CN110446956A - Optical laminate - Google Patents

Optical laminate Download PDF

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Publication number
CN110446956A
CN110446956A CN201880020357.2A CN201880020357A CN110446956A CN 110446956 A CN110446956 A CN 110446956A CN 201880020357 A CN201880020357 A CN 201880020357A CN 110446956 A CN110446956 A CN 110446956A
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CN
China
Prior art keywords
weight
methyl
glass
optical laminate
film
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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.)
Pending
Application number
CN201880020357.2A
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Chinese (zh)
Inventor
杉野晶子
村重毅
稻垣淳一
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Nittosan Engineering Co Ltd
Nitto Denko Corp
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Nittosan Engineering Co Ltd
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Publication of CN110446956A publication Critical patent/CN110446956A/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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • 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
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J175/02—Polyureas
    • 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
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering

Abstract

The present invention, which provides, a kind of has glass-film and again operational excellent optical laminate.Optical laminate of the invention successively has: glass-film, polarizer and adhesive phase, and the optical laminate is 5N/25mm or less to the bonding force of glass plate.In one embodiment, above-mentioned adhesive phase with a thickness of 5 μm~100 μm.In one embodiment, above-mentioned glass-film with a thickness of 20 μm~200 μm.

Description

Optical laminate
Technical field
The present invention relates to optical laminates.
The prior art
Currently, image display device is the base that the resin film comprising polarizing film is fitted in display element by adhesive Plate is then further manufactured glass gluing by bonding agent or adhesive on the resin film.It is aobvious in such image In the manufacture of showing device, it was found that, mostly can be by the glass and the tree when fitting bad (bonding position offset, foreign matter sandwich) Bonding agent or adhesive freezing cutting between adipose membrane, then remove the resin film from the substrate of the display element.However, In the case where using such stripping technology, operation is more and many and diverse, and generation makes the productivity of image display device be deteriorated Problem.
In addition, in recent years, performing image display the light and thin of device, and have and require inclining for flexibility To propose using the optical laminate (patent document 1) being made of thinner glass.Thin glass has been used needing to remove When the optical laminate of glass, due to the fragility of the thin glass, therefore, it is difficult to as described above using the method based on freezing cutting.
For the optical laminate comprising glass, fit in after other components when being removed again Operability (operational again) becomes problem, it is desirable that improves again operational.
Existing technical literature
Patent document
Patent document 1: International Publication No. 2013-175767 bulletin
Summary of the invention
Problems to be solved by the invention
The present invention is completed to solve above-mentioned existing project, and its purpose is to provide have glass-film and grasp again The excellent optical laminate of the property made.
The method used for solving the problem
Optical laminate of the invention successively has: glass-film, polarizer and adhesive phase, the optical laminate Bonding force to glass plate is 5N/25mm or less.
In one embodiment, described adhesive layer with a thickness of 5 μm~100 μm.
In one embodiment, the glass-film with a thickness of 20 μm~200 μm.
In one embodiment, described adhesive layer includes (methyl) acrylic adhesives.
In one embodiment, described adhesive layer includes carbamates adhesive.
Another way according to the present invention provides a kind of image display device.The image display device includes the optics Laminated body.
In one embodiment, described image display device has the optical laminate in the outermost of visible side.
The effect of invention
Have glass-film and again operational excellent optical laminate according to the present invention it is possible to provide.
Detailed description of the invention
Fig. 1 is the constructed profile of the optical laminate of an embodiment of the invention.
Symbol description
10 glass-films
20 polarizers
30 adhesive phases
100 optical laminates
Specific embodiment
A. the overall structure of optical laminate
Fig. 1 is the constructed profile of the optical laminate of an embodiment of the invention.The optical laminate 100 is successively Have: glass-film 10, polarizer 20 and adhesive phase 30.Optical laminate 100 can according to need in glass-film 10 and rise The protective film 40 of protection polarizer 20 is further equipped between polariscope 20.In addition, although not shown, but also can according to need and rising Protective film is configured between polariscope 20 and adhesive phase 30.Glass-film 10, polarizer 20 and protective film 40 can be by any appropriate Adhesive or bonding agent be bonded.
Optical laminate 100 of the invention has glass-film 10, therefore hardness is very high.In addition, due to optics of the invention Laminated body 100 has polarizer 20 in the side of glass-film 10, therefore glass-film 10 can be prevented damaged, excellent impact resistance. In the present invention, the impact for being applied to the surface (face with polarizer opposite side) of glass-film 10 can be released effectively to polarizer 20 sides, it can be considered that excellent impact resistance as described above.Moreover, glass-film 10 has the function of protecting polarizer 20.That is, In the present invention, glass-film 10 and polarizer 20 are mutually protected each other respectively.Therefore, it is possible to reduce protection component can obtain To lightweight and slim optical laminate.In addition, the gas barrier property due to glass-film 10 is high, polarizer 20 can be prevented bad Change.Further, since the change in size of glass-film 10 is small, therefore the expansion or receipts of optical laminate 100 of the invention can be inhibited Contracting.As a result, available durability is high and the optical laminate 100 being inhibited such as peels off, floats.
Optical laminate of the invention be preferably 5N/25mm to the bonding force of glass plate hereinafter, more preferably 3N/25mm with Under, further preferably 1.5N/25mm or less.In the present specification, bonding force measures in the following manner: by optical layer The adhesive phase side of stack fits in glass plate, then, in the environment of 23 DEG C/humidity of temperature 55%, with 90 ° of peel angle, Peeling rate 300mm/ points are removed and are measured.Detailed measuring method is explained below.
Since the bonding force of optical laminate of the invention to glass plate is above range, then it is operational excellent.More Specifically, above-mentioned optical laminate is fitted in adherend (for example, display element substrate etc. constitutes image display device Component) when, in case of any unfavorable condition (for example, positional shift, foreign matter sandwich), must just remove optics stacking Body, but at this point, if it is the bonding force to glass plate be above range optical laminate, then glass-film can be prevented to be broken, hold Easily it is removed from adherend.
Optical laminate of the invention is preferably 0.005N/25mm or more to the lower limit value of the bonding force of glass plate, more excellent It is selected as 0.01N/25mm or more, further preferably 0.1N/25mm or more.In such range, though at high heat and/or Under high humility, it is also possible to prevent a problem that peeling off, floating.
The thickness of optical laminate of the invention is preferably 50 μm~500 μm, more preferably 100 μm~300 μm.
Optical laminate of the invention can also have other layers.As other layers, can enumerate for example: anti-reflecting layer, Antiglare layer, antistatic layer, conductive layer etc..It can also be in the surface configuration diaphragm of adhesive phase.The diaphragm can protect adhesive Layer is up to optical laminate is for actual use.
