CN106795415B - Adhesive phase, polarizing film and laminated body with adhesive phase - Google Patents

Adhesive phase, polarizing film and laminated body with adhesive phase Download PDF

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Publication number
CN106795415B
CN106795415B CN201580054572.0A CN201580054572A CN106795415B CN 106795415 B CN106795415 B CN 106795415B CN 201580054572 A CN201580054572 A CN 201580054572A CN 106795415 B CN106795415 B CN 106795415B
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monomer
adhesive phase
film
methyl
mass
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CN106795415A (en
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米川雄也
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Soken Chemical and Engineering Co Ltd
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Soken Chemical and Engineering Co Ltd
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    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C09J201/08—Carboxyl groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a kind of polarizing film adhesive phase that can be played durability in high temperatures and humid conditions, reduce light leakage and the excellent adhesion between polycyclic alkene class film.The adhesive phase is characterized in that, the contact angle of adhesive layer surface and water at 90 ° hereinafter, and the adhesive phase obtained by the copolymer and (B) of the monomer mixture comprising (A) containing following monomers (a1)~(a5) relative to the adhesive composition of isocyanates crosslinking agent that 100 parts of the copolymer (A) are 0.1~5 mass parts: 30~98.8 mass % of monomer of (a1) containing polyoxyalkylenes or alkoxyalkyl；(a2) 0.1~10 mass % of hydroxyl monomer；(a3) 0.1~10 mass % of carboxyl group-containing monomer；(a4) 1~69.8 mass % of (methyl) alkyl acrylate monomer；(a5) 0~30 mass % of co-polymerized monomer other than (a1)~(a4)；Wherein, monomer (a1)~(a5) adds up to 100 mass %.

Description

Adhesive phase, polarizing film and laminated body with adhesive phase
Technical field
Polarizing film and laminated body the present invention relates to adhesive phase, with adhesive phase.
Background technique
In recent years, image display device is applied not only to indoor purposes, is also act as Vehicular display device or field mapping sometimes A part of instrument.
The optical films such as the polarizing coating conformed on image display device are by making have the polarized components such as dichromatic pigment It is adsorbed on the polymeric membranes such as polyvinyl alcohol, stretches and is orientated to make.Protection is usually provided on the surface of polyvinyl alcohol film Film.As the protective film of polyvinyl alcohol film, tri acetyl cellulose (TAC) film is used mostly all the time.The suction of known TAC film Moist height, and TAC film can under high wet heat condition due to the environment difference between room temperature and deformation occurs, and polarize therewith The deformation of piece entirety.Moreover it is known that polarizing film is brittle, so if deformation occurs can then generate asking for cracking for polarizing film Topic.
In recent years, the protective film as polyvinyl alcohol film in the image device for requiring durability gradually uses polycyclic Olefines (COP) film replaces TAC film.COP film has the advantages that low in brittleness and hygroscopicity compared with TAC film.It is required that COP film The high-durability of polarizing film overall shrinkage and inhibition are equally because of polyethylene caused by with that can resist because of polyvinyl alcohol film contraction The performance of " light leakage " of image display device caused by alcohol film is shunk.Moreover, COP film has the physical property different from TAC film, because This in the case where will be used for previous adhesive be bonded between TAC film and clung body and be used for occasion be bonded between COP film and clung body, There is a problem of that adaptation is bad.
To solve the above-mentioned problems, one kind is disclosed in patent document 1 to improve under high-temperature atmosphere to polyolefin or ring-type Acrylic compounds for the purpose of the stationarity of polyolefin, comprising core hydriding terpene phenol (core water adds テ Le ペ Application Off ェ ノ ー Le) resin Adhesive composition.However, the leakage when adhesive phase obtained by above-mentioned acrylic pressure-sensitive adhesive compositions to be used for polarizing film Xanthophyll cycle performance is insufficient.
In addition, being disclosed in patent document 2 a kind of comprising making containing ester ring type monomer or containing the monomer component of aromatic ring monomer The low Polar Crystal Slab adhesive of heavy polymer made of copolymerization.However, the durability of above-mentioned adhesive or with COP film it Between adaptation and insufficient.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2007-224258 bulletin
Patent document 2: Japanese Patent Laid-Open 2005-53976 bulletin
Summary of the invention
The technical problems to be solved by the invention
Technical problem to be solved by the present invention lies in provide one kind can play under hot conditions and wet condition it is excellent Adaptation and institute of the different durability, reduction light leakage and glass substrate and protective film between the polarizing film of polycyclic alkene class film State the adhesive phase of the excellent adhesion between the optical films such as polarizing film and phase difference film.
Technical scheme applied to solve the technical problem
The present inventor is to solve such technical problem and have made intensive studies.As a result, it has been found that using adhesive phase The contact angle of surface and water is mixed at 90 ° or less and by the copolymer that the monomer mixture of the specific monomer comprising specific quantity obtains Under the occasion for the adhesive phase that adhesive composition made of conjunction is formed, it is able to solve above-mentioned technical problem, so as to complete this Invention.
It is for polarizing film to be conformed to image display device that is, through the invention, providing a kind of adhesive phase Adhesive phase, the adhesive layer surface of the adhesive phase and the contact angle of water at 90 ° hereinafter, and the adhesive phase by comprising (A) copolymer of the monomer mixture containing following monomers (a1)~(a5) and (B) are relative to 100 mass of the copolymer (A) Part is that the adhesive composition of the isocyanates crosslinking agent of 0.1~5 mass parts obtains:
(a1) 30~98.8 mass % of monomer containing polyoxyalkylenes or alkoxyalkyl；
(a2) 0.1~10 mass % of hydroxyl monomer；
(a3) 0.1~10 mass % of carboxyl group-containing monomer；
(a4) 1~69.8 mass % of (methyl) alkyl acrylate monomer；
(a5) 0~30 mass % of co-polymerized monomer other than above-mentioned (a1)~(a4)；
Wherein, above-mentioned monomer (a1)~(a5) adds up to 100 mass %.
Described adhesive layer is especially effective in the case where the polarizing film has occasion of the polycyclic alkene class film as protective film.
The present invention can also be the polarizing film with adhesive phase, have in at least one side of the polarizing film this viscous Mixture layer.
Through the invention, a kind of laminated body is additionally provided, by further conforming to the polarizing film with adhesive phase It is obtained on glass substrate.
The glass substrate is particularly preferably the glass substrate for being used for image display device.
The effect of invention
Through the invention, it is possible to provide excellent durability and glass substrate can be played under hot conditions and wet condition It is between adaptation and the optical films such as polarizing film and phase difference film between the polarizing film of polycyclic alkene class film with protective film The adhesive phase of excellent adhesion.Moreover, described adhesive layer also can be reduced the light leakage of image display device.
The simple declaration of attached drawing
[Fig. 1] Fig. 1 is the sectional view for schematically showing laminated body an example of an embodiment of the present invention.
[Fig. 2] Fig. 2 is the sectional view for schematically showing laminated body an example of an embodiment of the present invention.
Specific embodiment
In the following, referring to attached drawing, the present invention is described in detail.In addition, in the present invention, unless otherwise stated, " part " It indicates " mass parts ", " % " expression " quality % ".
1. adhesive phase
The adhesive phase of present embodiment is characterized in that, is by comprising copolymer (A) described below and isocyanic acid Esters crosslinking agent (B) is formed by adhesive phase as the adhesive composition of neccessary composition, and the adhesive phase is by hereafter The measuring method measure with the contact angle of water at 90 ° or less.
1.1. contact angle
In general, so-called contact angle, refers to the angle of generated liquid contact portion when liquid touches on the surface of solids. The contact angle is characterized at the surface tension (surface energy) between solid and liquid and the surface tension between solid and liquid When mechanical balance state between solid and liquid wetability important physical property, be the important indicator of wetting phenomena, by Young (Young) formula (1) provides.
γ s=γ lcos θ+γ sl ... (1)
θ: contact angle
γ s: the surface tension (surface energy) of solid
γ l: the surface tension (surface energy) of liquid
γ sl: the surface tension between solid and liquid
The inventors discovered that by make the contact angle θ of adhesive layer surface and water at 90 ° or less, further preferably at 40 ° Above 90 ° hereinafter, the adhesive phase of the excellent adhesion between polycyclic alkene class film can be obtained.Big with the contact angle of water Under 90 ° of occasion, the adaptation between adhesive phase and polycyclic alkene class film is bad.And in occasion of the contact angle less than 40 ° Under, the case where and durability excessively high there are the hydrophily of adhesive phase deteriorates.In addition, if with the contact angle of water at 50 ° or more 90 ° hereinafter, the balance then between adaptation and durability is especially excellent, therefore more preferably.
