CN102177450A - Polarizing plate - Google Patents

Polarizing plate Download PDF

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Publication number
CN102177450A
CN102177450A CN2009801405905A CN200980140590A CN102177450A CN 102177450 A CN102177450 A CN 102177450A CN 2009801405905 A CN2009801405905 A CN 2009801405905A CN 200980140590 A CN200980140590 A CN 200980140590A CN 102177450 A CN102177450 A CN 102177450A
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CN
China
Prior art keywords
polarization plates
film
diallyl
protective film
polarizer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2009801405905A
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Chinese (zh)
Inventor
野口隼也
望月典明
田中兴一
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Nippon Kayaku Co Ltd
Polatechno Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
Polatechno Co Ltd
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Publication of CN102177450A publication Critical patent/CN102177450A/en
Pending legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J139/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J139/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
    • C09J139/02—Homopolymers or copolymers of vinylamine
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Disclosed is a polarizing plate which is characterized in that a protective film is on at least one side of the plate, and that the protective film is bonded with a polarizing element using an adhesive which contains at least a polymerized product of a diallylamine compound. Also disclosed is the adhesive. The adhesive can bond a polarizing element with a protective film or the like which uses not only TAC but also an acrylic resin film, an olefin resin film (a cycloolefin film or a polyolefin film) and the like, without adversely affecting the polarizing element or a surface treatment layer. The polarizing plate obtained by using the adhesive has excellent wet heat resistance and water resistance.

Description

Polarization plates
Technical field
The present invention relates to use the polarization plates of the tackifier that contains the diallyl amine polymer.
Background technology
Usually polarizer is made by being adsorbed on the polyvinyl alcohol resin film back uniaxial tension as the iodine of dichromatism pigment or dichroic dye orientation.This polarizer is if directly use; bad mechanical strength then; therefore usually fit by the film of handling through saponification that tri acetyl cellulose constituted (below, be called TAC in this manual) etc. as its protective film, and be used for image display device such as liquid crystal indicator as polarization plates.Gluing common use polyvinyl alcohol (PVA) (PVA) the class tackifier of this polarizer and protective film.
In recent years, to the requirement height of each characteristic of polarization plates, just seeking the raising of polarization characteristic for example, the reduction of birefringence, the raising of total light transmittance, the control of moisture permeability, the raising of physical strength (pencil hardness, rub resistance), the raising of permanance etc. and further improving.In order to tackle these requirements, carrying out the improvement of polarizer and protective film.For example; for protective film, studying the olefine kind resin film that uses physical strength and permanance higher (polyolefin resin films such as cycloolefin based resin film such as norborene film and polypropylene), acrylic resin film, vinylester resin film etc. as protective film than normally used TAC.
But, when using the protective film beyond these TAC, can produce the problem of the tackiness variation between protective film and polarizer.To this, disclosed method is in patent documentation 1 and 2: when for example using norborene class film as protective film, carry out gluing with the light-cured type tackifier.But; use the method for light-cured type tackifier; illuminate condition according to light; might cause the deterioration of the surface-treated layer that polarizer or hard conating are such; therefore; just seek non-light-cured type, and also having the exploitation of the tackifier of excellent permanance and tackiness for the protective film beyond the above-mentioned TAC.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-111105
Patent documentation 2: TOHKEMY 2007-177169
Summary of the invention
The objective of the invention is to; even non-light-cured type and when using protective film except that cellulosic resins such as above-mentioned TAC for example polyolefin resin film such as acrylic resin film or cycloolefin resinoid and acrylic resin is as protective film; with the exploitation of the also good tackifier of the tackiness of polarizer, and exploitation gluing by this tackifier and that have the polarization plates of excellent anti-high humid (high humidity Hot patience).
The inventor etc. have carried out wholwe-hearted research for solving described problem; new discovery as a result; be used for the gluing of protective film and polarizer by containing the diallyl amine polymer as the tackifier of tackiness composition; not only TAC etc. comprises the protective film of cellulosic resin etc.; even under for the situation of protective film that comprises acrylic resin, cycloolefin resinoid or other olefine kind resin etc.; also can protective film and polarizer is gluing powerfully; and can improve various performances significantly, thereby finish the present invention as polarization plates.
That is, the present invention relates to:
(1) a kind of polarization plates is characterized in that, and is with the tackifier that contains diallylamine (diallylamine) base polymer that protective film and polarizer is gluing.
As above-mentioned (1) described polarization plates, it is characterized in that (2) protective film is any one in the film that comprises acrylic resin, the film that comprises olefine kind resin, the film that comprises cellulosic resin and the PET film.
As each described polarization plates in above-mentioned (1)～(2), it is characterized in that (3) the diallyl amine polymer is the homopolymer of diallyl aminated compounds or the multipolymer of diallyl aminated compounds.
As each described polarization plates in above-mentioned (1)～(3), it is characterized in that (4) the diallyl amine polymer is the diallyl amine polymer of epihalohydrins modification.