Optical laminate of the invention can be preferred for image display device.More specifically, optical layer of the invention Stack can be used for the substrate etc. of the display element of image display device.In another mode of the invention, one can be provided Kind has the image display device of above-mentioned optical laminate.In one embodiment, optical laminate of the invention can match Set the outermost in the visible side of image display device.Before the optical laminate being configured so that can be used as image display device Face protection board and function.
B. glass-film
Any suitable glass-film can be used in above-mentioned glass-film.Above-mentioned glass-film, which carries out classification according to composition, can enumerate example Such as: soda-lime glass, borate glass, alumina silicate glass, quartz glass.In addition, carrying out classification according to alkali composition can lift such as nothing Alkali glass, glass with lower alkali content.The alkali metal component of above-mentioned glass is (for example, Na2O、K2O、Li2O content) be preferably 15 weight % with Under, more preferably 10 weight % or less.
The thickness of above-mentioned glass-film is preferably 20 μm~200 μm, more preferably 50 μm~150 μm.In such range, The optical laminate that available flexibility is excellent and glass-film is not easy to break, productivity is excellent.
Light transmission of the above-mentioned glass-film at wavelength 550nm is preferably 85% or more.Above-mentioned glass-film is in wavelength 550nm Under refractive index be preferably 1.4~1.65.
The density of above-mentioned glass-film is preferably 2.3g/cm3~3.0g/cm3, more preferably 2.3g/cm3~2.7g/cm3.Such as Fruit is the glass-film of above range, then the optical laminate of available lightweight.
The forming method of above-mentioned glass-film can use any suitable method.Typically, above-mentioned glass-film can incite somebody to action Mixture comprising the reducing agents such as the defoaming agents such as the main materials such as silica, aluminium oxide, saltcake, antimony oxide and carbon is 1400 DEG C~1600 DEG C at a temperature of melt, be shaped to lamellar, then cooled down and made.The forming method of above-mentioned glass-film can It enumerates such as drawing method, fusion method, floating glass plate method processed under discharge orifice.The glass-film of plate is shaped to by these methods in order to carry out Thin plate improves flatness, can according to need and carries out chemical polishing with hydrofluoric acid equal solvent.
C. polarizer, protective film
C-1. polarizer
The thickness of above-mentioned polarizer is not particularly limited, and can use thickness appropriate according to purpose.The thickness represents Property be 1 μm~80 μm or so.In one embodiment, slim polarizer can be used, the thickness of the polarizer is preferred For 20 μm hereinafter, more preferably 15 μm hereinafter, further preferably 10 μm hereinafter, particularly preferably 6 μm or less.Notice is in this wise Using thin polarizer, available slim optical laminate.
Above-mentioned polarizer, which is preferably shown under any wavelength of wavelength 380nm~780nm, absorbs dichroism.The list of polarizer Body transmissivity is preferably 40.0% or more, and more preferably 41.0% or more, further preferably 42.0% or more, particularly preferably 43.0% or more.The degree of polarization of polarizer is preferably 99.8% or more, and more preferably 99.9% or more, further preferably 99.95% or more.
It is preferred that above-mentioned polarizer is iodine system polarizer.In more detail, above-mentioned polarizer can be by the polyvinyl alcohol containing iodine Resinoid (hereinafter referred to as " PVA resinoid ") film is constituted.
The PVA resinoid for being used to form above-mentioned PVA resin film can use any suitable resin.It can enumerate for example Polyvinyl alcohol, ethylene-vinyl alcohol copolymer.Polyvinyl alcohol can obtain and by saponifying polyvinyl acetate.Ethylene-vinyl Alcohol copolymer can be obtained by by vinyl-vinyl acetate copolymer saponification.The saponification degree of PVA resinoid is usually 85 to rub You are %~100 mole %, and preferably 95.0 moles of %~99.95 mole %, more preferably 99.0 moles of %~99.93 rub You are %.Saponification degree can be found out according to JIS K 6726-1994.It, can be with by using the PVA resinoid of such saponification degree Obtain the polarizer of excellent in te pins of durability.When saponification degree is excessively high, there is the hidden danger that gelation occurs.
The average degree of polymerization of PVA resinoid can suitably be selected according to purpose.Average degree of polymerization is usually 1000~ 10000, preferably 1200~5000, more preferably 1500~4500.It should be noted that average degree of polymerization can be according to JIS K 6726-1994 and find out.
It as the manufacturing method of above-mentioned polarizer, can enumerate for example: PVA resin film monomer is stretched and dyed Method (I)；The method (II) that laminated body (i) with resin base material and polyvinyl alcohol resin layer is stretched and dyed Deng.Method (I) is conventional process well known in the art, therefore detailed description will be omitted.Above-mentioned manufacturing method (II) preferably include with Lower process: to the laminated body (i) with resin base material and the polyvinyl alcohol resin layer for the side for being formed in the resin base material into Row is stretched, is dyed, and makes polarizer on the resin base material.Laminated body (i) can be by the coating comprising polyvinyl alcohol resin Liquid is coated on resin base material and dries and formed.In addition, polyvinyl alcohol resin film can also be transferred to tree by laminated body (i) It is formed on aliphatic radical material.The details of above-mentioned manufacturing method (II) is for example recorded in Japanese Unexamined Patent Publication 2012-73580 bulletin, This specification quotes the bulletin as reference.
C-2. protective film
As said protection film, any suitable resin film can be used.As the forming material of protective film, can enumerate Such as: the cellulosic resins such as the polyester resins such as polyethylene terephthalate (PET), triacetyl cellulose (TAC), drop The olefine kind resins such as the cyclenes such as borneol vinyl resin hydrocarbon resins, polyethylene, polypropylene, (methyl) acrylic resin etc..Its In, preferably polyethylene terephthalate (PET).It should be noted that " (methyl) acrylic resin " refers to propylene Acid resin and/or methacrylic resin.
In one embodiment, it as above-mentioned (methyl) acrylic resin, can be used with glutarimide knot (methyl) acrylic resin of structure.(methyl) acrylic resin with glutarimide structure is (hereinafter, also referred to as glutaryl Imide resin) it is recorded in such as Japanese Unexamined Patent Publication 2006-309033 bulletin, Japanese Unexamined Patent Publication 2006-317560 bulletin, Japan spy Open 2006-328329 bulletin, Japanese Unexamined Patent Publication 2006-328334 bulletin, Japanese Unexamined Patent Publication 2006-337491 bulletin, Japan Special open 2006-337492 bulletin, Japanese Unexamined Patent Publication 2006-337493 bulletin, Japanese Unexamined Patent Publication 2006-337569 bulletin, day This special open 2007-009182 bulletin, Japanese Unexamined Patent Publication 2009-161744 bulletin, Japanese Unexamined Patent Publication 2010-284840 bulletin. This specification is quoted these and is recorded as reference.
Said protection film is laminated with above-mentioned polarizer by any suitable adhesive layer.It is used when making polarizer Resin base material can be removed before by the stacking of protective film and polarizer or after lamination.