1.2. adhesive composition
1.2.1. copolymer (A)
Copolymer (A) (hereinafter also referred to as " (A) ingredient ") is the monomer using monomer (a1)~(a4) as neccessary composition The copolymer of mixture.
(1) monomer (a1)
Monomer (a1) is the monomer containing polyoxyalkylenes or alkoxyalkyl.Monomer (a1) is preferably free of bridging property base Group.As crosslinkable groups, such as hydroxyl, carboxyl can be enumerated.In addition, monomer (a1) is preferably (methyl) acrylate.
Monomer (a1) can for example be indicated with formula (a-1).
CH2=CR1-COOR2…(a-1)
R1For hydrogen atom or methyl, R2For the group indicated with formula (g-1).
-(R3O)nR4…(g-1)
R3For alkylidene, R4For alkyl, the integer that n is 1 or more.The carbon number of alkylidene is usually 1~10, and preferably 1~5. The carbon number of alkyl is usually 1~10, and preferably 1~4.N is preferably 1~20, and more preferably 1~4, further preferably 1~2.
As monomer (a1), it is more that such as (methyl) alkyl acrylate oxygroup alkyl ester, single (methyl) alkyl acrylate oxygroup can be enumerated Alkylene glycols ester.As (methyl) alkyl acrylate oxygroup alkyl ester, such as (methyl) methoxyethyl methyl esters, (methyl) can be enumerated Acrylic acid 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 3- methoxyl group propyl ester, (methyl) third Olefin(e) acid 3- ethyoxyl propyl ester, (methyl) acrylic acid 4- methoxybutyl, (methyl) acrylic acid 4- Ethoxybutyl.As list (first Base) the more alkylene glycols esters of alkyl acrylate oxygroup, for example single (methyl) methoxyethyl binaryglycol ester, single (methyl) can be enumerated Methoxyethyl dipropylene glycol ester, single (methyl) ethioxy triglycol ester, single (methyl) ethioxy two Glycol ester, list (methyl) methoxyethyl triglycol ester.
As monomer (a1), from the viewpoint of reactivity, the R of preferred formula (a-1) in above-mentioned substance2For alkoxyalkyl (methyl) alkoxyalkyl acrylate.
Monomer (a1) both can be used alone one kind, it is possible to use two or more.
By making (A) ingredient include the structural unit from monomer (a1), adhesive phase can play the tune of birefringence Whole effect, therefore photoelastic coefficient optimum value can be made, the light leakage of image display device can be prevented.From making described adhesive layer From the viewpoint of having appropriate anchoring to the polarizing film of clung body, the content of monomer (a1) is 30~98.8 in monomer mixture Quality %, preferably 50~98.8 mass %, more preferably 50~98.3 mass %.In addition, as an implementation, monomer The content of monomer (a1) is also possible to 50~97.7 mass % in mixture.
(2) monomer (a2)
The hydroxyl monomer of monomer (a2) can make (A) ingredient have the crosslinking being crosslinked with isocyanates crosslinking agent (B) Point.In order to ensure the durability of adhesive phase, the content of monomer (a2) is 0.1~10 mass % in monomer mixture, preferably 0.1~5 mass %, more preferably 0.1~2 mass %.
Monomer (a2) also has polymeric double bond other than hydroxyl.But exclude that there is carboxyl from monomer (a2) Monomer.
As monomer (a2), such as (methyl) hydroxyalkyl acrylate, (methyl) acrylic acid alkylene glycols ester can be enumerated.Specifically For, as (methyl) hydroxyalkyl acrylate, such as (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) acrylic acid 2- hydroxypropyl can be enumerated Ester, (methyl) acrylic acid 4- hydroxy butyl ester, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 8- hydroxyl monooctyl ester, (methyl) propylene Sour 2- hydroxyl -3- phenoxy-propyl.As (methyl) acrylic acid alkylene glycols ester, such as polyethylene glycol (methyl) propylene can be enumerated Acid esters, (methyl) propylene acid propylene glycol ester, polypropylene glycol (methyl) acrylic acid.
Monomer (a2) both can be used alone one kind, it is possible to use two or more.
(3) monomer (a3)
By being copolymerized the monomer mixture comprising monomer (a3) carboxyl group-containing monomer, can obtain having (A) of carboxyl at Point.(A) carboxyl of ingredient forms hydrogen bond in adhesive composition, can assign adhesive phase whereby with cohesive force, improve viscous The durability of mixture layer.Moreover, can be improved bonding of the adhesive phase to clung body by using (A) ingredient with carboxyl Power.From obtaining with from the viewpoint of high-durability adhesive phase, the content of monomer (a3) is 0.1~10 matter in monomer mixture Measure %, preferably 0.1~5 mass %, more preferably 0.1~2 mass %, particularly preferably 0.6~2 mass %.In addition, conduct A kind of embodiment, the content of monomer (a3) is also possible to 1.2~2 mass % in monomer mixture.
Monomer (a3) carboxyl group-containing monomer also has the group comprising polymeric double bond other than carboxyl.
As monomer (a3), (methyl) acrylic acid, carboxylic (methyl) acrylate can be enumerated, without (methyl) propylene Acyl group has carboxyl and the monomer of polymeric double bond etc..As (methyl) acrylate containing carboxyl, such as (first can be enumerated Base) β-acryloxypropionic acid, (methyl) acrylic acid 5- carboxylic pentyl ester.There is carboxyl and polymerization as without (methyl) acryloyl group Property double bond monomer, can enumerate itaconic acid, maleic acid, fumaric acid, butenoic acid, methacrylate etc. containing the monomer of carboxyl or its acid Acid anhydride (maleic anhydride etc.).Wherein, from the viewpoint of copolymerizable, monomer (a3) is preferably (methyl) acrylic acid and contains carboxyl (methyl) acrylate.
(4) monomer (a4)
Monomer (a4) (methyl) alkyl acrylate monomer is without in polyoxyalkylenes, alkoxyalkyl and crosslinkable groups It is any.
The carbon number of the alkyl of monomer (a4) (methyl) alkyl acrylate monomer is usually 1~24.It, can as monomer (a4) It is different to enumerate such as (methyl) acrylate methyl esters, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid Propyl ester, (methyl) propylene N-butyl, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid positive penta Ester, (methyl) the just own ester of acrylic acid, the positive heptyl ester of (methyl) acrylic acid, (methyl) 2-EHA, (methyl) acrylic acid N-octyl, (methyl) Isooctyl acrylate monomer, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) acrylic acid Positive last of the ten Heavenly stems ester, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate, (first Base) octadecyl acrylate, (methyl) acrylic acid isooctadecane base ester.
Monomer (a4) both can be used alone one kind, it is possible to use two or more.
From the viewpoint of the light leakage for adjusting adhesive phase of the invention, the carbon atom number of the abovementioned alkyl chain of monomer (a4) Preferably 1~20, more preferably 1~10.In addition, from the viewpoint of the photoelastic coefficient for adjusting adhesive phase of the invention, The content of monomer (a4) is 1~69.8 mass %, preferably 1~50 mass %, more preferably 1~49.3 matter in monomer mixture Measure %.
(5) monomer (a5)
Monomer mixture also may include monomer (a5) co-polymerized monomer other than above-mentioned (a1)~(a4).As monomer (a5) It can enumerate for example: (methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- diethylamino ethyl ester, N, N- Dimethylaminopropyl (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acryloyl Amine, N, N- dimethyl aminoethyl (methyl) acrylamide, N, N- dimethylaminopropyl (methyl) acrylamide, N- isopropyl The amide-containings such as (methyl) acrylamide, t-octyl (methyl) acrylamide, diacetone alcohol (methyl) acrylamide or amino (methyl) acrylic monomer；Other nitrogenous lists such as acrylamide, pentamethvl (methyl) acrylate, acryloyl morpholine Body；(methyl) benzyl acrylate, (methyl) acrylic acid 2- naphthalene ester, (methyl) phenoxyethyl acrylate etc. have on esteratic site (methyl) acrylate monomer of aromatic ring yl；(methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc. have alicyclic ring (methyl) acrylate monomer of base；(methyl) glycidyl acrylate, (methyl) tetrahydrofurfuryl acrylate etc. have ether ring (methyl) acrylate；Acrylonitrile etc. has the monomer of acryloyl group；Styrene, α-methylstyrene, o-methyl styrene, The styrene monomers such as p-methylstyrene；The vinyl carboxylates such as vinyl acetate；Vinylpyridine, N- ethenyl pyrrolidone Ketone, caprolactam, the macromonomer for containing vinyl (methyl) acryloyl group.
