CN110291167A - Polarizing coating adhesive composition, polarizing coating adhesive phase, the polarizing coating with adhesive phase, liquid crystal display panel and liquid crystal display device - Google Patents

Polarizing coating adhesive composition, polarizing coating adhesive phase, the polarizing coating with adhesive phase, liquid crystal display panel and liquid crystal display device Download PDF

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Publication number
CN110291167A
CN110291167A CN201880011246.5A CN201880011246A CN110291167A CN 110291167 A CN110291167 A CN 110291167A CN 201880011246 A CN201880011246 A CN 201880011246A CN 110291167 A CN110291167 A CN 110291167A
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polarizing coating
methyl
weight
adhesive phase
mentioned
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CN110291167B (en
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吉川贵博
中村恒三
森本有
加藤惠
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Nitto Denko Corp
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Nitto Denko Corp
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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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)
  • Adhesive Tapes (AREA)
  • Liquid Crystal (AREA)
  • Optical Filters (AREA)

Abstract

The present invention provides a kind of polarizing coating adhesive composition, contains (methyl) acrylic polymer, pigment, free-radical generating agent and antioxidant.The ageing stability of polarizing coating adhesive composition of the invention is good, is able to maintain by the wide colour gamut of pigment bring.

Description

Polarizing coating adhesive composition, polarizing coating adhesive phase, with the inclined of adhesive phase Vibrating diaphragm, liquid crystal display panel and liquid crystal display device
Technical field
The present invention relates to polarizing coating adhesive composition and the adhesive phases formed by the adhesive composition.In addition, The present invention relates to the optical films with adhesive phase that at least one side in polarizing coating is formed with above-mentioned adhesive phase.In addition, this hair The bright liquid crystal display panel for being related to having used the above-mentioned optical film with adhesive phase, the liquid crystal display device with above-mentioned liquid crystal display panel.
Background technique
For image display device etc., from the point of view of its image forming mode, polarization is configured on the two sides of liquid crystal cells Element be it is essential, be usually pasted with polarizing coating.When the polarizing coating is pasted on liquid crystal cells, usually using bonding Agent.In addition, in order to reduce the loss of light, for polarizing coating is bonding with liquid crystal cells, usually each materials'use bonding Agent is closely sealed to carry out.In this case, due to having many advantages, such as to be not necessarily to carry out the drying process for making polarizing coating cementation, because Adhesive usually using being arranged at obtained from the single side of polarizing coating band adhesive phase by this in the form of adhesive phase in advance Polarizing coating.
It is coloured in addition, proposing by adding dyestuff or pigment in above-mentioned adhesive phase, to be assigned to polarizing coating It gives arbitrary tone and obtains the liquid crystal display (patent document 1) of high contrast.In recent years, image display device is required bright Brightness, vividness (that is, wide colour gamut), organic EL display device (OLED) is concerned, and liquid crystal display device is also required Wide colour gamut.For example, proposing as the method for making the wide colour gamut of liquid crystal display device by containing in specific wavelength (560 ~610nm) range show that polarizing film is laminated on above-mentioned liquid crystal cells by the adhesive phase of pigment for absorbing maximum wavelength One or both sides (patent document 2,3).
Existing technical literature
Patent document
Patent document 1: real No. 3052812 specifications of passing the imperial examinations of Japan
Patent document 2: Japanese Unexamined Patent Publication 2011-039093 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2014-092611 bulletin
Summary of the invention
Problem to be solved by the invention
Usually as the adhesive composition for forming polarizing coating adhesive phase, use with (methyl) acrylic polymer Close the acrylic pressure-sensitive adhesive compositions that object is basic polymer.In above-mentioned acrylic pressure-sensitive adhesive compositions, in addition to (first Base) other than acrylic polymer, also use free-radical generating agent (such as peroxide) as crosslinking agent sometimes, formed through from Adhesive phase after being crosslinked by base.In addition, viscous preparing above-mentioned acrylic compounds by the heat or radiation-curing of monomer component In the case where (methyl) acrylic polymer in mixture composite, contain free radical polymerization in above-mentioned adhesive composition Initiator.
It is well known, however, that when further containing pigment in the adhesive composition containing above-mentioned free-radical generating agent, by certainly It is generated free radicals by base producing agent, which can be such that pigment decomposes.As a result, being formed by above-mentioned adhesive composition viscous Even if mixture layer has initially been coloured by pigment, also can gradually fade.In this way, pigment within the adhesive layer through when In the case where deterioration, it is difficult to keep by the wide colour gamut of pigment bring.
The purpose of the present invention is to provide a kind of containing (methyl) acrylic polymer, pigment and free-radical generating agent The ageing stability of polarizing coating adhesive composition, the composition is good, is able to maintain by the wide colour gamut of pigment bring.