As each described polarization plates in above-mentioned (1)～(4), it is characterized in that (5) gluing surface of the polarizer side of protective film is through corona treatment or Cement Composite Treated by Plasma.
(6) as each described polarization plates in above-mentioned (1)～(5), it is characterized in that tackifier contains the amine silane coupling agent.
As each described polarization plates in above-mentioned (1)～(6), it is characterized in that (7) polarizer comprises the polyvinyl alcohol resin film that contains the dichromatism pigment.
(8) a kind of image display device is characterized in that, has each described polarization plates in above-mentioned (1)～(7).
(9) a kind of polarization plates use tackifier wherein, contains the diallyl amine polymer with respect to the tackifier total amount with the concentration of 5～25 weight %.
(10) as above-mentioned (9) described polarizing coating use tackifier, wherein, the diallyl amine polymer is the diallyl amine polymer of epihalohydrins modification.
(11) as above-mentioned (9) or (10) described polarizing coating use tackifier, wherein, further contain the amine silane coupling agent.
(12) a kind of manufacture method of polarization plates is characterized in that, with protective film and polarizer crimping, carries out drying then under the situation that has the aqueous adhesive that contains the diallyl amine polymer on the whole gluing surface of protective film and polarizer.
(13) a kind of resin molding sticks with glue agent, wherein, contains diallyl amine polymer and amine silane coupling agent.
(14) as each described polarization plates in above-mentioned (1)～(6), wherein, in the film of thickness 80 μ m, the moisture permeability of protective film (JIS K7129B) is 100～0.1g/m 2Below 24 hours.
The invention effect
According to polarization plates of the present invention; not only under the situation of the protective film that comprises cellulosic resins such as TAC; even under the situation of the protective film that comprises acrylic resin and olefine kind resin (cycloolefin resinoid or polyolefin resin), vinyl esters resin etc.; also can protective film and polarizer is gluing powerfully, and can improve the permanance of polarization plates, the particularly permanance under wet heat condition significantly.In addition, also can use the more excellent protective film of more excellent protective film such as, thermotolerance higher and rub resistance or optical characteristics etc., therefore can improve mechanical property and optical characteristics etc. than cellulosic resin hardness such as TAC.
Embodiment
Below, explain the present invention.
Polarization plates of the present invention can by use contain the diallyl amine polymer as the aqueous adhesive of tackiness composition with protective film and polarizer is gluing obtains.
The tackifier that uses in the polarization plates of the present invention is the composition that contains the diallyl amine polymer, is generally waterborne compositions.
Diallyl amine polymer of the present invention (polymkeric substance of diallyl amines) can be any one of the multipolymer of the homopolymer of diallylamine compounds (diallyl amines), diallyl aminated compounds or their modifier.The modifier of the polymkeric substance (homopolymer or multipolymer) of common diallyl aminated compounds, the diallyl amine polymer of preference such as halogenated epoxide modification, more preferably epihalohydrins modifier, preferred especially chloropropylene oxide modifier the diallyl amine polymer of epihalohydrins or chloropropylene oxide modification (below be also referred to as).
The homopolymer of diallyl aminated compounds can be enumerated the homopolymer of diallyl aminated compounds described later.
The multipolymer of diallyl aminated compounds preferably contains the multipolymer of aftermentioned diallyl aminated compounds as principal ingredient.The multipolymer that one of preferred multipolymer forms at least 2 kinds of copolymerization of above-mentioned diallyl aminated compounds.The multipolymer that contains other polymerism composition except that the diallyl aminated compounds for example can be enumerated: at least a and (methyl) acrylic acid (acrylic or methacrylic acid) of above-mentioned diallyl aminated compounds or its salt, (methyl) acrylamide (acrylamide or Methacrylamide) or its salt etc. have the multipolymer of the compound of (methyl) acryloyl group.The content of these other polymerism compositions (mol ratio) is 0～40 mole of % with respect to the multipolymer total amount in the multipolymer that contains these other polymerism compositions, more preferably 0～20 mole of %, further preferred 0～10 mole of %, all the other are diallyl aminated compounds composition.
The diallyl amine polymer of halogenated epoxide modification can be enumerated the homopolymer or the halo glycidyl compounds such as multipolymer and epihalohydrins that make the diallyl aminated compounds and react resulting modifier, more preferably the chloropropylene oxide modifier.
Diallyl aminated compounds in above-mentioned (diallyl amines) can be set forth in has 2 by CH on the nitrogen-atoms 2=CR-CH 2The amines of the group (following also only be called " (methyl) allyl ") that-(R is hydrogen atom or methyl) is represented.This amines can be any one of secondary amine or tertiary amine or their salt or quaternary ammonium salt.