The thickness of said protection film is preferably 5 μm~55 μm, and more preferably 10 μm~50 μm, further preferably 15 μm~ 45μm。
D. adhesive phase
The thickness of adhesive phase is preferably 5 μm~100 μm, more preferably 10 μm~70 μm.It, can be in such range Appropriate adjustment bonding force, can be especially less likely to occur removing when glass-film fracture, can be from adherend easily The optical laminate of removing and the excellent in te pins of durability of adhesive phase.
As long as above-mentioned adhesive phase can get effect of the invention, any suitable adhesive may include.It is preferred that Above-mentioned adhesive phase includes (methyl) acrylic adhesives and/or carbamates adhesive.When using these adhesives, It can be especially less likely to occur the optical laminate of glass-film fracture when removing with appropriate adjustment bonding force.
D-1. (methyl) acrylic adhesives
(methyl) acrylic adhesives include (methyl) acrylic polymer.
The content ratio of (methyl) acrylic polymer in (methyl) acrylic adhesives is preferably 40 weight % ~99.9 weight %, the more preferably 50 weight % of weight %~99.5, further preferably 60 weight of weight %~99 %.
(methyl) acrylic polymer is comprising (methyl) acrylic monomer as the polymer for constituting monomer component. (methyl) acrylic polymer can be only a kind, or two or more.(methyl) acrylic monomer can be only 1 Kind, or two or more.
(methyl) acrylic polymer preferably comprise (methyl) alkyl acrylate as constitute polymer monomer at Point.It as (methyl) alkyl acrylate, can enumerate for example: (methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) third The own ester of olefin(e) acid, (methyl) 2-EHA, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) The positive nonyl ester of acrylic acid, 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) Acrylic acid n-dodecane base ester, (methyl) acrylic acid n-tridecane base ester, (methyl) n-myristyl base ester etc. have carbon (methyl) alkyl acrylate of the alkyl of atomicity 1~18.Wherein, it is however preferred to have (the first of the alkyl of carbon atom number 4~13 Base) alkyl acrylate, more preferably (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) alkyl acrylate It can be only a kind, or two or more.
Relative to whole monomer components (100 weight %) of composition (methyl) acrylic polymer, (methyl) acrylic acid The content ratio of Arrcostab is preferably the 70 weight % of weight %~98, more preferably the 80 weight % of weight %~98, further excellent It is selected as the 85 weight % of weight %~98, particularly preferably 90 weight of weight %~98 %.
The monomer component for constituting (methyl) acrylic polymer can further include hydroxyl monomer.As hydroxyl Monomer can be enumerated for example: (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, 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) propylene Amide, vinyl alcohol, allyl alcohol, 2- hydroxyethyl vinylethers, 4- hydroxy butyl vinyl ether, diethylene glycol monovinyl base ether etc.. Hydroxyl monomer can be only a kind, or two or more.
Relative to whole monomer components (100 weight %) of composition (methyl) acrylic polymer, hydroxyl monomer Content ratio is preferably the 0.1 weight % of weight %~15, more preferably 0.5 weight %~13 weight %, and further preferably 0.5 The weight % of weight %~10, particularly preferably 1 weight of weight %~8 %.
From the viewpoint of it cross-linked structure can be imported (methyl) acrylic polymer and obtain cohesiveness appropriate, Constituting in the monomer component of (methyl) acrylic polymer may include such as polyfunctional monomer.It, can as polyfunctional monomer To enumerate for example: ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) third Olefin(e) acid ester, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, trimethylol propane three (methyl) Acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, divinylbenzene, N, N '- Methylene-bisacrylamide etc..Polyfunctional monomer can be only a kind, or two or more.
Relative to whole monomer components (100 weight %) of composition (methyl) acrylic polymer, polyfunctional monomer Content ratio is preferably the 0.1 weight % of weight %~30, more preferably 0.1 weight of weight %~10 %.In such range, It can be especially less likely to occur the optical laminate of glass-film fracture when removing with appropriate adjustment bonding force.
The monomer component for constituting (methyl) acrylic polymer can also include other monomers.It, can as other monomers To enumerate for example: cyano-containing monomer, vinyl acetate monomer, aromatic vinyl monomer, amide-containing monomer, list containing imide Body, emulsion stability, containing epoxy based monomers, vinyl ether monomers, N- acryloyl morpholine etc..Wherein, from improving cohesiveness, resistance to From the viewpoint of hot, preferably cyano-containing monomer, vinyl acetate monomer, aromatic vinyl monomer.In addition, being bonded from improving Power, with the functional group to play a role as crosslink sites from the viewpoint of, preferably amide-containing monomer, contain imide Monomer, contains epoxy based monomers, vinyl ether monomers, N- acryloyl morpholine at emulsion stability.Other monomers can be only a kind, It may be two or more.
As cyano-containing monomer, can enumerate for example: acrylonitrile, methacrylonitrile etc..
It as vinyl acetate monomer, can enumerate for example: the ethylene such as vinyl acetate, vinyl propionate, vinyl laurate Esters.
As aromatic vinyl monomer, can enumerate for example: styrene, chlorostyrene, 1-chloro-4-methyl-benzene, Alpha-Methyl Styrene, other substituted phenylethylenes etc..
As amide-containing monomer, can enumerate for example: acrylamide, Methacrylamide, acrylamide, N- Vinyl pyrrolidone, N, N- dimethylacrylamide, N, N- dimethylmethacryl amide, N, N- acrylamide, N, N- diethyhnethacrylamide, N, N '-methylene-bisacrylamide, N, N- Dimethylaminopropyl acrylamide, N, N- Dimethylaminopropyl Methacrylamide, diacetone acrylamide etc..
As monomer containing imide, can enumerate for example: N-cyclohexylmaleimide, isopropylmaleimide, N- N-cyclohexylmaleimide, clothing health acid imide etc..
It as emulsion stability, can enumerate for example: (methyl) acrylate, (methyl) acrylic acid N, N- diformazan Base amino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester etc..
As epoxy based monomers are contained, can enumerate for example: (methyl) glycidyl acrylate, (methyl) propylene acid methyl Ethylene oxidic ester, allyl glycidyl ether etc..
As vinyl ether monomers, can enumerate for example: methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether-glycidyl Ether etc..
Relative to whole monomer components (100 weight %) of composition (methyl) acrylic polymer, other monomers contain It is proportional preferably 0~40 weight %, more preferably higher than 0 weight % and for 40 weight % hereinafter, further preferably greater than 0 Weight % and be 35 weight % hereinafter, further preferably greater than 0 weight % and be 30 weight % or less.
From the viewpoint of inhibiting the increase to the bonding force of adherend, the list of (methyl) acrylic polymer is constituted Body ingredient does not preferably include carboxyl group-containing monomer, monomer containing sulfonic group, phosphorous acid-based monomers, monomer containing anhydride group.That is, other monomers In preferably do not include carboxyl group-containing monomer, monomer containing sulfonic group, phosphorous acid-based monomers, monomer containing anhydride group.
