film
The thickness of adhesive phase is set as 0.15 μm, in addition to this, has got similarly surface protection film with reference example 2-1 2-10。
<embodiment 1>
Surface protection film obtained in polarizing film obtained in reference example 1-1 and reference example 2-1 is punched into A4 ruler respectively It is very little.Using doubling roller, by after punching polarizing film and surface protection film be bonded by the adhesive phase of surface protection film, obtain The polarizing film of belt surface protective film is arrived.Evaluation by the polarizing film of obtained belt surface protective film for above-mentioned (3)~(4). Show the result in table 1.
<embodiment 2~8 and the Comparative Examples 1 to 5>
It has been bonded polarizing film and surface protection film according to combination shown in table 1, in addition to this, similarly to Example 1 The polarizing film of belt surface protective film is arrived.By the polarizing film of obtained belt surface protective film for evaluation same as Example 1. Show the result in table 1.It should be noted that " SPV " in table 1 indicates that surface protection film, " 1-2 ", " 2-5 " etc. indicate reference example Number.
<evaluation>
According to table 1, the optical laminate of the belt surface protective film of the embodiment of the present invention realizes surface protection film The removing of very good high speed, and significantly suppress bubble, excellent appearance.
Industrial applicibility
The optical laminate of belt surface protective film of the invention is suitable for various image display devices.

Claims (10)

1. a kind of optical laminate of belt surface protective film, with optical laminate and surface protection film, wherein
The surface protection film has substrate and adhesive phase, and strippingly fits in optics stacking by the adhesive phase Body,
The adhesive phase of the surface protection film with a thickness of 2 μm hereinafter, and the adhesive phase surface roughness Sa1For 30nm with Under,
The surface roughness Sa in the face of the optical laminate contacted with the adhesive phase2For 30nm or less.
2. the optical laminate of belt surface protective film according to claim 1, wherein described adhesive layer with a thickness of 1 μ M or less.
3. the optical laminate of belt surface protective film according to claim 1 or 2, wherein the surface of described adhesive layer Roughness Sa1For 10nm or less.
4. the optical laminate of belt surface protective film described in any one of claim 1 to 3, wherein the optical layer The surface roughness Sa in the face of stack contacted with described adhesive layer2For 10nm or less.
5. the optical laminate of belt surface protective film according to any one of claims 1 to 4, high speed peeling force are 0.20N/25mm or less.
6. the optical laminate of belt surface protective film according to any one of claims 1 to 5, wherein the surface is protected Cuticula with a thickness of 15 μm~60 μm.
7. the optical laminate of belt surface protective film described according to claim 1~any one of 6, wherein the surface is protected Cuticula further has antistatic layer in the side opposite with described adhesive layer of the substrate.
8. the optical laminate of belt surface protective film according to any one of claims 1 to 7, wherein constitute described viscous The base resin of the adhesive of mixture layer is selected from organic silicon resin, acrylic resin, urethane based resin and rubber Resin.
9. the optical laminate of belt surface protective film described according to claim 1~any one of 8, wherein the optical layer Stack includes polarizer.
10. the optical laminate of belt surface protective film according to claim 9, wherein the polarizer with a thickness of 3 μm ~30 μm.
CN201910103207.4A 2018-02-01 2019-02-01 The optical laminate of belt surface protective film Pending CN110109211A (en)

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Application publication date: 20190809