Monomer (a5) both can be used alone one kind, it is possible to use two or more.The content of monomer (a5) in monomer mixture For 0~30 mass %, preferably 0~20 mass %.
(6) monomer (a1)~(a4) total amount
Adhesive phase of the invention is from the excellent durability of realization and reaches between glass substrate and polycyclic alkene class film High adhesion and polycyclic alkene class film between high adhesion from the viewpoint of, the above-mentioned monomer in the monomer mixture (a1), the total amount of (a2), (a3) and (a4) can be 70~100 mass %, preferably 80~100 mass %.
(7) polymerization
(A) there is no particular limitation for the polymerization of ingredient, can pass through the public affairs such as polymerisation in solution, emulsion polymerization, suspension polymerisation The method known is polymerize, but can come treatment process when manufacturing adhesive composition from the copolymer for using polymerization to obtain From the viewpoint of carrying out in a comparatively simple manner and in a short time, preferably it is polymerize by polymerisation in solution.
At least one of organic solvent, monomer and polymerization initiator can also be sequentially added in reaction system.As having Solvent can enumerate for example: benzene, toluene, ethylbenzene, n-propylbenzene, tert-butyl benzene, ortho-xylene, meta-xylene, paraxylene, The aromatic hydrocarbons such as naphthane, decahydronaphthalene, aromatic petroleum naphtha；N-hexane, normal heptane, normal octane, isooctane, n-decane, cinene, oil The aliphatic series class such as gas, naphtha, turpentine oil or alicyclic ring same clan hydrocarbon；Ethyl acetate, n-butyl acetate, n-amyl acetate, acetic acid 2- hydroxyl The esters such as ethyl ester, acetic acid 2- butoxyethyl, acetic acid 3- methoxybutyl, methyl benzoate；Acetone, methyl ethyl ketone, methylisobutylketone, The ketone such as isophorone, cyclohexanone, methyl cyclohexanone；Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethyl two The glycol ethers such as alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether；Methanol, ethyl alcohol, normal propyl alcohol, isopropanol, positive fourth The alcohol such as alcohol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol.These organic solvents can use individually, and two or more can also be used in mixed way.
In these organic solvents, it is preferable to use being not easy to make that chain tra nsfer occurs in polymerization reaction when polymerizeing (A) ingredient Organic solvent, such as ester, ketone especially are easy to carry out etc. to consider, preferably from the dissolubility of (A) ingredient, polymerization reaction Use ethyl acetate, methyl ethyl ketone, acetone etc..
As above-mentioned polymerization initiator, can be used can be in organic peroxide, azo used in conventional solution polymerization Compound etc..As such organic peroxide, such as tert-butyl hydroperoxide, cumyl hydroperoxide, peroxide can be enumerated Change diisopropylbenzene (DIPB), benzoyl peroxide, lauroyl peroxide, peroxidating hexanoyl, di-isopropyl peroxydicarbonate, peroxidating two Two 2- ethylhexyl of carbonic acid, tert-Butyl peroxypivalate, 2,2- bis- (peroxidating 4,4- di-t-butyl cyclohexyl) propane, 2,2- Two (bis- tert-amylcyclohexyl of peroxidating 4,4-) propane, 2,2- bis- (bis- t-octyl cyclohexyl of peroxidating 4,4-) propane, 2,2- bis- (bis- α of peroxidating 4,4--cumyl cyclohexyl) propane, 2,2- bis- (peroxidating 4,4- di-t-butyl cyclohexyl) butane, bis- (mistake of 2,2- Aoxidize bis- t-octyl cyclohexyl of 4,4-) butane etc.；As azo-compound, 2,2'- azodiisobutyronitrile can be enumerated, 2,2'- is even Two -2,4- methyl pentane nitrile of nitrogen, two -4- methoxyl group -2,4- methyl pentane nitrile of 2,2'- azo etc..
These polymerization initiators can use individually, and two or more can also be used in mixed way.
In these polymerization initiators, preferably the polymerization of graft reaction will not be caused to cause in the polymerization reaction of (A) ingredient Agent, particularly preferred azo-compound.The dosage of polymerization initiator is usually 0.01 relative to 100 mass parts of monomer mixture total amount ~2 mass parts, preferably 0.1~1.0 mass parts.
In addition, not damaging the purpose of the present invention and effect when (A) ingredient included in manufacture adhesive composition In the range of fruit, chain-transferring agent can be used as needed.
As such chain-transferring agent, can enumerate for example: cyanoacetic acid；The Arrcostab that the carbon number of cyanoacetic acid is 1~8； Bromoacetic acid；The Arrcostab that the carbon number of bromoacetic acid is 1~8；The aromatic compounds such as anthracene, phenanthrene, fluorenes, 9- phenyl fluorenes；Paranitroanilinum, nitre The aromatic nitro compounds such as base benzene, dinitrobenzene, paranitrobenzoic acid, p-nitrophenol, para-nitrotoluene；Benzoquinones, 2,3,5, The quinone derivatives such as 6- tetramethyl -1,4-benzoquinone；The borane derivatives such as tri-n-butylbo-rane；Carbon tetrabromide, carbon tetrachloride, 1,1,2,2- The halogenated hydrocarbons such as the chloro- 1- propylene of tetrabromoethane, tribromo-ethylene, trichloro ethylene, trichlorobromomethane, bromoform, 3-；Trichloroacetaldehyde, The aldehyde such as furfural；The alkyl hydrosulfide that carbon number is 1~18；The aromatic mercaptans such as benzenethiol, toluenethiol；Thioacetic acid, thioacetic acid The Arrcostab that carbon number is 1~10；The hydroxyalkylmercaptan that carbon number is 1~12；Firpene, terpinolene (タ ー ピ ノ レ Application) etc. terpenes Alkene.
The polymerization temperature of (A) ingredient is manufactured in normally about 30~180 °, preferably 40~150 °, more preferable 50~90 ° of model In enclosing.Reaction time is usually 4~20 hours.In addition, including unreacted in the polymer obtained by solution polymerization process etc. Monomer occasion under, in order to remove the monomer, can be purified by the reprecipitation method carried out with methanol etc..
(8) physical property of (A) ingredient
(8-1) weight average molecular weight and the coefficient of dispersion
From between the adaptation and polycyclic alkene class film improved between glass substrate and polycyclic alkene class film adaptation, From the viewpoint of preventing light leakage and improving durability, the weight average molecular weight (Mw) of (A) ingredient is preferably 400,000~2,000,000, more Preferably 750,000~1,500,000.If the Mw of (A) ingredient is less than 400,000, durability is bad, and if the Mw of (A) ingredient is greater than 2000000, then it is unable to fully reduce light leakage.
From the viewpoint of the adhesive phase for obtaining the excellent adhesion between polycyclic alkene class film, point of (A) ingredient Dissipating coefficient (PDI, Mw/Mn) is preferably 10~20, and more preferably 11~15.If the PDI of (A) ingredient is within the above range, (A) production quantity of low molecular weight is few in ingredient, can obtain the adhesive phase of excellent in te pins of durability.
Here, the Mw and Mn of (A) ingredient be by using GPC (gel permeation chromatography) in embodiment documented by item Standard polystyren is converted under part to acquire.
(8-2) glass transition temperature
From can prevent light leakage and improve the sight of the adaptation between durability and clung body and polycyclic alkene class film Point considers that the glass transition temperature (Tg) of (A) ingredient is preferably -70~0 DEG C, more preferably -50~-10 DEG C.In addition, this hair In bright, the Tg of (A) ingredient is the value calculated by following formula (2) (FOX formula).
1/TgA=Wa1/Tga1+Wa2/Tga2+Wa3/Tga3+Wa4/Tga4+Wa5/Tga5····(2)
(in formula, TgAIndicate the glass transition temperature (K) of (A) ingredient, Tga1、Tga2、Tga3、Tga4、Tga5It respectively indicates By the glass transition temperature (Tg (K)) of monomer (a1), (a2), (a3), (a4), (a5) homopolymer being modulated into, Wa1、Wa2、 Wa3、Wa4、Wa5Respectively indicate the structural unit that monomer (a1), (a2), (a3), (a4), (a5) are come from included in (A) ingredient Measure the weight fraction in entire infrastructure unit.)