(methyl) acrylic polymer can be poly- by that will constitute the monomer component of (methyl) acrylic polymer It closes and obtains.As polymerization, can enumerate for example: polymerisation in solution, emulsion polymerization, bulk polymerization, suspension polymerisation, photopolymerization (active energy ray polymerization) etc..Wherein, from the viewpoint of cost, productivity, preferably polymerisation in solution.Obtained (methyl) third Olefin(e) acid quasi polymer can be any one of random copolymer, block copolymer, alternate copolymer, graft copolymer etc..
The weight average molecular weight of (methyl) acrylic polymer is preferably 100,000~5,000,000, more preferably 200,000~400 Ten thousand, further preferably 300,000~3,000,000.
The glass transition temperature (Tg) of (methyl) acrylic polymer be preferably 0 DEG C hereinafter, more preferably -10 DEG C with Under.Glass transition temperature (Tg) is that the glass transition temperature of the homopolymer obtained by each monomer is set as to Tgn (DEG C) Shi Li It is found out with following 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) Indicate that the glass transition temperature of the homopolymer obtained by each monomer, n indicate the type of each monomer.
From the viewpoint of it can obtain cohesiveness appropriate, (methyl) acrylic adhesives may include crosslinking agent. It as crosslinking agent, can enumerate for example: isocyanates crosslinking agent, epoxies crosslinking agent, melamine class crosslinking agent, aziridine Class crosslinking agent and metal-chelating species crosslinking agent etc..Wherein, excellent from the viewpoint of it can give full play of effect of the invention It is selected as isocyanates crosslinking agent, epoxies crosslinking agent.Crosslinking agent can be only a kind, or two or more.
As isocyanates crosslinking agent, can enumerate for example: tetramethylene diisocyanate, hexamethylene diisocyanate Etc. lower aliphatics polyisocyanates, cyclopentylene diisocyanate, cyclohexylene diisocyanate, two isocyanide of isophorone The alicyclic isocyanates such as acid esters class, 2,4 toluene diisocyanate, 4,4 '-methyl diphenylene diisocyanates, xyxylene The aromatic isocyanates such as diisocyanate class, trimethylolpropane/toluene di-isocyanate(TDI) trimer addition product (trade name " Coronate L " Nippon Polyurethane Industry corporation), trimethylolpropane/hexa-methylene diisocyanate Ester trimer addition product (trade name " Coronate HL " Nippon Polyurethane Industry corporation), six methylenes (trade name " Coronate HX " Nippon Polyurethane Industry is public for the isocyanuric acid ester body of group diisocyanate Department's system) etc. isocyanate addition products etc..
As epoxies crosslinking agent, can enumerate for example: bisphenol-A, the epoxylite of epoxychloropropane type, ethylene shrink Glycerin ether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-HD Glycidol ether, trihydroxymethylpropanyltri diglycidyl ether, diglycidylaniline, diamines glycidyl group amine, N, N, N ', N '-four glycidyl group m-xylene diamine (trade name " TETRAD-X " Mitsubishi Gas Chemical Co., Ltd system), 1,3- it is bis- (N, N- diglycidyl amino methyl) hexamethylene (trade name " TETRAD-C " Mitsubishi Gas Chemical Co., Ltd system) etc..
Relative to 100 parts by weight of (methyl) acrylic polymer, the use level of crosslinking agent be preferably 0.01 parts by weight~ 15 parts by weight, more preferably 0.1 parts by weight~10 parts by weight, further preferably 0.1 parts by weight~8 parts by weight, particularly preferably For 0.5 parts by weight~5 parts by weight.Pass through the use level by crosslinking agent relative to 100 parts by weight of (methyl) acrylic polymer It is set as in above range, can be especially less likely to occur the light of glass-film fracture when removing with appropriate adjustment bonding force Learn laminated body.
(methyl) acrylic adhesives may include crosslinking catalyst.As crosslinking catalyst, can enumerate for example: titanium The metals classes such as sour four N-butyls, tetraisopropyl titanate, ferric acetyl acetonade (III), butyl tin oxide, tin dilaurate dioctyl tin are handed over Join catalyst (especially tin class crosslinking catalyst).Crosslinking catalyst can be only a kind, or two or more.
Relative to 100 parts by weight of (methyl) acrylic polymer, the use level of crosslinking catalyst is preferably 0.001 weight Part~0.05 parts by weight, more preferably 0.003 parts by weight~0.04 parts by weight, further preferably 0.005 parts by weight~0.03 Parts by weight.
(methyl) acrylic adhesives may include crosslinking delay agent.As crosslinking delay agent, can enumerate for example: second Methyl acetoacetate, ethyl acetoacetate, acetoacetate monooctyl ester, acetoacetate oil base ester, lauryl acetoacetate rouge, acetoacetate are hard The beta-diketons such as the 'beta '-ketoesters such as rouge ester, acetylacetone,2,4-pentanedione, 2,4- acetyl butyryl, benzoyl acetone.Wherein, from the present invention can be given full play to Effect from the viewpoint of, preferably acetylacetone,2,4-pentanedione.Crosslinking delay agent can be only a kind, or two or more.
Relative to 100 parts by weight of (methyl) acrylic polymer, the use level of crosslinking delay agent is preferably 0.1 parts by weight ~10 parts by weight, more preferably 0.1 parts by weight~5 parts by weight, further preferably 0.1 parts by weight~3 parts by weight.
Within the scope of the effect of the invention, (methyl) acrylic adhesives may include plasticizer, anti-aging agent, The additives such as colorant (pigment, dyestuff etc.), antistatic agent, tackifying resin.In addition, (methyl) acrylic adhesives can wrap Containing any suitable solvent.
D-2. carbamates adhesive
Carbamates adhesive includes polyurethane based resin.
The content ratio of polyurethane based resin in carbamates adhesive is preferably the 40 weight % of weight %~99, The more preferably 50 weight % of weight %~95, further preferably 60 weight of weight %~90 %.
Polyurethane based resin can be only a kind, or two or more.
Polyurethane based resin can be such that polyalcohol (A) reacts with polyfunctional isocyanate compound (B) to obtain.
It can be only a kind as polyalcohol (A), or two or more.
It as polyalcohol (A), can enumerate for example: polyester polyol, polyether polyol, polycaprolactone polyol, poly- carbon Acid esters polyalcohol, castor-oil plant oils polyalcohol etc..
As polyester polyol, such as can be obtained and making the esterification of polyol component and sour component.
It as polyol component, can enumerate for example: ethylene glycol, diethylene glycol, 1,3-BDO, 1,4-butanediol, new Pentanediol, 3- methyl-1,5- pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4- diethyl -1,5- pentanediol, 1,2- Hexylene glycol, 1,6-HD, 1,8- ethohexadiol, 1,9- nonanediol, 2- methyl-1,8- ethohexadiol, 1,8- decanediol, octadecane two Alcohol, glycerine, trimethylolpropane, pentaerythrite, hexanetriol, polypropylene glycol etc..