Preferred diallyl aminated compounds can be enumerated by following formula (a)
(CH 2＝CR-CH 2) 2N(R 1) n (a)
(in the formula, R represents hydrogen atom or methyl, R 1The alkyl of expression C1～C4, n represents 0～2 integer, n is 2 o'clock, R 1Can be the same or different) represented compound or its salt (addition salts).
Above-mentioned have 2 (methyl) allylic secondary amine (n of above-mentioned formula (a) is) at 0 o'clock or its salt can be enumerated diallylamine or DMAA and inorganic or acylate thereof on nitrogen-atoms.This inorganic or acylate can be enumerated hydrochloride, sulfate, phosphate, acetate and the oxalates etc. of above-mentioned amine.
Above-mentioned have 2 (methyl) allylic tertiary amines (n of above-mentioned formula (a) is) at 1 o'clock or its salt can be enumerated diallyl (C1～C4 alkyl) amine or diallyl (C1～C4 alkylidene) diamines or its inorganic or acylates such as diallyl methyl amine, diallyl ethylamine and diallyl butylamine, preferred diallyl (C1～C4 alkyl) amine or its salt on nitrogen-atoms.More specifically, can enumerate hydrochloride, sulfate, phosphate, acetate or the oxalates etc. of diallyl methyl amine, diallyl ethylamine or diallyl butylamine.The salt of diallyl methyl amine or diallyl ethylamine more preferably.Preferred salt hydrochlorate in the salt.
In addition, above-mentioned have the salt that 2 (methyl) allylic quaternary ammonium salts (n of above-mentioned formula (a) is) can be enumerated diallyl two (C1～C4 alkyl) ammonium ions such as diallyl dimethyl ammonium salt and diallyl diethyl ammonium salt and inorganic or organic ion at 2 o'clock on nitrogen-atoms, particularly can enumerate diallyldimethylammonium chloride, diallyl dimethyl ammonium bromide, diallyl diethyl ammonium chloride, diallyl dibutyl ammonium chloride and diallyl Methylethyl ammonium chloride etc.
About the homopolymer of diallyl aminated compounds used in the present invention, respectively the independent polymerization of above-mentioned diallyl aminated compounds is got final product.In addition, multipolymer can obtain by 2 kinds of above-mentioned diallyl aminated compoundss of combination or with at least a of above-mentioned diallyl aminated compounds and other polymerizable monomer polymerization at least.In addition, their modifier can be by homopolymer or multipolymer that makes them and the compound that contains epoxy radicals, epihalohydrins for example, and more preferably halogenated compound (halo glycidyl compound) reaction that contains glycidyl such as chloropropylene oxide obtains.
Preferred diallyl amine polymer can be enumerated diallyl list or two (C1～C4 alkyl) amine polymer and epihalohydrins modifier thereof.This polymkeric substance can be any one of the multipolymer more than 2 kinds that comprises a kind of polymkeric substance of diallyl list or two (C1～C4 alkyl) amine or comprise diallyl list or two (C1～C4 alkyl) amine.The more preferably polymkeric substance of diallyl C1～C4 alkyl amine and epihalohydrins modifier thereof.
Diallyl amine polymer among the present invention is water miscible macromolecule, and this high molecular number-average molecular weight is about 100～about 1,000,000, preferred about 1,000～about 500,000, more preferably from about 10,000～about 100,000, further preferred about 30,000～about 100,000.
Tackifier of the present invention is considered from the balance of the quality retention time of adhesive power and tackifier, can contain diallyl amine polymer 1.0～40 weight % with respect to the tackifier total amount, preferred 2～30 weight %, more preferably 5～25 weight %, further preferred 8～20 weight %.All the other are adjuvant and aqueous solvent (for example be the mixed solvent of water or water and boiling points such as methyl alcohol or the ethanol water-soluble solvent lower than water separately, preferred is water separately) arbitrarily.Also can contain other tackiness composition beyond the diallyl amine polymer as adjuvant arbitrarily, but usually preferably only with the diallyl amine polymer as the tackiness composition.
Preferably adjuvant can be enumerated coupling agent arbitrarily, preferred amines one type of silane coupling agent.The addition of this coupling agent is 0～20 weight % with respect to the diallyl amine polymer in the tackifier, preferred 0～10 weight %, more preferably 0～6 weight %.
In order to give full play to the effect of coupling agent, with respect to the diallyl amine polymer in the tackifier, preferably add more than the 0.5 weight %, more preferably 1 weight % is above and be this coupling agent below the upper limit of above-mentioned scope.
Therefore, preferred tackifier, contain diallyl amine polymer 1.0～40 weight % with respect to the tackifier total amount, preferred 2～30 weight %, more preferably 5～25 weight %, further preferred 8～20 weight %, and contain coupling agent preferred amines one type of silane coupling agent 0.5～20 weight % with respect to the diallyl amine polymer, preferred 1～10 weight %, more preferably 1～6 weight %, all the other are water.
Below, when being recited as " % " in this manual, short of special declaration is promptly represented weight %.