In addition, (X is the occasion for example in monomer (aX) comprising two or more monomers (such as (aX-1) and (aX-2)) 1~5 integer) under, related item is write as the form of following formula (3) with monomer (aX) in above formula (2).
WaX/TgaX=WaX-1/TgaX-1+WaX-2/TgaX-2····(3)
(in formula, TgaX-1、TgaX-2It respectively indicates by the glass transition of monomer (aX-1), (aX-2) homopolymer being modulated into Temperature (Tg (K)), WaX-1、WaX-2Respectively indicate the structural unit included in (A) ingredient from monomer (aX-1), (aX-2) Measure the weight fraction in entire infrastructure unit.)
In addition, by above formula (2), TgAWith absolute temperature (K) calculating, it can be converted into Celsius temperature as needed (℃).In addition, the Tg of the representative homopolymer being modulated by monomer is recorded in such as " polymer handbook " fourth edition In (Polymer Handbook Forth Edition, Wiley-Interscience, 2003) etc..
1.2.2. isocyanates crosslinking agent (B)
Isocyanates crosslinking agent (B) (hereinafter also referred to as " (B) ingredient ") as long as can be under room temperature or heating (A) crosslinking agent of ingredient crosslinking is not particularly limited, and it can be mentioned, for example sub- xylene diisocyanate, toluene diisocynate Ester, chlorophenylene diisocyanates, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, two The isocyanate-monomers such as phenylmethane diisocyanate plus diphenyl hydrogen methane diisocyanate make these substances and trihydroxy methyl third Isocyanate compound or isocyanuric acid carboxylate etc. obtained from addition reaction occur for alcoholic compound more than divalents such as alkane etc..
In addition, can also enumerate keeps isocyanate compound and well known polyether polyol or polyester polyol, acrylic acid more Carbamate prepolymer type obtained from addition reaction occurs for first alcohol, polybutadiene polyol, polyisoprene polyol etc. Isocyanates etc..Wherein, it is preferable to use toluene di-isocyanate(TDI) and its derivative etc. are used as (B) ingredient.
From the viewpoint of it can reach defined gel fraction (such as 50~90%), (B) ingredient is combined in adhesive Content in object is 0.1~5 mass parts, preferably 0.2~1 mass parts relative to 100 mass parts of (A) ingredient.
1.2.3. other ingredients
The adhesive composition of present embodiment also may include as needed other than (A) ingredient and (B) ingredient at Point.For example, the adhesive composition of present embodiment can also be blended with (C) silane idol within the scope of the effect of the invention Join agent (being also referred to as " (C) ingredient " sometimes below), (D) ionic compound (being also referred to as " (D) ingredient " sometimes below), (E) Organic solvent (being also referred to as " (E) ingredient " sometimes below), antioxidant, ultraviolet absorbing agent, tackifier, plasticizer etc..
(C) silane coupling agent
Adhesive composition by making present embodiment includes (C) ingredient, in the adhesive group using present embodiment Object is closed under the occasion that clung body surface forms adhesive phase, the bonding between clung body and adhesive can be kept well. (C) ingredient can enumerate for example: vinyltrimethoxysilane, vinyltriethoxysilane and methacryloxypropyl three The silicon compound containing polymerism unsaturated group such as methoxy silane；3- glycidoxypropyltrime,hoxysilane, 3- ring Oxygen propoxypropyl methyl dimethoxysilane and 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane etc. contain epoxy group The silicon compound of structure；3- TSL 8330, N- (2- amino-ethyl) 3- TSL 8330 and The silicon compounds containing amino such as N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane；3- chloro propyl front three Oxysilane；Oligomeric silane coupling agent.Wherein, having can be with the function of functional group reactions included in (A) ingredient Group silane coupling agent due to be not susceptible under high humid and warm environment removing and it is preferred that.From can keep well with clung body it Between bonding from the viewpoint of, content of (C) ingredient in adhesive composition relative to 100 mass parts of (A) ingredient can be 0.1 ~5 mass parts, preferably 0.2~1 mass parts.
(D) ionic compound
In addition, the adhesive composition of present embodiment also may include ionic compound (D).
As (D) ingredient, can enumerate for example by anion and cation constitute at 25 DEG C for liquid or it is solid from Sub- compound can specifically enumerate alkali metal salt, ionic liquid (being liquid at 25 DEG C), surfactant etc..By making this reality The adhesive composition for applying mode includes (D) ingredient, polyoxyalkylenes or alkoxy from (a1) ingredient for constituting (A) ingredient The oxygen atom of alkyl and the cation coordination of composition (D) ingredient, so as to realize high antistatic performance.
As above-mentioned alkali metal salt, the chemical combination constituted such as the alkali metal cation by lithium, sodium, potassium and anion can be enumerated Object can specifically enumerate sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, potassium chlorate, potassium nitrate, sodium nitrate, sodium carbonate, thiocyanic acid Sodium, LiBr, LiI, LiBF4、LiPF6, LiSCN, sodium acetate, sodium alginate, sodium lignosulfonate, toluenesulfonic acid sodium salt, LiCF3SO3、 Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(CF3SO2)3C etc..
As the cation for constituting above-mentioned ionic liquid, can enumerate pyridylium, piperidines cation, pyrrolidones sun from Son, the cation with pyrrolin skeleton, the cation with pyrrole skeleton, glyoxaline cation, tetrahydropyrimidine cation, dihydro Pyrimidine cation, pyrazoles cation, dihydropyazolo cationic (ピ ラ ゾ リ ニ ウ system カ チ オ Application), tetraalkylammonium cation, Trialkylsulfonium cation, tetraalkyl phosphine cation etc. can enumerate Cl as the anion for constituting above-mentioned ionic liquid-、Br-、I-、 AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)2N-、 (CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -(n=2~3), (CN)2N-、C4F9SO3 -、(C2F5SO2)2N-、 C3F7COO-、(CF3SO2)(CF3CO)N-Deng.
In addition, as above-mentioned ionic liquid, can enumerate be made of these cations and anion is liquid at 25 DEG C Ionic compound.As such ionic liquid, 2- methyl-1-pyrroles's tetrafluoroborate, 1- ethyl-2- benzene can be specifically enumerated Base indoles tetrafluoroborate, 1,2- dimethyl indole tetrafluoroborate, 1- ethyl carbazole tetrafluoroborate, 1- ethyl -3- methyl Tetrafluoroborate, 1- ethyl-3-methylimidazole acetate, 1- ethyl-3-methylimidazole trifluoroacetate, 1- ethyl -3- Methylimidazole hyptafluorobutyric acid salt, 1- ethyl-3-methylimidazole fluoroform sulphonate, 1- ethyl-3-methylimidazole perfluor fourth sulfonic acid Bis- (trifluoro methylsulfonyl) imines of salt, 1- ethyl-3-methylimidazole dicyandiamide salt, 1- ethyl-3-methylimidazole, 1- ethyl -3- first Bis- (the five fluorine second sulphonyl) imines of base imidazoles, methylation 1- ethyl-3-methylimidazole three (trifluoro methylsulfonyl), 1- butyl -3- methyl Tetrafluoroborate, 1- butyl -3- methylimidazole hexafluorophosphate, 1- butyl -3- methylimidazole trifluoroacetate, 1- fourth Base -3- methylimidazole hyptafluorobutyric acid salt, 1- butyl -3- methylimidazole fluoroform sulphonate, 1- butyl -3- methylimidazole perfluor fourth Bis- (trifluoro methylsulfonyl) imines of sulfonate, 1- butyl -3- methylimidazole, bromination 1- hexyl -3- methylimidazole, chlorination 1- hexyl - 3- methylimidazole, 1- hexyl -3- methyl imidazolium tetrafluoroborate, 1- hexyl -3- methylimidazole hexafluorophosphate, 1- hexyl -3- Methylimidazole fluoroform sulphonate, 1- octyl -3- methyl imidazolium tetrafluoroborate, 