It as sour component, can enumerate for example: succinic acid, dimethyl succinic acid, adipic acid, pimelic acid, azelaic acid, the last of the ten Heavenly stems two Acid, 1,12 dodecanedioic acid, 1,14- tetracosandioic acid, dimeric dibasic acid, 2- methyl-1,4- cyclohexane cyclohexanedimethanodibasic, 2- ethyl -1,4- Cyclohexane cyclohexanedimethanodibasic, terephthalic acid (TPA), M-phthalic acid, phthalic acid, 1,4- naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acids, it Acid anhydrides etc..
As polyether polyol, can enumerate for example by with water, low molecular polylol (propylene glycol, ethylene glycol, the third three Alcohol, trimethylolpropane, pentaerythrite etc.), bisphenols (bisphenol-A etc.), dihydroxy benzenes (catechol, resorcinol, to benzene two Phenol etc.) etc. be used as initiator, make polyethers obtained from the epoxides addition polymerization such as ethylene oxide, propylene oxide, epoxy butane Polyalcohol.It can specifically enumerate for example: polyethylene glycol, polypropylene glycol, poly- four methylenes glycol etc..
As polycaprolactone polyol, can enumerate such as opening by cyclic ester monomers 6-caprolactone, σ-valerolactone Caprolactone obtained from cyclopolymerization is birdsed of the same feather flock together esterdiol.
It as polycarbonate polyol, can enumerate for example: carry out above-mentioned polyol component and phosgene (phosgene) Polycarbonate polyol obtained from polycondensation reaction；Make above-mentioned polyol component and dimethyl carbonate, diethyl carbonate, carbonic acid two Propyl ester, diisopropyl carbonate, dibutyl carbonate, carbonic acid ethyl butyl ester, ethylene carbonate, propylene carbonate, diphenyl carbonate, carbon The carbonic diesters class such as sour dibenzyl ester carries out polycarbonate polyol obtained from transesterification condensation；It is applied in combination on of more than two kinds State copolymerization polycarbonate polyalcohol obtained from polyol component；Make above-mentioned various polycarbonate polyols and carboxylated compound Carry out polycarbonate polyol obtained from esterification；Carry out above-mentioned various polycarbonate polyols and hydroxy-containing compounds Polycarbonate polyol obtained from etherification reaction；Keep above-mentioned various polycarbonate polyols and ester compounds progress transesterification anti- Polycarbonate polyol obtained from answering；Above-mentioned various polycarbonate polyols and hydroxy-containing compounds is set to carry out ester exchange reaction Obtained from polycarbonate polyol；Make above-mentioned various polycarbonate polyols carry out condensation polymerization with dicarboxylic acid compound to react Obtained from polyesters polycarbonate polyol；Above-mentioned various polycarbonate polyols are copolymerized with epoxides to be obtained Copolyether class polycarbonate polyol；Deng.
As castor-oil plant oils polyalcohol, can enumerate for example reacts Castor Oil Fatty Acid with above-mentioned polyol component and obtains The castor-oil plant oils polyalcohol arrived.Castor oil obtained from for example reacting Castor Oil Fatty Acid with polypropylene glycol can specifically be enumerated Class polyalcohol.
In one embodiment, the polyalcohol (triol) with 3 OH bases can be used as polyalcohol (A).Make When with triol, it with appropriate adjustment bonding force, can be especially less likely to occur the optics stacking of glass-film fracture when removing Body.The content ratio of polyalcohol (triol) in polyalcohol (A) with 3 OH bases is preferably the 50 weight % of weight %~100, more The preferably 70 weight % of weight %~100, the further preferably 80 weight % of weight %~100, further preferably 90 weights The weight % of %~100 is measured, the particularly preferably 95 weight % of weight %~100, are most preferably essentially 100 weight %.
As polyalcohol (A), the polyalcohol that number-average molecular weight Mn is 400~20000 is preferably comprised.Number in polyalcohol (A) The content ratio for the polyalcohol that average molecular weight Mn is 400~20000 is preferably 50 weight %~100 weight %, and more preferably 70 The weight % of weight %~100, the further preferably 90 weight % of weight %~100, particularly preferably 95 weights of weight %~100 % is measured, is most preferably essentially 100 weight %.
In one embodiment, essential component is used as using the polyalcohol (triol) with 3 OH bases at polyalcohol (A) In the case where, it is 2000~6000 that triol that number-average molecular weight Mn is 7000~20000 and number-average molecular weight Mn, which is applied in combination, Triol and number-average molecular weight Mn be 400~1900 triol, be more preferably applied in combination number-average molecular weight Mn be 8000~15000 Triol, number-average molecular weight Mn be 2000~5000 triol and number-average molecular weight Mn be 500~1800 triol, into one Step preferably be applied in combination the triol that number-average molecular weight Mn is 8000~12000, the triol that number-average molecular weight Mn is 2000~4000, And the triol that number-average molecular weight Mn is 500~1500.When such 3 kinds of triols are applied in combination, can with appropriate adjustment bonding force, The optical laminate of glass-film fracture when removing can be especially less likely to occur.
Polyfunctional isocyanate compound (B) can be only a kind, or two or more.
As polyfunctional isocyanate compound (B), can be fitted using can be used in any of urethane reaction When polyfunctional isocyanate compound.As such polyfunctional isocyanate compound (B), can enumerate for example: more officials It can aliphatic category isocyanate compound, multifunctional alicyclic kind isocyanate, multifunctional aromatic isocyanate compound Deng.
It as multifunctional aliphatic kind isocyanate compound, can enumerate for example: trimethylene diisocyanate, four Asias Methyl diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2- trimethylene diisocyanate, 1, 3- tetramethylene diisocyanate, ten dimethylene diisocyanates, 2,4,4- trimethyl hexamethylene diisocyanate etc..
As multifunctional alicyclic kind isocyanate compound, can enumerate for example: 1,3- cyclopentene diisocyanate, 1, 3- cyclohexane diisocyanate, 1,4- cyclohexane diisocyanate, isophorone diisocyanate, two isocyanide of hydrogenated methylene diphenyld Acid esters, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenation tetramethyl xylylene diisocyanate Deng.
It as multifunctional aromatic diisocyanate cpd, can enumerate for example: phenylene diisocyanate, 2,4- toluene Diisocyanate, 2,6- toluene di-isocyanate(TDI), 2,2 '-'-diphenylmethane diisocyanates, 4,4 '-diphenylmethane diisocyanates Ester, 4,4 '-toluidine diisocyanates, 4,4 '-diphenyl ether diisocyanates, 4,4 '-biphenyl diisocyanates, 1,5- naphthalene two Isocyanates, xylylene diisocyanate etc..
It as polyfunctional isocyanate compound (B), can enumerate for example: above-mentioned various polyfunctional isocyanate's chemical combination The trimethylolpropane adduct of object, reacted with water made of biuret body, the trimer with isocyanurate ring etc..Separately Outside, above compound can also be applied in combination.