Tackifier of the present invention is suitable for the gluing of polarization plates and protective film, but also preferably sticks with glue agent as other resin film stacked.Particularly, contain diallyl amine polymer and silane coupling agent, more preferably the aqueous adhesive of amine silane coupling agent preferably sticks with glue agent as resin film stacked, the diallyl amine polymer that contains the epihalohydrins modification sticks with glue agent as the tackifier of gluing composition is preferably as resin film.Be used for gluing resin film as long as then be not particularly limited for film of synthetic resin, can be for being selected between the film of the same race in the films such as polyolefin film, mylar, acryl resin film, vinylidenechloride film, silicone resin film or between film not of the same race any one.
About tackifier of the present invention, the tackiness composition be the diallyl amine polymer can with acid form salt, usually with formation salt such as hydrochloric acid, therefore, during use preferably to use after the alkaline aqueous solution activate.Preferred alkaline aqueous solution for example can be enumerated: the aqueous solution of alkali compounds such as alkali metal hydroxide such as NaOH, potassium hydroxide, calcium hydroxide, baryta hydrate and cesium hydroxide.The aqueous solution of usually preferred NaOH or potassium hydroxide etc.
Thereby the addition of this alkali compounds preferably can make addition can make the diallylamine base polymer form the amount of free state in the acid neutralization of diallyl amine polymer.Usually with respect to the total amount of the diallyl amine polymer in this tackifier, the amount of alkali compounds can add 1.0～30%, preferred 3～10% aqueous solution.
When tackifier of the present invention contains as the silane coupling agent of any composition, preferred amines one type of silane coupling agent, consider from the aspect that improves adhesive power, more preferred.That the addition of silane coupling agent is generally with respect to diallyl amine polymer of the present invention is about 0～and about 20%, preferred about 0.1～about 10%, more preferably from about 0.5～about 6%.According to occasion, above-mentioned further preferred range can be 0.5～3% or 1～3%.
The concrete example of amine silane coupling agent for example can be enumerated: N-β-(N-vinyl benzyl aminoethyl)-γ-An Bingjisanjiayangjiguiwan hydrochloride (eastern beautiful DOW CORNING Co., Ltd. system, trade name: SZ-6032), γ-An Bingjisanjiayangjiguiwan (eastern beautiful DOW CORNING Co., Ltd. system, trade name: SZ-6083), γ-diallyl aminopropyl trimethoxysilane (eastern beautiful DOW CORNING Co., Ltd. system, trade name: AX43-065), N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane (Shin-Etsu Chemial Co., Ltd's system, trade name: KBM-602), N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan (Shin-Etsu Chemial Co., Ltd's system, trade name: KBM-603), N-β-(aminoethyl)-gamma-aminopropyl-triethoxy-silane (Shin-Etsu Chemial Co., Ltd's system, trade name: KBE-603), γ-An Bingjisanjiayangjiguiwan (Shin-Etsu Chemial Co., Ltd's system, trade name: KBM-903), gamma-aminopropyl-triethoxy-silane (Shin-Etsu Chemial Co., Ltd's system, trade name: KBE-903), N-phenyl-γ-An Bingjisanjiayangjiguiwan (Shin-Etsu Chemial Co., Ltd's system, trade name: KBM-573), γ-(2-aminoethyl) aminopropyl trimethoxysilane (eastern beautiful DOW CORNING Co., Ltd. system, trade name: SH6020), and γ-(2-aminoethyl) aminopropyl methyl dimethoxysilane (eastern beautiful DOW CORNING Co., Ltd. system, trade name: SH6023) wait aminopropyl three (C1～C3 alkoxy) silane compound or aminopropyl two (C1～C3 alkoxy) C1～C3 alkyl silane cpd.The amino of this silane compound can have 1～2 substituting group that is selected from the group that is made of phenyl, amino C1～C3 alkyl, C2～C3 unsaturated aliphatic group (preferred vinyl or allyl) and benzyl.
In the scope of not damaging effect of the present invention (for example with respect to solid constituent total amount and coupling agent add up to 0～20%), also can contain the adjuvant beyond the silane coupling agent, but can not contain them usually in the tackifier of the invention described above.
In order to improve tackiness, the protective film in the polarization plates of the present invention is preferably implemented various surface treatments.Particularly protective film is that film surfaces such as acrylic resin film, olefine kind resin film are hydrophobicity and contact angle when being the above film of 30 degree etc., preferred enforcement with so that adhesive surface becomes hydrophilic surface treatment.
This surface treatment for example can be enumerated: solvent surface treatment, mechanicalness surface treatment and the processing of ammeter face etc., preferred ammeter face is handled.The ammeter face is handled and for example can be enumerated: corona treatment, Cement Composite Treated by Plasma, atmosphere pressure discharging processing and ultraviolet and ozone processing etc.The degree of handling is according to the material of employed protective film and surface state etc. and different, but preferably becomes the protective film that about 0 degree mode above and below about 20 degree is handled with the contact angle of the water of the protective film gluing surface after handling.Preferred corona treatment or Cement Composite Treated by Plasma during above-mentioned ammeter face is handled, preferred especially corona treatment.