1- octyl -3- methylimidazole hexafluorophosphate, Bis- (trifluoro methylsulfonyl) imines of 1- hexyl -2,3- methylimidazole tetrafluoroborate, 1,2- dimethyl -3- propyl imidazole, 1- first Base pyrazoles tetrafluoroborate, 3- methylpyrazole tetrafluoroborate, tetrahexyl ammonium bis- (trifluoro methylsulfonyl) imines, diallyl dimethyl Base ammonium tetrafluoroborate, diallyl dimethyl ammonium fluoroform sulphonate, diallyl dimethyl ammonium bis- (trifluoro methylsulfonyls) are sub- Amine, diallyl dimethyl ammonium bis- (five fluorine second sulphonyl) imines, N, N- diethyl-N- methyl-N- (2- methoxy ethyl) ammonium four Borofluoride, N, N- diethyl-N- methyl-N- (2- methoxy ethyl) ammonium fluoroform sulphonate, N, N- diethyl-N- methyl- N- (2- methoxy ethyl) ammonium bis- (trifluoro methylsulfonyl) imines, N, N- diethyl-N- methyl-N- (2- methoxy ethyl) ammonium are double (five fluorine second sulphonyl) imines, glycidyltrimetiiylammonium ammonium fluoroform sulphonate, bis- (the trifluoro methylsulphurs of glycidyltrimetiiylammonium ammonium Acyl) imines, bis- (the five fluorine second sulphonyl) imines of glycidyltrimetiiylammonium ammonium, 1- butyl-pyridinium (trifluoro methylsulfonyl) trifluoroacetyl Amine, 1- butyl -3- picoline (trifluoro methylsulfonyl) trifluoroacetamide, 1- ethyl-3-methylimidazole (trifluoro methylsulfonyl) trifluoro Acetamide, N, N- diethyl-N- methyl-N- (2- methoxy ethyl) ammonium (trifluoro methylsulfonyl) trifluoroacetamide, diallyl two Methyl ammonium (trifluoro methylsulfonyl) trifluoroacetamide, glycidyltrimetiiylammonium ammonium (trifluoro methylsulfonyl) trifluoroacetamide, N, N- bis- Methyl-N ethyl-N- propyl ammonium bis- (trifluoro methylsulfonyl) imines, N, bis- (the trifluoro methylsulphurs of N- dimethyl-N-ethyl-N- butyl ammonium Acyl) imines, N, N- dimethyl-N-ethyl-N- amyl ammonium bis- (trifluoro methylsulfonyl) imines, N, N- dimethyl-N-ethyl-N- hexyl Ammonium bis- (trifluoro methylsulfonyl) imines, N, N- dimethyl-N-ethyl-N- heptyl ammonium bis- (trifluoro methylsulfonyl) imines, N, N- dimethyl- N- ethyl-N- nonyl ammonium bis- (trifluoro methylsulfonyl) imines, N, bis- (trifluoro methylsulfonyl) imines of N- dimethyl-N, N- dipropylammonium, N, N- dimethyl-N-propyl-N- butyl ammonium bis- (trifluoro methylsulfonyl) imines, N, N- dimethyl-N-propyl-N- amyl ammonium bis- (three Fluorine methylsulfonyl) imines, N, N- dimethyl-N-propyl-N- hexyl ammonium bis- (trifluoro methylsulfonyl) imines, N, N- dimethyl-N-propyl- N- heptyl ammonium bis- (trifluoro methylsulfonyl) imines, N, N- dimethyl-N-butyl-N- hexyl ammonium bis- (trifluoro methylsulfonyl) imines, N, N- Dimethyl-N-butyl-N- heptyl ammonium bis- (trifluoro methylsulfonyl) imines, N, the bis- (fluoroforms of N- dimethyl-N-amyl-N- hexyl ammonium Sulphonyl) imines, N, bis- (trifluoro methylsulfonyl) imines of N- dimethyl-N, N- dihexyl ammonium, bis- (the trifluoro methylsulphurs of trimethyl heptyl ammonium Acyl) imines, N, N- diethyl-N- Methyl-N-propyl ammonium bis- (trifluoro methylsulfonyl) imines, N, N- diethyl-N- methyl -- V-pentyl Ammonium bis- (trifluoro methylsulfonyl) imines, N, N- diethyl-N- methyl-N- heptyl ammonium bis- (trifluoro methylsulfonyl) imines, N, N- diethyl- Bis- (trifluoro methylsulfonyl) imines of N- propyl-N- amyl ammonium, bis- (trifluoro methylsulfonyl) imines of triethyl group propyl ammonium, triethyl group amyl ammonium Bis- (trifluoro methylsulfonyl) imines, triethyl group heptyl ammonium bis- (trifluoro methylsulfonyl) imines, N, N- dipropyl-N- methyl-N ethyl ammonium Bis- (trifluoro methylsulfonyl) imines, N, N- dipropyl-N- methyl -- V-pentyl ammonium bis- (trifluoro methylsulfonyl) imines, N, N- dipropyl-N- Butyl-N- hexyl ammonium bis- (trifluoro methylsulfonyl) imines, N, N- dipropyl-N, N- dihexyl ammonium bis- (trifluoro methylsulfonyl) imines, N, N- dibutyl-N- methyl -- V-pentyl ammonium bis- (trifluoro methylsulfonyl) imines, N, the bis- (trifluoros of N- dibutyl-N- methyl-N- hexyl ammonium Methylsulfonyl) imines, bis- (trifluoro methylsulfonyl) imines of tricaprylmethylammonium, N- methyl-N ethyl-N- propyl-N- amyl ammonium bis- (three Fluorine methylsulfonyl) imines etc..
As above-mentioned surfactant, nonionic surfactant, cationic surfactant, anionic surface can be used Any one of activating agent and amphoteric surfactant.
As above-mentioned nonionic surfactant, can enumerate for example: polyoxyethylene laurel ether, polyoxyethylene stearyl ether etc. are poly- Ethylene oxide alkyl ether；The polyoxyethylene alkyl phenyl ethers such as NONIN HS 240, ethylene nonyl phenyl ether；Single laurel The higher fatty acids sorbitol esters such as sour sorbitol ester, monostearate sorbitol ester, three oleic acid sorbitol esters；Polyoxy second The polyoxyethylene sorbitols high-grade aliphatic esters such as alkene D-sorbite monolaurate；Vinlub 73, polyoxy second The polyoxyethylene higher fatties acid esters such as alkene monostearate；The higher fatty acids such as monoolein, glyceryl monostearate are sweet Grease；The polyoxies alkane alkene such as polyoxyethylene, polyoxypropylene, polybutylene；And their block copolymer.
As above-mentioned cationic surfactant, such as alkyl trimethylammonium chloride, chlorination dialkyl dimethyl can be enumerated Ammonium, benzalkonium chloride salt, alkyl dimethyl QAE quaternary aminoethyl sulfate etc..
It as above-mentioned anionic surfactant, can enumerate for example: sodium laurate, enuatrol, the sweet ammonia of N- acyl-N-methyl The carboxylates such as acid sodium-salt, polyoxyethylene laurel ether carboxylic acid sodium, neopelex, dialkylsulfosuccinic, The sulfonate such as phthalic acid dimethyl -5- sodium sulfonate (ジ メ チ Le -5- ス Le ホ イ ソ Off タ レ ー ト Na ト リ ウ system), laurel The sulfuric acids such as alcohol sodium sulphate, polyoxyethylene laurel ether sodium sulphate, ethylene nonyl phenyl ether sodium sulphate, polyoxyethylene laural The phosphate ester salts such as alcohol sodium phosphate, ethylene nonyl phenyl ether sodium phosphate.
As above-mentioned amphoteric surfactant, such as carboxylic acid glycine betaine type surfactant, aminocarboxylate, miaow can be enumerated Oxazoline glycine betaine, lecithin, alkyl amine oxide.
In addition, in addition to this, as (D) ingredient, it is possible to use electric conductive polymer, conductive carbon, ammonium chloride, aluminium chloride, Copper chloride, iron chloride, ammonium sulfate etc..
Wherein, it is preferable to use alkali metal salt is used as (D) ingredient.
Under the occasion that the adhesive composition of present embodiment includes (D) ingredient, (D) ingredient is in adhesive composition Content relative to 100 mass parts of (A) ingredient can be 0.1~10 mass parts, preferably 0.5~5 mass parts.
(E) organic solvent
The adhesive composition of present embodiment preferably comprises (E) ingredient to adjust its coating.As (E) at Point, the organic solvent illustrated in " (7) polymerization " column can be enumerated.(E) content of ingredient in the composition is relative to (A) 100 mass parts of ingredient can be 50~90 mass parts, preferably 60~90 mass parts.
1.2.4. the manufacture of adhesive composition
The adhesive composition of present embodiment usually can be by making by above-mentioned (A) and (B) ingredient and as needed Any ingredient is mixed simultaneously or is modulated with random order mixing.In addition, being mixed to (A) ingredient and (B) ingredient When, under the occasion for modulating (A) ingredient by polymerisation in solution, can by (B) ingredient be added comprising polymerization after (A) at In the solution divided；Under the occasion for modulating (A) ingredient by bulk polymerization, due to polymerization after be difficult to uniformly be mixed It closes, adds (B) ingredient preferably in the polymerization process and mix.