For the equivalent proportion of NCO base and OH base in polyalcohol (A) and polyfunctional isocyanate compound (B), with NCO Base/OH base meter, for greater than 1.0 and 5.0 hereinafter, preferably 1.1~5.0, more preferably 1.2~4.0, further preferably 1.5 ~3.5, particularly preferably 1.8~3.0.
Polyurethane binding preferably comprises the anti-deterioration agents such as antioxidant, ultraviolet absorbing agent, light stabilizer.Anti- deterioration Agent can be only a kind, or two or more.Anti-deterioration agent is particularly preferably antioxidant.
In addition, carbamates adhesive can within the scope of the effect of the invention containing it is any suitable its Its ingredient.It as such other ingredients, can enumerate for example: other resin components, thickening in addition to polyurethane based resin Agent, inorganic filler, organic filler, metal powder, pigment, foil-like object, softening agent, plasticizer, antiaging agent, conductive agent, purple Ultraviolet absorbers, antioxidant, light stabilizer, surface lubricant, levelling agent, resist, heat-resisting stabilizing agent, polymerization inhibitor, lubrication Agent, solvent etc..
Carbamates adhesive may include modified silicon oil.
In the case where carbamates adhesive includes modified silicon oil, relative to 100 parts by weight of polyurethanes resin, Its content ratio is preferably 0.001 parts by weight~50 parts by weight, more preferably 0.01 parts by weight~40 parts by weight, further preferably For 0.01 parts by weight~30 parts by weight, particularly preferably 0.01 parts by weight~20 parts by weight, most preferably 0.01 parts by weight~10 Parts by weight.
As modified silicon oil, any suitable modified silicon oil can be used within the scope of the effect of the invention.Make For such modified silicon oil, the modified silicon oil that can for example obtain from Shin-Etsu Chemial Co., Ltd can be enumerated.As changing Property silicone oil, preferably polyether modified silicon oil.As polyether modified silicon oil, can enumerate for example: the polyether modified silicon oil of side chain type, The polyether modified silicon oil etc. of two tip types.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, but the present invention is not by any limit of these embodiments It is fixed.In addition, in case of no particular description, " part " and " % " in embodiment is weight basis.
The manufacture of [Production Example 1] polarizer A
Prepare have 7 moles of % isophthalic acid units noncrystalline polyethylene terephthalate (hereinafter also referred to as " PET ") (IPA be copolymerized PET) film (thickness: 100 μm) is used as thermoplastic resin substrate, sided corona treatment (58W/ is implemented to surface m2/ point).On the other hand, prepare to be added to the acetoacetyl modified PVA (the Nippon Synthetic Chemical Industry Co., Ltd of 1 weight % System, trade name: GOHSEFIMER Z200 (average degree of polymerization: 1200, saponification degree: 98.5 moles of %, acetoacetylation degree: 5 Mole %) PVA (degree of polymerization 4200, saponification degree 99.2%), and prepare the PVA aqueous solution that PVA resinoid is 5.5 weight % Coating liquid, by make it is dry after 12 μm of film thickness in a manner of applied, pass through under 60 DEG C of atmosphere heated-air drying into Row drying in 10 minutes has made the laminated body that PVA resinoid layer is equipped on substrate.
Then, the laminated body free end is stretched into (assisting tension in atmosphere) to 1.8 with 130 DEG C in air first Times, generate stretching laminated body.Then, carry out following process: by will stretch laminated body 30 DEG C of fluid temperature boric acid not It is impregnated 30 seconds in dissolved aqueous solution, the PVA layer for being orientated the PVA molecule for including in stretching laminated body is insoluble.In In the boric acid undissolved water solution of this process, relative to 100 parts by weight of water, boric acid content is 3 parts by weight.By by the tensile layer Stack dyeing, generates coloring laminated body.For colouring laminated body, by stretch laminated body 30 DEG C of liquid temperature include iodine and Any time is impregnated in the dyeing liquor of potassium iodide, so that the monomer transmissivity for constituting the PVA layer of the polarizer ultimately generated is 40 ~44%, dye the PVA layer for including in stretching laminated body using iodine as a result,.In this process, dyeing liquor using water as Iodate potassium concn in the range of iodine concentration is set as 0.1~0.4 weight %, is set as the range of 0.7~2.8 weight % by solvent It is interior.The ratio between concentration of iodine and potassium iodide is 1 to 7.Then, following process is carried out: by the way that boric acid of the laminated body at 30 DEG C will be coloured It is impregnated 60 seconds in crosslinking aqueous solution, crosslinking Treatment is implemented each other to the PVA for the PVA resin layer for being adsorbed with iodine.In this process Boric acid crosslinking aqueous solution in, relative to 100 parts by weight of water, boric acid content is 3 parts by weight, and relative to 100 parts by weight of water, iodine Change potassium content is 3 parts by weight.
Then, draft temperature is set as 70 DEG C in boric acid aqueous solution, along identical with the stretching in air previous Obtained coloring laminated body is stretched to 3.05 times (stretching in boric acid aqueous solution) by direction, and having obtained final stretching ratio is 5.50 Optical film laminate again.Optical film laminate is taken out from boric acid aqueous solution, with iodate potassium content relative to 100 weight of water Part is that the aqueous cleaning of 4 parts by weight is attached to the boric acid of PVA layer surface.By the drying process using 60 DEG C of hot winds to cleaning Optical film laminate afterwards is dried.The polarizer A for including in obtained optical film laminate with a thickness of 5 μm.
The manufacture of [Production Example 2] polarizer B
By 60 μm of thickness of polyvinyl alcohol film speed than between different rollers one in 30 DEG C, the iodine solution of 0.3% concentration It is stretched to 3 times on one side within Edge Coloring 1 minute.Then, the boric acid comprising 4% concentration, 60 DEG C of the potassium iodide of 10% concentration it is water-soluble It is impregnated on one side in liquid 0.5 minute, is stretched to total stretching ratio on one side and reaches 6 times.Then, by the iodine comprising 1.5% concentration Change and impregnated 10 seconds in 30 DEG C of aqueous solutions of potassium, is cleaned, then, drying in 4 minutes is carried out at 50 DEG C, has obtained thickness The polarizer B of 22 μm of degree.
The manufacture of [Production Example 3] (methyl) acrylic adhesives A
Acrylic acid 2- ethyl hexyl is put into the four-neck flask for having stirring blade, thermometer, nitrogen ingress pipe, cooler 200 parts by weight of ester, 10 parts by weight of acrylic acid 2- hydroxy methacrylate, 2,2 '-azodiisobutyronitrile, 0.4 weight as polymerization initiator Part, 312 parts by weight of ethyl acetate, import nitrogen while being slowly stirred, by the fluid temperature in flask be maintained at 65 DEG C it is attached The polymerization reaction for closely carrying out about 6 hours is prepared for (methyl) acrylic polymer solution (A1) that weight average molecular weight is 500,000.