In addition, being mentioned the purpose of the present invention is to provide the adhesive phase formed by above-mentioned polarizing coating adhesive composition For the optical film with adhesive phase with the adhesive phase, and then provide the liquid crystal for having used the optical film with adhesive phase Panel, and then the liquid crystal image display device for having used the liquid crystal display panel is provided.
Solution to the problem
The inventors of the present invention have made intensive studies to solve the above-mentioned problems, as a result, it has been found that the bonding of following polarizing coatings Agent composition, so as to complete the present invention.
That is, containing (methyl) acrylic polymer, color the present invention relates to a kind of polarizing coating adhesive composition Element, antioxidant and free-radical generating agent.
In above-mentioned polarizing coating adhesive composition, above-mentioned pigment be can be used in 470~510nm of wave-length coverage and wave At least any wave-length coverage in long 570~610nm of range has the pigment of maximum absorption wavelength.
In above-mentioned polarizing coating adhesive composition, tetraazatetradecane porphyrin class pigment is can be used in above-mentioned pigment.
In above-mentioned polarizing coating adhesive composition, relative to above-mentioned 100 parts by weight of (methyl) acrylic polymer, Preferably comprise above-mentioned 0.01~5 parts by weight of pigment.
In above-mentioned polarizing coating adhesive composition, peroxide is can be used in above-mentioned free-radical generating agent.
In above-mentioned polarizing coating adhesive composition, relative to above-mentioned 100 parts by weight of (methyl) acrylic polymer, Preferably comprise above-mentioned 0.01~2 parts by weight of free-radical generating agent.
In above-mentioned polarizing coating adhesive composition, phenolic antioxidant is can be used in above-mentioned antioxidant.
In above-mentioned polarizing coating adhesive composition, relative to above-mentioned 100 parts by weight of (methyl) acrylic polymer, Preferably comprise above-mentioned 0.1~5 parts by weight of antioxidant.
In above-mentioned polarizing coating adhesive composition, the dosage (A) of preferably above-mentioned free-radical generating agent and above-mentioned antioxygen The weight rate (A/B) of the dosage (B) of agent is 4 or less.
Above-mentioned polarizing coating adhesive composition can further contain crosslinking agent.
Moreover, it relates to which a kind of polarizing coating adhesive phase, is formed by above-mentioned polarizing coating with adhesive composition.
The gel fraction of above-mentioned polarizing coating adhesive phase is preferably 50~98 weight %.
Above-mentioned polarizing coating adhesive phase is with a thickness of 20 μm, before saving 500 hours preferably at 85 DEG C Transmissivity (T1) and save after transmissivity (T2) difference (T1-T2) absolute value be 50% or less.
Polarizing coating adhesive phase described in any one of 1~13 according to claim 1, wherein above-mentioned polarizing coating is used viscous Mixture layer is with a thickness of 20 μm, before the transmissivity (T2) and preservation after saving 500 hours preferably at 85 DEG C Transmissivity (T1) ratio (T2/T1) be 2 or less.
Moreover, it relates to which a kind of polarizing coating with adhesive phase, is formed with above-mentioned in at least side of polarizing coating Polarizing coating adhesive phase.
Moreover, it relates to a kind of liquid crystal display panel, wherein glue above-mentioned band in at least any surface of above-mentioned liquid crystal cells The polarizing coating of mixture layer is fit together with liquid crystal cells by the adhesive phase of the polarizing coating with adhesive phase.
In addition, the present invention relates to a kind of liquid crystal display device, with above-mentioned liquid crystal display panel.
The effect of invention
Polarizing coating of the invention uses adhesive composition in addition to (methyl) acrylic polymer as basic polymer In addition, also contain pigment.Pass through the light using a part of wavelength of pigment absorption, the color of adjustable liquid crystal display device entirety It adjusts, vividness can be improved by wide colour gamutization.Especially in 570~610nm of 470~510nm of wave-length coverage and wave-length coverage In at least any wave-length coverage have maximum absorption wavelength pigment can absorb RGB other than wave-length coverage (wave-length coverage 470 570~610nm of~510nm and wave-length coverage) color performance institute it is unwanted shine, to inhibit above-mentioned unwanted hair Light is effective to wide colour gamut.
In addition, polarizing coating adhesive composition of the invention contains the free-radical generating agents such as peroxide.The free radical Producing agent for example can be used as the crosslinking agent for (methyl) acrylic polymer and play a role, and can will be used by polarizing coating The gel fraction control for the adhesive phase that adhesive composition is formed is desired range, can form the adhesive of good appearance Layer.