1.3. the formation of adhesive phase
Adhesive phase of the invention is formed by above-mentioned adhesive with composition.Described adhesive layer can be for example, by carrying out on The cross-linking reaction in adhesive composition is stated to obtain, can specifically be obtained by being crosslinked (A) ingredient with (B) ingredient.It is viscous The formation condition of mixture layer is for example as described below.Above-mentioned adhesive composition is coated on supporting mass, temperature is according to solvent kind Class and it is different, but usually 50~150 DEG C, preferably carried out at 60~100 DEG C usually 1~10 minute, preferably 2~7 minutes Drying and remove solvent, formed film.The film thickness of dry coating is usually 5~75 μm, and preferably 10~50 μm.
Adhesive phase is preferably formed under the following conditions.Above-mentioned adhesive composition is coated on supporting mass, above-mentioned Under the conditions of paste stripping film on the film that is formed after, usual 5~60 DEG C, preferably 15~40 DEG C and usual 30~70%RH, It is preferred that being conserved in the environment of 40~70%RH usual 3 days or more, preferably 7~10 days.If under cooking conditions as described above It is crosslinked, then crosslinked (network polymers) can be efficiently formed.
As the coating method of adhesive composition, well known method can be used, such as pass through spin-coating method, cutter painting method, roller Coating, stick coating method, scraper coating, die coating method, gravure coating method form the coating drying means of specific thickness.
It as supporting mass and stripping film, can enumerate for example: the polyester film of polyethylene terephthalate (PET) etc.；It is poly- The plastic foil of the polyolefin films such as ethylene, polypropylene, vinyl-vinyl acetate copolymer etc..
In addition, the adhesive composition of present embodiment is from preventing light leakage and improve durability and clung body and poly- From the viewpoint of adaptation between cyclenes hydrocarbon membranes, the gel fraction of the adhesive composition of present embodiment is preferably 50~ 90%, more it is selected as 60~80%.
When the above-mentioned gel fraction of the adhesive composition of present embodiment can be for example, by modulating adhesive composition The type or dosage of (a2) ingredient in used monomer mixture and (a3) ingredient, as (B) ingredient crosslinking agent kind Class or dosage are adjusted.In addition, above-mentioned gel fraction can obtain in the following manner: 0.1g will be calculated as with dry weight The adhesive by crosslinking of (dry weight (1)) collects in sample bottle, after ethyl acetate 30cc is added in sample bottle Concussion 24 hours, is filtered the content of the sample bottle with the stainless steel metal mesh of 200 purposes, to metal at 100 DEG C Its dry weight (dry weight (2)) is measured after the drying of online residue progress 2 hours, (4) find out gel according to the following formula Score.
Gel fraction (%)=(dry weight (2)/dry weight (1)) × 100 (4)
2. polarizing film
As polarizing film, it is used to form the polarizing film of the image display devices such as liquid crystal display device.In addition, this theory In bright book, " polarizing film " comprising the meaning of " polarizing coating " to use.
As polarizing film, well known polarizing film so far can be used, can enumerate for example with polarizer and configuration described The polarizing film of protective film on the single or double of polarizer.
As polarizer, can enumerate it for example after containing polarized component in the film for making to be made of polyvinyl alcohol resin Stretched film obtained from stretching.As polyvinyl alcohol resin, such as polyvinyl alcohol, polyvinyl formal, poly- second can be enumerated Enol acetal, ethylene vinyl acetate copolymer it is saponified.As polarized component, such as iodine or dichroism dye can be enumerated Material.
As protective film, can enumerate such as acetylcellulose as tri acetyl cellulose, diacetyl cellulose etc. Film, polycarbonate membrane, poly (ether sulfone) film, the polycyclic alkene class film being made of cellulose.It wherein, is poly- in the protective film of polarizer Under the occasion of cyclenes hydrocarbon membranes, the contraction that protective film occurs by heating is small, thus preferably.
The thickness of polarizing film is usually 30~250 μm, and preferably 50~200 μm.
Further, it is also possible to which being laminated on above-mentioned polarizing film has it such as antiglare layer, phase separation layer, angle of visibility improve layer The layer of its function.
In the present invention, " polycyclic alkene class film " refers to the skeleton from polycyclic olefin in structural unit including at least 50% Substance.Polycyclic alkene class film can be polycyclic olefin copolymer, at this point, polycyclic olefin copolymer can be for example, by Ziegler (Ziegler) ethylene and polycyclic olefin (such as tetracyclododecane) are copolymerized to obtain.
As polycyclic alkene class film, commercially available polycyclic alkene class film can be used.It, can example as commercially available polycyclic alkene class film Citing such as ZEONOR film (ゼ オ ノ ア Off ィ Le system, Zeon Corp's (Japanese ゼ オ Application) manufacture), ARTON film (JSR Co., Ltd.'s manufacture) etc..
In addition, the surface of polarizing film is preferably through sided corona treatment.Untreated polycyclic alkene class film has near 100 ° Contact angle, by implementing sided corona treatment, contact angle is reduced to 40~50 °.And the contact angle of traditional binders is near 110 °, Even the polycyclic alkene class film by sided corona treatment, bonding also extremely difficult between adhesive and polycyclic alkene class film.Phase Than under, the contact angle of invention adhesives layer is at 90 ° hereinafter, having for the polycyclic alkene class film Jing Guo sided corona treatment high Adaptation.
3. polarizing film and laminated body with adhesive phase
Polarizing film with adhesive phase is the polarization that above-mentioned adhesive phase is formed in at least one side on polarizing film surface Piece.It is not particularly limited, can be enumerated using direct stick coating method etc. in polarizing film in the method that polarizing film surface forms adhesive phase Adhesive phase of the invention is transferred to polarizing film table by the method that makes it dry and cure after coating adhesive composition on surface The method for curing it behind face.Desirable shape under the occasion that adhesive phase is transferred to polarizing film surface, as adhesive phase State, can enumerate for example only the double-sided adhesive sheet with adhesive phase, with substrate and the above-mentioned bonding being formed on substrate two sides The double-sided adhesive sheet of oxidant layer, the single side bonding sheet with substrate and the above-mentioned adhesive phase being formed in substrate one side and this A little bonding sheets are pasted with the bonding sheet of the cover film by lift-off processing on the face of adhesive phase not contacted with substrate.Substrate With cover film in above-mentioned one column of adhesive phase illustrated by material it is identical.The formation condition of adhesive phase or gel fraction with it is upper It is identical to state documented condition in one column of adhesive phase.The film thickness of adhesive phase from maintain bond properties from the viewpoint of be usually 5~75 μm, preferably 10~50 μm.The film thickness of substrate and cover film is not particularly limited, but usually 10~125 μm, preferably It is 25~75 μm.
Liquid crystal cell is manufactured by the way that the above-mentioned polarizing film with adhesive phase to be arranged on the substrate surface of liquid crystal cell. Here liquid crystal cell has liquid crystal layer construction clamped by two pieces of substrates.
Adhesive phase of the invention can be used to manufacture following laminated body, wherein the polarizing film have polarizer and The protective film on the polarizer is configured, the laminated body is by the polarizer, the protective film, adhesive of the invention Layer and glass substrate are laminated in this order.
Fig. 1 is the sectional view for schematically showing laminated body an example (laminated body 100) of an embodiment of the present invention.Such as figure Shown in 1, laminated body 100 includes glass substrate 10, polycyclic alkene class film 32 and is arranged in glass substrate 10 and polycyclic alkene class Adhesive phase 20 between film 32.Laminated body 100 includes polarizing coating 30, and polarizing coating 30 may include polycyclic alkene class film 32.
More specifically, laminated body 100 includes glass substrate 10, setting adhesive phase 20 on the glass substrate 10, is situated between By the polarizing coating 30 of the setting of adhesive phase 20 on the glass substrate 10.Polarizing coating 30 has polycyclic alkene class film 32, setting poly- Polyvinyl alcohol film 34 in cyclenes hydrocarbon membranes 32 and the TAC film 36 being arranged on polyvinyl alcohol film 34.Glass substrate 10 and poly- Cyclenes hydrocarbon membranes 32 are bonded via adhesive phase 20.
Fig. 2 is the sectional view for schematically showing another example of laminated body (laminated body 200) of an embodiment of the present invention.Such as Shown in Fig. 2, laminated body 200 includes glass substrate 10, polycyclic alkene class film (phase difference film) 32 and polarizing coating 130, and glass Substrate 10, polycyclic alkene class film 32 and polarizing coating 130 are laminated in this order.Polycyclic alkene class film 32 can be phase difference film.