It is added in obtained (methyl) acrylic polymer solution (A1) (100 parts by weight of solid component) as crosslinking Isocyanuric acid ester body (Nippon Polyurethane Industry corporation, the commodity of the hexamethylene diisocyanate of agent Name: Coronate HX) 0.6 parts by weight, as the dibutyl tin dilaurate of crosslinking catalyst, (1 weight % ethyl acetate is molten Liquid) 0.6 parts by weight, silane coupling agent (Shin-Etsu Chemial Co., Ltd's system, trade name: KBM403) 0.1 parts by weight, it is maintained at Near 25 DEG C, mixing in about 1 minute is carried out, is prepared for (methyl) acrylic adhesives A.
The manufacture of [Production Example 4] (methyl) acrylic adhesives B
Match in (methyl) acrylic polymer solution (A1) (100 parts by weight of solid component) made in Production Example 3 Cooperation is isocyanuric acid ester body (the Nippon Polyurethane Industry public affairs of the hexamethylene diisocyanate of crosslinking agent Department's system, trade name: Coronate HX) 1.0 parts by weight, dibutyl tin dilaurate (the 1 weight % second as crosslinking catalyst Acetate solution) 0.6 parts by weight, silane coupling agent (Shin-Etsu Chemial Co., Ltd's system, trade name: KBM403) 0.1 weight Part, it is prepared for (methyl) acrylic adhesives B.
The manufacture of [Production Example 5] carbamates adhesive C
As polyalcohol (A), triol (Asahi Glass Co., Ltd's system, trade name: PREMINOL S3011, Mn=are used 10000) 85 parts by weight, triol (Sanyo Chemical Industries Co., Ltd.'s system, trade name: SANNIX GP-3000, Mn=3000) 13 weight Part, triol (Sanyo Chemical Industries Co., Ltd.'s system, trade name: SANNIX GP-1000, Mn=1000) 2 parts by weight, cooperation is as more Multifunctional alicyclic kind isocyanate compound (the Nippon Polyurethane of functional isocyanate compound (B) Industry corporation, trade name: Coronate HX) 18 parts by weight, catalyst (chemistry Industry Co., Ltd, Japan system, commodity Name: ferric acetyl acetonade (III)) 0.04 parts by weight, Irganox1010 (BASF AG's system) 0.50 weight as anti-deterioration agent Part, aliphatic ester (isopropyl myristate, Kao Corp's system, trade name: EXCEPARL IPM, Mn=270) 30 weight Part, 1- ethyl-3-methylimidazoleBis- (fluorine methylsulfonyl) inferior amine salts (Di-ichi Kogyo Seiyaku Co., Ltd.'s system, trade name: AS110) polyether modified silicon oil (Shin-Etsu Chemial Co., Ltd's system, KF-6004) 0.01 weight of 1.5 parts by weight, two tip types Part, 241 parts by weight of ethyl acetate as retarder thinner are measured, is stirred with disperser, has obtained carbamates bonding Agent C.
The manufacture of [Production Example 6] (methyl) acrylic adhesives D
In the four-neck flask for having stirring blade, thermometer, nitrogen ingress pipe, cooler, by 99 weight of butyl acrylate Measure part, 1 parts by weight of acrylic acid 4- hydroxybutyl, 2,2 '-azodiisobutyronitrile, 0.1 parts by weight and acetic acid as polymerization initiator 100 parts by weight of ethyl ester are put into together, and nitrogen is imported while being slowly stirred and carries out nitrogen displacement, then, by the liquid in flask Temperature is maintained near 55 DEG C, is carried out 8 hours polymerization reactions, is prepared for (methyl) acrylic acid of weight average molecular weight 1,600,000 Quasi polymer solution (A2).
Relative to obtained (methyl) acrylic polymer solution (A2) (100 parts by weight of solid component), cooperate isocyanide Acid esters crosslinking agent (MITSUI TAKEDA CHEMICALS corporation, trade name: Takenate D110N, trimethylolpropane benzene Diformazan group diisocyanate) 0.1 parts by weight, polyether compound (Asahi Glass's carbamate corporation, trade name: Excestar 2420) 1 parts by weight are prepared for (methyl) acrylic adhesives D.
The manufacture of [Production Example 7] (methyl) acrylic adhesives E
Relative to (methyl) acrylic polymer solution (A2) (100 parts by weight of solid component) prepared in Production Example 6, Cooperate isocyanate crosslinking (MITSUI TAKEDA CHEMICALS corporation, trade name: Takenate D110N, three hydroxyl first Base propane xylylene diisocyanate) 0.3 parts by weight, silane coupling agent (Shin-Etsu Chemial Co., Ltd's system, trade name: KBM403) 0.1 parts by weight are prepared for (methyl) acrylic adhesives E.
[Production Example 8] manufactures (methyl) acrylic adhesives F
In the four-neck flask for having stirring blade, thermometer, nitrogen ingress pipe, cooler, by 100 weight of butyl acrylate Measure part, 3 parts by weight of acrylic acid, 1 parts by weight of acrylic acid 2- hydroxy methacrylate, the 2,2 '-azodiisobutyronitriles as polymerization initiator 0.1 parts by weight and 100 parts by weight of ethyl acetate are put into together, and nitrogen is imported while being slowly stirred and carries out nitrogen displacement, so Afterwards, the fluid temperature in flask is maintained near 55 DEG C, carries out 8 hours polymerization reactions, is prepared for weight average molecular weight 1,800,000 (methyl) acrylic polymer solution (A3).
Relative to obtained (methyl) acrylic polymer solution (A3) (100 parts by weight of solid component), cooperate isocyanide Acid esters crosslinking agent (Nippon Polyurethane Industry corporation, trade name: Coronate L, trimethylolpropane Toluene di-isocyanate(TDI) adduct) 0.5 parts by weight, silane coupling agent (Shin-Etsu Chemial Co., Ltd's system, trade name: KBM403) 0.1 parts by weight are prepared for (methyl) acrylic adhesives F.
[embodiment 1]
Successively be bonded by bonding agent glass-film (Nippon Electric Glass Co., Ltd's system, trade name: OA10, size: 400mm × 40mm, thickness: 100 μm), protective film (acrylic resin films that 40 μm of thickness) and polarizer A, obtained layer Stack a.
(methyl) acrylic adhesives A is coated on the polyethylene terephthalate that single side implements organosilicon processing The organosilicon process face of ester film heats 3 minutes at 110 DEG C, forms 25 μm of thickness of adhesive phase A.By adhesive phase A It is transferred to the side polarizer A of above-mentioned laminated body a, has obtained optical laminate A.
[embodiment 2]
(production of optical laminate)
By bonding agent be bonded glass-film (Nippon Electric Glass Co., Ltd's system, trade name: OA10, size: 400mm × 40mm, thickness: 100 μm) and polarizer A, obtain laminated body b.