In addition; this protective film uses film of synthetic resin usually, for example can enumerate: acrylic resin film, olefine kind resin film (the cyclic olefin resins film is or/and polyolefin resin film), cellulosic resin film and PET film (polyethylene terephthalate thin film) etc.These protective films can be implemented antireflection and handle, prevent dazzling surface treatments such as optical processing and/or hard conating processing on the face of an opposite side with gluing surface as required.
The protective film that the preferred moisture permeability of protective film in the polarization plates of the present invention is low, preferably the moisture permeability (JIS K7129B) (40 ℃, 90%RH) in the film of thickness 80 μ m is 100g/m 2Protective film below 24 hours, lower limit is not particularly limited.For example can enumerate about 100g/m in the practical application 224 hours～about 0.1g/m 224 hours, 50g/m more preferably from about 224 hours～about 0.1g/m 224 hours, further preferred about 35g/m 224 hours～about 0.1g/m 224 hours protective film.Consider preferred acrylic resin film or olefine kind resin film from moisture permeability and/or permanance.
Aforesaid propylene acid resin film can be enumerated the homopolymer that comprises (methyl) acrylic monomers ((methyl) acrylic acid or (methyl) acrylate) or the film etc. of the multipolymer of the multipolymer of (methyl) acrylic monomers or at least a kind of (methyl) acrylic monomers and other polymerizable monomer more than 2 kinds.
(methyl) acrylic monomers for example can be enumerated: alkyl methacrylate such as acrylate such as methacrylate such as cyclohexyl methacrylate, methacrylic acid tert-butyl group cyclohexyl, methyl methacrylate and methyl acrylate, ethyl acrylate, butyl acrylate, isopropyl acrylate, 2-EHA and alkyl-acrylates etc.
In addition, can can enumerate with other polymerizable monomer of above-mentioned (methyl) acrylic monomers copolymerization: no substituted phenylethylene, o-methyl styrene, p-methylstyrene, 2,4-dimethyl styrene, ethyl styrene, aromatic ethenyl compound classes such as alpha-alkyl substituted phenylethylene such as alkyl-substituted styrenes such as t-butyl styrene and α-Jia Jibenyixi, Alpha-Methyl-p-methylstyrenes; Vinyl cyanide such as vinyl cyanide and methacrylonitrile class; Maleimides such as N-phenylmaleimide and N-cyclohexyl maleimide; Unsaturated carboxylic acid anhydrides classes such as maleic anhydride; Unsaturated acids such as maleic acid; And siloxane (シ ロ キ サ Application) class monomer etc.As required, these monomers also can be used in combination more than 2 kinds.
Above-mentioned olefine kind resin film can be enumerated cyclic olefin resins films such as polyolefin resin films such as ethylene-propylene copolymer and norbornene resin etc.Norbornene resin can be enumerated and for example make norborene, dicyclo [2.2.1] heptene-2, C1～C4 alkyl or C1～C4 alkoxy-5-dicyclo [2.2.1] heptene-2, dicyclo [2.2.1] heptene-2-5-carboxylic acid or dicyclo [2.2.1] heptene-2-5, the resin that norbornene monomer ring-opening polymerizations such as (for example C1～C4 Arrcostabs) of the ester of 6-dicarboxylic acid or ring opening copolymer form, makes resin that the norbornene monomer addition polymerization forms and norbornene monomer and ethene or alpha-olefin (resin of forming of olefinic monomer addition copolymerization such as (C3～C8) alpha-olefin) etc. for example.
Above-mentioned cellulosic resin film can be enumerated cellulose acylate films such as diacetyl cellulose, tri acetyl cellulose and cellulose-acetate propionate (common cellulose (C1～C4) acylate film) etc.
In addition, the PET film can use any one of commercially available PET film.
The employed polarizer of polarization plates of the present invention (polaroid) if having then is not particularly limited the function from the light polarization of light source, can use the light that absorbs specific direction and makes the light of the absorption-type polarizer of its polarization and reflection specific direction and make any one of reflective polarizer element of its polarization.The absorption-type polarizer for example can be enumerated: the hydrophilic macromolecule films such as polyvinyl alcohol film that will contain dichromatism pigments such as dyestuff or multivalence iodide ion carry out the resulting polarizer of uniaxial tension; Forming the resulting polarizer of polyene structure with dewatering by acid before and after the polyvinyl alcohol film uniaxial tension; And the solution that on the oriented film through being oriented to the certain orientation processing, is coated with the dichromatism pigment that manifests the lyotropic liquid crystal state, remove the resulting polarizer etc. that desolvates then.On the other hand, reflective polarizer element for example can be enumerated: comprise the different a plurality of duplexers of birefringence polarizer, have cholesterol liquid crystal and polarizer that 1/4 wavelength plate combines and the polarizer that on substrate, is provided with small wiregrating etc. of selecting the echo area.In order more effectively to obtain effect of the present invention, preferred use hydrophilic macromolecule films such as the polyvinyl alcohol film polarization characteristic excellence, that will contain dichromatism pigments such as dyestuff or multivalence iodide ion to carry out the resulting polarizer of uniaxial tension, perhaps forming the resulting polarizer of polyene structure dewatering by acid before and after the polyvinyl alcohol film uniaxial tension as polarizer.