As described above, polarizing coating of the invention is with existing simultaneously pigment and free-radical generating agent in adhesive composition, because This, exist by free-radical generating agent generate free radical caused by pigment fade hidden danger.But it is of the invention inclined by making Vibrating diaphragm adhesive composition contains antioxidant, can use antioxidant and captures free radical, it is suppressed that the colour fading (decomposition) of pigment, Can through when stably keep wide colour gamut.
Specific embodiment
Polarizing coating adhesive composition of the invention contain (methyl) acrylic polymer, pigment, antioxidant and from By base producing agent.Hereinafter, being illustrated to these ingredients.
<(methyl) acrylic polymer>
Pressure-sensitive adhesive for optical films composition of the invention contains (methyl) acrylic polymer as basic polymer As principal component.Principal component refers to the ingredient that content ratio is most in all solids ingredient that adhesive composition is included, The ingredient more than 50 weight % is accounted for for example, referring in all solids ingredient that adhesive composition is included, more refers to account for and is more than The ingredient of 70 weight %.
As (methyl) alkyl acrylate for the main framing for constituting above-mentioned (methyl) acrylic polymer, can example go out (methyl) alkyl acrylate that the atomic number of alkyl carbon of straight-chain or branched is 1~18.They can be used alone or group It closes and uses.The average carbon atom number of these alkyl is preferably 3~9.
As (methyl) alkyl acrylate for the main framing for constituting above-mentioned (methyl) acrylic polymer, can example go out (methyl) alkyl acrylate that straight-chain or branched and the carbon atom number of alkyl are 1~18.These alkyl can individually make With or be applied in combination.The average carbon atom number of these alkyl is preferably 3~9.
In addition, considering from viewpoints such as adhesion characteristic, durability, the adjustment of phase difference, the adjustment of refractive index, can be used (methyl) alkyl acrylate containing aromatic rings as (methyl) phenoxyethyl acrylate, (methyl) benzyl acrylate.
In order to improve cementability, heat resistance, a kind can be imported by being copolymerized in above-mentioned (methyl) acrylic polymer Above comonomer, the comonomer has (methyl) acryloyl group or vinyl etc., and there are the polymerisms of unsaturated double-bond Functional group.It as the specific example of such comonomer, can enumerate for example: (methyl) acrylic acid 2- hydroxy methacrylate, (first Base) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) propylene Sour 8- hydroxyl monooctyl ester, (methyl) acrylic acid 10- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid 12- hydroxylauric ester, acrylic acid (4- hydroxyl first Butylcyclohexyl) the hydroxyls monomer such as methyl esters；(methyl) acrylic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, The carboxyl group-containing monomers such as itaconic acid, maleic acid, fumaric acid, crotonic acid；The monomers containing anhydride group such as maleic anhydride, itaconic anhydride；Propylene The caprolactones addition product of acid；Styrene sulfonic acid, allyl sulphonic acid, 2- (methyl) acrylamide-2-methylpro panesulfonic acid, (methyl) The monomers containing sulfonic group such as acryamidopropanesulfonic acid, (methyl) acrylic acid sulfonic acid propyl ester, (methyl) propane sulfonic acid；2- Phosphorous acid-based monomers such as hydroxyethyl acryloyl phosphate etc..
In addition, the example of the monomer as modified purpose, can also enumerate: (methyl) acrylamide, N, N- dimethyl (first Base) acrylamide, N- butyl (methyl) acrylamide, N- methylol (methyl) acrylamide, N- hydroxymethyl-propane (methyl) third Acrylamide etc. (N- substitution) amides monomer；(methyl) acrylate, (methyl) acrylic acid N, N- dimethylaminoethyl (methyl) the acrylic acid alkylaminoalkyl esters monomers such as ester, (methyl) tbutylaminoethylacrylate；(methyl) acrylic acid (methyl) alkoxyalkyl acrylate class monomer such as methoxy acrylate, (methyl) ethoxyethyl acrylate；N- (methyl) third Alkene acyl-oxygen methylene succinimide, N- (methyl) acryloyl -6- oxygroup hexa-methylene succinimide, N- (methyl) propylene The succinimides class monomers such as eight methylene succinimide of acyl -8- oxygroup, N- acryloyl morpholine；N- cyclohexyl maleimide The maleimides monomers such as amine, N- isopropylmaleimide, N- lauryl maleimide, N-phenylmaleimide； N- methyl clothing health acid imide, N- ethyl clothing health acid imide, N- butyl clothing health acid imide, N- octyl clothing health acid imide, N-2- ethyl Clothing health acid imide monomers such as hexyl clothing health acid imide, N- cyclohexyl clothing health acid imide, N- lauryl clothing health acid imide etc..