Polycyclic alkene class film 32 is Nian Jie via adhesive phase 20 with polarizing coating 130.In addition, glass substrate 10 and polycyclic alkene Class film 32 is bonded via adhesive phase 22.Polarizing coating 130 has layer (the second polycyclic alkene class of polycyclic alkene class film or TAC film Film) 38, the polyvinyl alcohol film 34 being arranged on layer 38 and the TAC film 36 being arranged on polyvinyl alcohol film 34.Polycyclic alkene class Film (the first polycyclic alkene class film) 32 and layer (the second polycyclic alkene class film) 38 are Nian Jie via adhesive phase 20.
Adhesive phase 20,22 in Fig. 1 and Fig. 2 is formed in clung body (in the adhesive phase 20 and Fig. 2 in Fig. 1 Adhesive phase 22, clung body is glass substrate 10 or polycyclic alkene class film 32；For the adhesive phase 20 in Fig. 2, clung body Polycyclic alkene class film 32 or layer 38) surface on.It is formed in the method on the surface of clung body as by adhesive composition, Such as transfer printing can be enumerated: that is, adhesive composition is coated on the surface of the good mold release film of flatness (wall), It, will be on the adhering molding transfer to the surface of specific resin film after making dried coating film.
The laminated body of present embodiment can be used for such as image display device (especially liquid crystal display device).It is more specific and Speech, the laminated body of present embodiment can be used for such as touch screen image display device.Under the occasion, the stacking of present embodiment Glass substrate included in body is preferably liquid crystal display device glass substrate.
The glass substrate for constituting the laminated body of present embodiment can be the glass substrate for device used for image display.Make For image display device, can be such as TFT liquid crystal TV set, computer display, mobile phone, tablet computer (thin film transistor (TFT)) liquid crystal display device.
4. function and effect
Present embodiment for polarizing film to be conformed to the adhesive phase on image display device by by its adhesive The contact angle of layer is adjusted to having adaptation, the effect of excellent in te pins of durability kept between clung body well in prescribed limit Fruit.The monomer (a1) being used to form in the monomer mixture of (A) ingredient can bring appropriate anchoring and be prevented for adhesive phase Light leakage effect.That is, the present invention is the invention based on following novel and original creation design: by by the monomer (a1) comprising specific quantity (A) ingredient that the monomer mixture of monomer containing polyoxyalkylenes or alkoxyalkyl is formed, by the bonding comprising (A) ingredient The adhesive phase that agent composition is formed can obtain the adhesive phase with the elasticity modulus suitable for polycyclic alkene class film, thus energy Enough adaptations improved between polycyclic alkene class film, and then by controlling monomer (a2)~(a4) blending in prescribed limit It is interior and can be achieved at the same time leakproof light effect and durability.
[embodiment]
In the following, examples illustrate the present invention based on following, but the present invention is not limited to embodiments.
<heating residual components>
1g or so polymer solution is added in the tin plating disk by accurate weighing, after carrying out accurate weighing to total weight, It is heated 3 hours at 105 DEG C, measurement heating residual components (nV).Residual components are heated according to the benchmark of JIS K 5407:1997 It is measured.
<viscosimetric analysis>
The 500ml bottle for enclosing varnish equipped with polymer solution is immersed in 25 DEG C of thermostatic water bath and stands 12 hours Afterwards, viscosity is measured according to the measuring method of Type B adhesive.
<GPC determination condition>
For acrylic polymer, weight average molecular weight is found out with following conditions by gel permeation chromatography (GPC method) (Mw) and the coefficient of dispersion (PDI).
Measurement device: HLC-8120GPC (TOSOH Co., Ltd (Dong ソ ー (strain)) manufacture)
The composition of GPC column: 5 pedestal (all being manufactured by TOSOH Co., Ltd) below
(i) TSK-GEL HXL-H (guard column)
(ii)TSK-GEL G7000HXL
(iii)TSK-GEL GMHXL
(iv)TSK-GEL GMHXL
(v)TSK-GEL G2500HXL
Sample concentration: 1.0mg/cm is diluted to tetrahydrofuran3
Mobile phase solvent: tetrahydrofuran
Flow: 1.0cm3/min
Column temperature: 40 DEG C
It is converted into standard polystyren
[synthesis example 1] (synthesis of acrylic polymer 1)
8 mass parts acrylic acid are added into the flask equipped with agitating device, nitrogen ingress pipe, thermometer and the cooling tube that flows back Butyl ester, 90 mass parts acrylic acid 2- methoxy acrylates, 1 mass parts acrylic acid, 1 mass parts acrylic acid 2- hydroxyl ethyl ester and 140 mass The content of flask is heated to 70 DEG C while importing nitrogen into flask by part ethyl acetate.Then, under stiring to quilt 0.1 mass parts 2,2'- azodiisobutyronitrile (AIBN) is added in the flask that nitrogen has been sufficiently displaced from.On one side by the content in flask The temperature of object maintains 70 DEG C, carries out reaction 8 hours.140 mass are added into the reaction mixture after 8 hours Part ethyl acetate, obtains the polymer solution 1 comprising acrylic polymer 1.Adding at 105 DEG C of resulting polymers solution 1 Hot residual components (nV%) are 25.2%, and the viscosity at 23 DEG C is 5.2Pas.In addition, gained acrylic polymer 1 by The Mw of GPC measurement is 90.2 ten thousand, PDI 12.
[synthesis example 2~8 and 10~12] (synthesis of acrylic polymer 2~8 and 10~12)
Be changed in table 1 other than documented content in addition to by polymerizable monomer used in polymerization reaction, according to The identical mode of synthesis example 1 is synthesized, and the polymer solution comprising acrylic polymer 2~8 or 10~12 is made.As a result It is shown in table 1.
[synthesis example 9] (synthesis of acrylic polymer 9)
8 mass parts acrylic acid are added into the flask equipped with agitating device, nitrogen ingress pipe, thermometer and the cooling tube that flows back Butyl ester, 90 mass parts acrylic acid 2- methoxy acrylates, 1 mass parts acrylic acid, 1 mass parts acrylic acid 2- hydroxyl ethyl ester and 120 mass The content of flask is heated to 65 DEG C while importing nitrogen into flask by part ethyl acetate.Then, under stiring to quilt 0.05 mass parts AIBN is added in the flask that nitrogen has been sufficiently displaced from.The temperature of the content in flask is maintained 65 on one side DEG C, carry out reaction 3 hours.Then, while instilling 160 mass parts ethyl acetate, heating is until interior in flask It is tolerant to reach 75 DEG C, carry out reaction 5 hours.After reaction starts 8 hours, 120 mass parts acetic acid are added into reaction mixture Ethyl ester obtains the polymer solution 6 comprising acrylic polymer 6.The heating residual components (nV%) of resulting polymers solution 6 It is 20%, the viscosity at 23 DEG C is 3.8Pas.In addition, the Mw by GPC measurement of gained acrylic polymer 9 is 1,100,000, PDI is 24.
[table 1]
The numerical value unit of monomer is mass parts in table 1.
In addition, the abbreviation in table 1 indicates following meanings.
BA: butyl acrylate (Tg:-50 DEG C of homopolymer)
2EHA: 2-EHA (Tg:-70 DEG C of homopolymer)
MEA: acrylic acid 2- methoxy acrylate (Tg:-50 DEG C of homopolymer)
AA: acrylic acid (Tg:106 DEG C of homopolymer)
HEA: acrylic acid 2- hydroxyl ethyl ester (Tg:-15 DEG C of homopolymer)
[embodiment 1]
(1) production of adhesive composition
Into the polymer solution 1 comprising acrylic polymer 1 obtained by above-mentioned synthesis example 1, incorporation is relative to above-mentioned 100 mass parts of solid component of polymer solution 1 be following table 2 shown in mix proportions (B) ingredient and (C) ingredient, sufficiently Mixing.Here, solid component refers to the whole components from polymer solution other than organic solvent.
(2) production of bonding sheet
After defoaming, with scraper in the polyethylene terephthalate film (PET Jing Guo lift-off processing under 25 DEG C of liquid temperature Film) on be coated with the adhesive composition that is obtained by above-mentioned (1), it is 3 minutes dry at 90 DEG C, forms dry film thickness as 25 μm of painting Film.The PET film Jing Guo lift-off processing is further bonded on the reverse side of the adhesive surface of the above-mentioned PET film of film, 23 DEG C/50% After standing 7 days under RH environment and being cured, obtain with clamped by 2 pieces of PET films with a thickness of the viscous of 25 μm of adhesive phase Close piece.