Above-mentioned polarizer can be made by existing method.For example when comprising the polarizer of polyvinyl alcohol film of dichromatism pigments such as containing dyestuff and multivalence iodide ion, at first, with the polyvinyl alcohol film with swellings such as warm water after, impregnated in the staining trough that is dissolved with the dichromatism pigment, with this film dyeing.Then, the film that has dyeed is stretched towards the single shaft direction in the groove that contains the such crosslinking chemical of boric acid or borax, drying can obtain this polarizer thus.
The employed pigment that dyes can be enumerated: the IKI aqueous solution, (go into Jiang Zhenghao edits " functional pigmented application " (Machine can property pigment ying with), CMC publishes) azo compound of record in the 98th～100 page, C.I. direct yellow 12, C.I. direct yellow 28, C.I. Direct Yellow 44, C.I. direct orange 26, C.I. direct orange 39, C.I. direct orange 107, C.I. directly red 2, C.I. directly red 31, C.I. directly red 79, C.I. directly red 81, C.I. directly red 247, C.I. direct green 80, C.I. direct green 59, and TOHKEMY 2001-33627, TOHKEMY 2002-296417, TOHKEMY 2003-215338, WO2004/092282, TOHKEMY 2001-0564112, TOHKEMY 2001-027708, Japanese kokai publication hei 11-218611, the organic dyestuff of putting down in writing in Japanese kokai publication hei 11-218610 and the Japanese kokai publication sho 60-156759 communique etc.These dichromatism pigments except that free acid, can also be enumerated the salt of alkali metal salt (for example Na salt, K salt and Li salt etc.), ammonium salt, amine or complex salt (for example Cu complex compound, Ni complex compound and Co complex compound etc.) etc.Dichromatism that the performance of polarizer can have by the dichromatism pigment or the stretching ratio when stretching etc. are adjusted.
Polarization plates of the present invention by at the single face at least of above-mentioned polarizer, be generally the described tackifier of two-sided use and come stacked described protective film to carry out drying then to obtain.Dry condition is according to the moisture permeability of the concentration of employed tackifier or protective film and difference can be carried out about 10 minutes～about 150 minutes with 25～100 ℃.Polarization plates of the present invention is as long as single face is a protective film at least, and another side can be for glass substrate etc.Polarization plates of the present invention is generally the two-sided polarization plates that forms with the gluing protective film of described tackifier at polarizer.
In order to fit, usually, on the single face at least of the polarization plates of the present invention that obtains by the way, be formed with adhesive layer with other film or liquid crystal cells (liquid crystal セ Le).If the employed bonding agent of bonding coat transparent and do not have the optics anisotropy, then can use any tackifier with being not particularly limited, but preferably use acrylic tackifier.
Below the manufacture method of polarization plates of the present invention is described.
In the invention of the manufacture method of this polarization plates, also same with the invention of above-mentioned polarization plates, it is characterized in that, use and contain the aqueous adhesive of diallyl amine polymer as gluing composition.
That is, the manufacture method of polarization plates of the present invention is characterized in that, exists at the whole gluing surface of protective film and polarizer under the situation of the aqueous adhesive that contains the diallyl amine polymer protective film and polarizer crimping, carries out drying then.
Make and exist the method for the aqueous adhesive that contains the diallyl amine polymer to be not particularly limited on the two the whole gluing surface of protective film and polarizer.For example; can on the whole gluing surface of any one or both of protective film and polarizer, with methods such as coatings tackifier be existed, in addition; also can when crimping, between two films, supply with tackifier, thereby when crimping, make tackifier be present in the whole gluing surface of film.Like this; be present at the aqueous adhesive that contains the diallyl amine polymer under the state of whole gluing surface of protective film and polarizer, use roller etc. and, carry out drying then usually at normal temperatures with two film crimping; thus, can make polarization plates of the present invention.Crimping can be any one method, but the preferred usually crimping between roller.The amount of the tackifier on the film surface is according to the kind of suitable film etc. and different, but in the weight of the diallyl amine polymer in the tackifier, is roughly about 0.04～about 0.4g/m 2, preferably about 0.06g/m 2～about 0.4g/m 2
Drying was preferably carried out about 10 minutes～about 150 minutes under about 25～about 100 ℃ as previously mentioned.