(methyl) acrylic adhesives A is coated on the polyethylene terephthalate that single side implements organosilicon processing The organosilicon process face of ester film heats 3 minutes at 110 DEG C, forms 25 μm of thickness of adhesive phase A.By adhesive phase A It is transferred to the side polarizer A of above-mentioned laminated body b, has obtained optical laminate B.
[embodiment 3]
Successively be bonded by bonding agent glass-film (Nippon Electric Glass Co., Ltd's system, trade name: OA10, size: 400mm × 40mm, thickness: 100 μm), protective film (thickness: 40 μm of acrylic resin film), polarizer B and protective film (thickness: 40 μm of acrylic resin film), has obtained laminated body c.
(methyl) acrylic adhesives A is coated on the polyethylene terephthalate that single side implements organosilicon processing The organosilicon process face of ester film heats 3 minutes at 110 DEG C, forms 25 μm of thickness of adhesive phase A.By adhesive phase A It is transferred to the side polarizer B of above-mentioned laminated body c, has obtained optical laminate C.
[embodiment 4]
Laminated body a has been obtained similarly to Example 1.
(methyl) acrylic adhesives B is coated on to the polyethylene terephthalate film for implementing organosilicon processing Organosilicon process face, heated 3 minutes at 110 DEG C, form 12 μm of thickness of adhesive phase B.Adhesive phase B is transferred To the side polarizer A of above-mentioned laminated body a, optical laminate D has been obtained.
[embodiment 5]
Laminated body a has been obtained similarly to Example 1.
Carbamates adhesive C is coated on the polyethylene terephthalate that single side implements organosilicon processing The organosilicon process face of film heats 3 minutes at 110 DEG C, forms 25 μm of thickness of adhesive phase C.Adhesive phase C is turned Print has obtained optical laminate E to the side polarizer A of above-mentioned laminated body a.
[embodiment 6]
Laminated body a has been obtained similarly to Example 1.
(methyl) acrylic adhesives D is coated on to the polyethylene terephthalate film for implementing organosilicon processing Organosilicon process face, heated 3 minutes at 110 DEG C, form 25 μm of thickness of adhesive phase D.Adhesive phase D is transferred To the side polarizer A of above-mentioned laminated body a, optical laminate F has been obtained.
[embodiment 7]
Laminated body a has been obtained similarly to Example 1.
(methyl) acrylic adhesives E is coated on to the polyethylene terephthalate film for implementing organosilicon processing Organosilicon process face, heated 3 minutes at 110 DEG C, form 50 μm of thickness of adhesive phase E.Adhesive phase E is transferred To the side polarizer A of above-mentioned laminated body a, optical laminate G has been obtained.
[comparative example 1]
Laminated body a has been obtained similarly to Example 1.
Above-mentioned (methyl) acrylic adhesives F is coated on to the polyethylene terephthalate for implementing organosilicon processing The organosilicon process face of ester film heats 3 minutes at 110 DEG C, forms 25 μm of thickness of adhesive phase F.By adhesive phase F It is transferred to the side polarizer A of above-mentioned laminated body a, has obtained optical laminate H.
[comparative example 2]
Other than glass-film to be changed to 100 μm of thickness of polyethylene terephthalate film, similarly to Example 1 Ground has obtained optical laminate I.
<evaluation>
By optical laminate obtained in Examples and Comparative Examples for following evaluations.Show the result in table 1.
1. bonding force
Optical laminate is cut into 150mm × 25mm, the alkali-free glass plate of thickness 0.7mm is pasted on using laminating machine (Corning Incorporated's system, trade name: EG-XG) then carries out 15 minutes autoclave process at 50 DEG C, 5atm, keeps it completely close It closes, has made sample for evaluation.
To above-mentioned sample for evaluation, with cupping machine (Autograph SHIMAZU AG-1 10KN) 23 DEG C/it is wet Under conditions of degree 55%, 90 ° of peel angle, peeling rate 300mm/ points, optical laminate is removed from glass plate, determines light Learn the bonding force of laminated body.Measurement was sampled with 1 time/0.5 second interval, using its average value as measured value.
2. operational again
Optical laminate is pasted on having a size of 15 inches (diagonal lines) and with a thickness of the alkali-free glass of 0.7mm using laminating machine Glass (Corning Incorporated's system, trade name: EG-XG).Then, the autoclave process that 15 minutes are carried out at 50 DEG C, 0.5MPa, makes optics Laminated body is sealed at alkali-free glass completely, has made sample for evaluation.
For above-mentioned sample for evaluation, along from one jiao of optical laminate to diagonal direction by optical laminate from glass Removing has rated crackle, the fracture of glass-film.
◎: optical laminate absolutely not crackle can be operated easily again.
Zero: although optical laminate slightly crackle, can easily operate again.It is practical that above there is no problem.
△: optical laminate has crackle, but is not broken, and can operate again.It is practical that above there is no problem.
×: optical laminate is broken and can not operate again.
3. durability test
Optical laminate is pasted on having a size of 15 inches (diagonal lines) and with a thickness of the alkali-free glass of 0.7mm using laminating machine Glass (Corning Incorporated's system, EG-XG).Then, the autoclave process that 15 minutes are carried out at 50 DEG C, 0.5MPa, makes optical laminate It is sealed at alkali-free glass completely, has made sample for evaluation.
Processing (heat run) in 500 hours is implemented to above-mentioned sample for evaluation under 80 DEG C of atmosphere, is then pressed It is observed by the naked eye according to following benchmark and appearance is evaluated.
In addition, (adding after implementing processing in 500 hours to above-mentioned sample for evaluation under the atmosphere of 60 DEG C/90%RH Wet test), it is then observed by the naked eye according to following benchmark and appearance is evaluated.
◎: the absolutely not apparent variation such as foaming, peeling.
Zero: although slightly peeling off or foaming in end, practical above there is no problem.
△: there are peeling or foaming in end, but as long as not being specific use, it is practical on also there is no problem.
×: there is an obvious peeling in end, it is practical on there are problems.
[table 1]

Claims (7)

1. a kind of optical laminate, successively has: glass-film, polarizer and adhesive phase,
The optical laminate is 5N/25mm or less to the bonding force of glass plate.
2. optical laminate according to claim 1, wherein described adhesive layer with a thickness of 5 μm~100 μm.
3. optical laminate according to claim 1, wherein the glass-film with a thickness of 20 μm~200 μm.
4. optical laminate according to claim 1, wherein described adhesive layer includes (methyl) acrylic adhesive Agent.
5. optical laminate according to claim 1, wherein described adhesive layer includes carbamates adhesive.
6. a kind of image display device, it includes optical laminates described in claim 1.
7. image display device according to claim 6 has the optical laminate in the outermost of visible side.
CN201880020357.2A 2017-03-23 2018-03-19 Optical laminate Pending CN110446956A (en)

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KR20210066022A (en) 2021-06-04

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