(3) production of the polarizing film with adhesive phase
After defoaming, the adhesive composition obtained by (1) is coated on PET wall with scraper, it is 3 points dry at 90 DEG C Clock forms the film with a thickness of 25 μm.The coated surface of the sheet material, which is conformed to, has polycyclic alkene class (COP) on a surface On the COP film surface of the polarizing film of film, 1~7 day is stood under conditions of 23 DEG C of room temperature, humidity 65%, is obtained with adhesive phase Polarizing film.
[embodiment 2~9 and comparative example 1~3]
In addition to by embodiment 1 blending composition be changed in table 2 other than documented content, according to 1 phase of embodiment Same mode obtains adhesive composition, bonding sheet and the polarizing film with adhesive phase.
[evaluation]
(1) gel fraction
From being acquired on the bonding sheet obtained by embodiment and comparative example in 1g adhesive phase investment 50ml ethyl acetate, with vibration Machine (model: shaker SA-300, big and scientific Co., Ltd. (ヤ マ ト science Co., Ltd.) manufacture) is swung to be handled.With The stainless (steel) wire sieving gel ingredient of 200 mesh makes it dry.Then, the quality of sample after filtering is calculated divided by sample before filtering Quality obtained by be worth, as gel fraction.
(2) photoelastic coefficient
The evaluation obtained from embodiment and comparative example, will be with a thickness of 25 μm of adhesive phase with PET film is peeled on bonding sheet Repeatedly be bonded and be adjusted to the adhesive phase of 1mm thickness each other, with automatic length scanning type ellipsometer (M220 type, Japan Spectroscopy Corporation (light splitting society, Japan) manufacture) above-mentioned adjust to 1mm thickness is glued under conditions of measuring wavelength 600nm Mixture layer is measured, and obtained measured value is photoelastic coefficient.
(3) contact angle
The size that the polarizing film with adhesive phase obtained by embodiment and comparative example is cut into 50mm × 50mm, peels PET wall.The ion exchange water being filled in syringe is set to drop to the table of adhesive phase with 1 μ L of flow, 0.5 μ L/s of flow velocity On face, adhesive phase is measured with contact angle meter (OCA15EC that dataphysics Co., Ltd. (dataphysics society) manufactures) Contact angle.
(4) durability (heat-resisting humidity test)
The polarizing film with adhesive phase obtained by embodiment and comparative example is cut into the size of 150mm × 250mm, is made At test film.PET wall is peeled from test film, is affixed to test film on the single side of glass plate with laminating roll, then, It adjusts into the autoclave of 50 DEG C, 5 atmospheric pressure and is kept for 20 minutes, breadboard is made.Two pieces of identical breadboards are made.Wherein One piece of breadboard for heat resistant test and placed 500 hours under conditions of 80 DEG C.Another piece of breadboard is used for humidity test And it is placed 500 hours under conditions of 60 DEG C and humidity 95%RH.According to following benchmark respectively between glass plate-adhesive phase Interface it is peeling-off, blistering the case where etc. carry out visual confirmation.
(benchmark)
AA: the bad orders such as removing are not observed.
BB: the bad orders such as slight removing are observed.
CC: the bad orders such as apparent removing are observed.
(5) light leakage is tested
The polarizing film with adhesive phase obtained by embodiment and comparative example is cut into the size of 80mm × 140mm, is used Laminating roll in the mode that keeps polarization axle mutually orthogonal by polarizing plate sticking to the two sides with a thickness of the alkali-free glass plate of 1.1mm on, Then, it is kept for 20 minutes in adjusting the autoclave to 50 DEG C, 5 atmospheric pressure, breadboard is made.It is in temperature by the breadboard It places 500 hours under conditions of 80 DEG C, light leakage is observed according to following benchmark.
(benchmark)
AA: light leakage is not observed.
BB: a small amount of light leakage is observed.
CC: apparent light leakage is observed.
(6) adaptation between polarizing film (COP)
For the breadboard after above-mentioned humidity test, to the interface between the COP film surface and adhesive phase of polarizing film into Row visual confirmation is evaluated according to following benchmark.
(benchmark)
AA: the bad orders such as removing are not observed.
BB: the bad orders such as slight removing are observed.
CC: the bad orders such as local removing are observed.
DD: the bad orders such as significant removing are observed.
[table 2]
The numerical value unit of adhesive composition is mass parts in table 2.
In addition, the abbreviation in table 2 indicates following meanings.
L-45:TDI class curing agent ((comprehensive the to grind chemical society) manufacture of Soken Chemical & Engineering Co., Ltd.)
KBM403: silane coupling agent (organosilicon Co., Ltd., SHIN-ETSU HANTOTAI (SHIN-ETSU HANTOTAI's シ リ コ ー Application) manufacture)
From the result of table 2 it is understood that the bonding sheet of above-described embodiment 1~9 is since adhesive phase is by including above-mentioned (A) ingredient The contact angle of adhesive composition formation, adhesive layer surface and water with above-mentioned (B) ingredient is at 90 ° or less and described (A) Ingredient is the copolymer comprising meeting monomer (a1)~(a5) monomer mixture of rated condition, therefore via adhesive layer The excellent adhesion between adaptation and polycyclic alkene class film between glass substrate and polycyclic alkene class film, can be presented height Durability, and light leakage can be reduced.
In contrast, the bonding sheet of above-mentioned comparative example 1 is due to monomer in the monomer of above-mentioned (A) ingredient of the composition of adhesive phase (a1) content is lower than 30 mass %, thus photoelastic coefficient is improper, generates light leakage.Moreover, contact angle is greater than 90 °, therefore Adaptation between COP is also unable to get good result.In addition, the bonding sheet of above-mentioned comparative example 2 is due to composition (A) ingredient Monomer mixture in be free of monomer (a2), therefore durability is poor, and light leakage test can not also be evaluated.In addition, above-mentioned comparative example 3 Monomer mixture of the bonding sheet due to constituting above-mentioned (A) ingredient in the blended amount of monomer (a2) and (a3) it is excessive, it is durable Property is poor.
[symbol description]
10 glass substrates
20,22 adhesive phase
30,130 polarizing coating
32 phase difference films (polycyclic alkene class film)
34 polyvinyl alcohol (PVA) film
36 TAC films
38 polycyclic alkene class films or TAC film
100,200 laminated body

Claims (5)

1. a kind of adhesive phase is for polarizing film to be conformed to the adhesive phase on image display device, the adhesive phase Adhesive layer surface and water contact angle at 90 ° hereinafter, and the adhesive phase by comprising (A) containing following monomers (a1)~ (a5) copolymer of monomer mixture and (B) are the different of 0.1~5 mass parts relative to 100 mass parts of the copolymer (A) The adhesive composition of cyanate crosslinking agent obtains:
(a1) 30~98.8 mass % of monomer containing polyoxyalkylenes or alkoxyalkyl；
(a2) 0.1~10 mass % of hydroxyl monomer；
(a3) 1.2~10 mass % of carboxyl group-containing monomer；
(a4) 1~69.8 mass % of (methyl) alkyl acrylate monomer；
(a5) 0~30 mass % of co-polymerized monomer other than (a1)~(a4)；
Wherein, monomer (a1)~(a5) adds up to 100 mass %；
The monomer (a1) by formula (a-1) indicate,
CH2=CR1-COOR2···(a-1)
In formula (a-1), R1For hydrogen atom or methyl,
R2For the group indicated with formula (g-1)；
-(R3O)nR4···(g-1)
In formula (g-1), R3For alkylidene, R4For alkyl, the integer that n is 1 or more；
The coefficient of dispersion (Mw/Mn) of the copolymer (A) is 10~20.
2. adhesive phase as described in claim 1, which is characterized in that polarizing film has the polycyclic alkene class as protective film Film.
3. a kind of polarizing film with adhesive phase has bonding of any of claims 1 or 2 in at least one side of polarizing film Oxidant layer.
4. a kind of laminated body is obtained by conforming to the polarizing film as claimed in claim 3 with adhesive phase on glass substrate It arrives.
5. laminated body as claimed in claim 4, which is characterized in that the glass substrate is the glass for image display device Substrate.
CN201580054572.0A 2014-10-15 2015-10-02 Adhesive phase, polarizing film and laminated body with adhesive phase Active CN106795415B (en)

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