The employed protective film of this manufacture method comprises described resin film, and as long as be the protective film of polarization plates, then can use any one.
The employed aqueous adhesive that contains the diallyl amine polymer of this manufacture method, the aqueous adhesive illustrated with the explanation of the polarization plates of the invention described above is identical.Therefore, preferred aqueous adhesive further contains silane coupling agent, preferred amines one type of silane coupling agent except that the diallyl amine polymer.Preferred proportion of composing etc. are also identical with the proportion of composing that illustrates in the item of polarization plates etc., therefore, with reference to these explanations, omit detailed explanation at this.
In addition, the employed polarizer of this manufacture method is identical with the polarizer that illustrates in the explanation of the polarization plates of the invention described above.Therefore with reference to these explanations, in this detailed.
In the polarization plates preferred of the present invention that obtains in the above described manner, at least a side of polarizer have polarizer, driving fit in the adhesive layer that contains the diallyl amine polymer on the surface of this polarizer and driving fit in three layers of formation of the protective film of this adhesive layer.The opposite side of polarizer can be same as described above, in addition, also can constitute for other.More preferably the both sides of polarizer are the polarization plates of above-mentioned formation.
By polarization plates of the present invention being disposed in the light path of image display device, for example side of the liquid crystal cells at least of liquid crystal indicator etc. can obtain for example liquid crystal indicator of image display device of the present invention.Kind according to employed liquid crystal cells in the liquid crystal indicator has various patterns, but can use polarization plates of the present invention under any one situation.Can in the liquid crystal indicator of various patterns such as for example VA (vertical orientation) type, IPS (plane conversion) type, OCB (optical compensation curved) type, TN (twisted nematic) type, STN (STN Super TN) type, use polarization plates of the present invention.
In addition, between polarization plates of the present invention and liquid crystal cells, also can insert in order to improve the phase-contrast film of viewing angle characteristic or contrast.
Polarization plates of the present invention is suitable for liquid crystal projection apparatus.At this moment, can be used as the colored polarization plates of liquid crystal cells of red, green and blue light source separately being carried out switch usually.
Embodiment
Below, illustrate in greater detail the present invention by embodiment, but the present invention is not limited by these embodiment.
Embodiment 1
The preparation of＜tackifier 〉
Use contains the aqueous solution (Senka Co., Ltd. system, trade name: ユ ニ セ Application ス KCA101L, solid component concentration 20%) of the hydrochloride of chloropropylene oxide modified methyl diallyl amine polymer as tackifier of the present invention.During use, adjust solid component concentration to 11% thereby dilute this aqueous solution with water.In resulting solution, with respect to N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan (Shin-Etsu Chemial Co., Ltd's system, the trade name: KBM-603), obtain containing the tackifier of the present invention of coupling agent of this polymkeric substance adding 3%.Further, add 5% NaOH with respect to this polymkeric substance with aqueous solution therein, fully stir, obtain being used for the tackifier aqueous solution of gluing protective film.
The making of＜polarization plates 〉
Use corona unit (CORONA GENERATOR) (Kasuga Electric K. K.'s system, AGF-B10); to carry out 5 times condition in output power 0.25kW, speed 5m/ minute; acrylic resin film (Asahi Chemical Corp's system, HV film) to thick 80 μ m carries out corona treatment, obtains the protective film of gluing surface through corona treatment thus.Use will be adsorbed with the polarizer (Polatechno of Co., Ltd. system that the polyvinyl alcohol resin film stretching of dichroic dye forms; the SHC polarizer) as polarizer; 2 protective films that in above-mentioned, obtain on the face of corona treatment; be coated with the adhesive solvent that obtains in described; seize polarizer on both sides by the arms with this coated face, thereby at the gluing protective film in the two sides of polarizer.Then, heated 30 minutes and drying down, obtain polarization plates of the present invention thus at 70 ℃.
Embodiment 2
Remove to use the norbornene resin film (Japanese Zeon Co., Ltd. system, trade name Zeonor) of thick 40 μ m, to carry out 1 identical operations, obtain polarization plates of the present invention thus with embodiment as beyond the protective film.
Embodiment 3
Use is through tri acetyl cellulose film (the description Off イ of Fuji Le system Co., Ltd. system of the thickness 80 μ m of alkali treatment; trade name: TD-80U) (TAC film) is as protective film; protective film is pasted in both sides at polarizer; following dry 10 minutes at 70 ℃ then; in addition; carry out 1 identical operations, obtain polarization plates of the present invention thus with embodiment.
Comparative example 1
(The Nippon Synthetic Chemical Industry Co., Ltd's system, trade name: Gohsenol NH-26) 4% aqueous solution is carried out 1 identical operations with embodiment as the tackifier, is relatively used polarization plates thus except that using the PVA paste.
Tackiness is estimated
For the polarization plates of making in embodiment 1～3, the comparative example 1, the 40mm * 40mm sheet of each polarization plates sample was placed 100 hours under 85 ℃ of wet heat conditions, 85%RH, with having or not that visual inspection is peeled off.Its observations is shown in the table 1.
[table 1]
Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
Have or not and peel off Do not have Do not have Do not have Have
Comparative example 2
Use is by stick with paste (The Nippon Synthetic Chemical Industry Co., Ltd's system, trade name: Gohsefimer Z-200) add the tackifier that constituted forming of 0.8% the glyoxal as crosslinking chemical (The Nippon Synthetic Chemical Industry Co., Ltd's system) in 8% aqueous solution as tackifier at PVA, in addition, carry out 2 identical operations, relatively used polarization plates thus with embodiment.
Comparative example 3
Use is by stick with paste (The Nippon Synthetic Chemical Industry Co., Ltd's system, trade name: Gohsefimer Z-200) add the tackifier that constituted forming of 0.8% the glyoxal as crosslinking chemical (The Nippon Synthetic Chemical Industry Co., Ltd's system) in 8% aqueous solution as tackifier at PVA, in addition, carry out 3 identical operations, relatively used polarization plates thus with embodiment.
Water tolerance is estimated
For the polarization plates of making in embodiment 2～3, the comparative example 2～3, submerge the 40mm * 40mm sheet of each polarization plates sample in 60 ℃ the warm water and placed 400 hours, with having or not that naked eyes are confirmed to peel off.Its observations is shown in the table 2.
[table 2]
Embodiment 2 Embodiment 3 Comparative example 2 Comparative example 3
Have or not and peel off Do not have Do not have Have Have
From the comparison of embodiment 1～3 and comparative example 1 as can be known, under polarization plates of the present invention any one situation in acrylic resin film, norbornene resin film and TAC film, all has excellent anti-high humid, relatively, the polarization plates of comparative example 1 does not have anti-high humid fully.
In addition, from comparative example 2 and 3 and the comparison of embodiments of the invention 2 and 3 can be clear and definite, when using tackifier of the present invention, under the situation of any one in norbornene resin film and TAC film, all has sufficient water tolerance, relatively, when using existing P VA to stick with paste, can not obtain sufficient water tolerance.
Industrial applicability
As mentioned above, even the acrylic resin film that utilizes the polarization plates of adhesive of the present invention to use to be considered to the adhesivity difference or norbornene resin film etc. also have excellent anti-high humid and resistance to water as protective film always. Therefore; can useful life longevity geometric ratio TAC film more excellent resin film is as protective film; thereby can improve or improve performance or the durability of polarization plates, the durability such as mechanical strengths such as birefringence or poisture-penetrability, rub resistance, anti-high humid or resistance to water etc.

Claims (14)

1. a polarization plates is characterized in that, and is with the tackifier that contains the diallyl amine polymer that protective film and polarizer is gluing.
2. polarization plates as claimed in claim 1 is characterized in that, protective film is any one in the film that comprises acrylic resin, the film that comprises olefine kind resin, the film that comprises cellulosic resin and the PET film.
3. polarization plates as claimed in claim 1 is characterized in that, the diallyl amine polymer is the homopolymer of diallyl aminated compounds or the multipolymer of diallyl aminated compounds.
4. polarization plates as claimed in claim 1 is characterized in that, the diallyl amine polymer is the diallyl amine polymer of epihalohydrins modification.
5. polarization plates as claimed in claim 1 is characterized in that, the gluing surface of the polarizer side of protective film is through corona treatment or Cement Composite Treated by Plasma.
6. polarization plates as claimed in claim 1 is characterized in that tackifier contains the amine silane coupling agent.
7. polarization plates as claimed in claim 1, wherein, polarizer comprises the polyvinyl alcohol resin film that contains the dichromatism pigment.
8. an image display device is characterized in that, has each described polarization plates in the claim 1～7.
9. polarization plates use tackifier wherein, contains the diallyl amine polymer with respect to the tackifier total amount with the concentration of 5～25 weight %.
10. polarization plates use tackifier as claimed in claim 9, wherein, the diallyl amine polymer is the diallyl amine polymer of epihalohydrins modification.
11., wherein, further contain the amine silane coupling agent as claim 9 or 10 described polarization plates use tackifier.
12. the manufacture method of a polarization plates; it is characterized in that; under the situation that has the aqueous adhesive that contains diallyl amine polymer and silane coupling agent on the whole gluing surface of protective film and polarizer,, carry out drying then with protective film and polarizer crimping.
13. a resin molding sticks with glue agent, wherein, contains diallyl amine polymer and amine silane coupling agent.
14. polarization plates as claimed in claim 1, wherein, in the film of thick 80 μ m, the moisture permeability of protective film (JIS K7129B) is 100～0.1g/m 2Below 24 hours.
CN2009801405905A 2008-10-14 2009-10-09 Polarizing plate Pending CN102177450A (en)

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