In addition, vinyl acetate, vinyl propionate, n-vinyl pyrrolidone, first can also be used as modified monomer Base vinyl pyrrolidone, vinylpyridine, vinylpiperidone, vinyl pyrimidine, vinyl piperazine, vinylpyrazine, second Alkenyl pyrroles, vinyl imidazole, vinylAzoles, polyvinyl morpholinone, N- vinylcarboxylic acid amide type, styrene, Alpha-Methyl benzene The vinyl monomers such as ethylene, N- caprolactam；The cyanoacrylates monomer such as acrylonitrile, methacrylonitrile；(first Base) acrylic monomer containing epoxy group such as glycidyl acrylate；(methyl) polyalkylene glycol acrylate ester, (methyl) acrylic acid The glycols third such as polypropylene glycol ester, (methyl) acrylic methoxy glycol ester, (methyl) methoxyethyl polypropylene glycol ester Olefin(e) acid ester monomer；(methyl) tetrahydrofurfuryl acrylate, fluorine-containing (methyl) acrylate, organosilicon (methyl) acrylate, propylene Acrylic ester monomers such as sour 2- methoxy acrylate etc..It can also enumerate: isoprene, butadiene, isobutene, vinyl ethers Deng.
In addition, can also enumerate the silanes monomer etc. containing silicon atom as the monomer other than the above that can be copolymerized.Make It for silanes monomer, can enumerate for example: 3- acryloxypropyl triethoxysilane, vinyltrimethoxysilane, second Alkenyl triethoxysilane, 4- vinyl butyl trimethoxy silane, 4- vinyl butyl triethoxysilane, 8- vinyl are pungent Base trimethoxy silane, 8- vinyl octyltri-ethoxysilane, 10- Methacryloxydecyl trimethoxy silane, 10- Acryloxy ruthenium trimethoxysilane, 10- Methacryloxydecyl triethoxysilane, the 10- acryloxy last of the ten Heavenly stems Ethyl triethoxy silicane alkane etc..
In addition, tripropylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) third can be used as comonomer Olefin(e) acid ester, 1,6-hexylene glycols two (methyl) acrylate, bisphenol A diglycidyl ether two (methyl) acrylate, neopentyl glycol Two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, Ji Wusi Alcohol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, in oneself Carboxylate of (methyl) acrylic acid such as ester modified dipentaerythritol six (methyl) acrylate and polyalcohol etc. has 2 or more The polyfunctional monomer of the unsaturated double-bonds such as (methyl) acryloyl group, vinyl, and in polyester, epoxy, carbamate etc. Skeleton addition 2 or more is unsaturated double as (methyl) acryloyl group of functional group identical with monomer component, vinyl etc. Polyester obtained from key (methyl) acrylate, epoxy (methyl) acrylate, carbamate (methyl) acrylate etc..
Above-mentioned (methyl) acrylic polymer is in the weight rate for all constituting monomer with (methyl) acrylic acid alkyl Ester is as principal component, and the ratio of the above-mentioned comonomer in (methyl) acrylic polymer is not particularly limited, above-mentioned copolymerization The ratio of monomer all constitute monomers weight rates in preferably 0~20% or so, preferably 0.1~15% or so, more Preferably 0.1~10% or so.
In these comonomers, from the viewpoint of cementability, durability, it is preferable to use hydroxyl monomer, contain carboxyl Monomer.Hydroxyl monomer and carboxyl group-containing monomer can be applied in combination.These comonomers contain crosslinking agent in adhesive composition The reflecting point of Shi Chengwei and crosslinking agent.Hydroxyl monomer, carboxyl group-containing monomer etc. and the reactivity of intermolecular cross-linking agent are strong, Ke Yiti Coherency, the heat resistance for the adhesive phase that height obtains, therefore it is preferable to use.From the viewpoint of re-workability, preferred hydroxyl Monomer, in addition, from the viewpoint of taking into account durability and re-workability, preferred carboxyl group-containing monomer.
In the case where containing hydroxyl monomer as above-mentioned comonomer, ratio is preferably 0.01~15 weight %, More preferably 0.03~10 weight %, further preferably 0.05~7 weight %.Containing carboxyl group-containing monomer as above-mentioned copolymerization In the case where monomer, ratio is preferably 0.05~10 weight %, more preferably 0.1~8 weight %, and further preferably 0.2 ~6 weight %.
(methyl) acrylic polymer of the invention is the polymerization of 500,000~3,000,000 ranges usually using weight average molecular weight Object.In view of durability, particularly heat resistance, it is preferable to use the polymer that weight average molecular weight is 700,000~2,700,000, further excellent It is selected as 800,000~2,500,000.When weight average molecular weight is less than 500,000, from the viewpoint of heat resistance not preferably.In addition, weight average molecular weight When greater than 3,000,000, a large amount of retarder thinner is needed in order to be adjusted to the viscosity for coating, leads to increased costs, therefore not It is preferred that.It is measured by GPC (gel permeation chromatography) and is converted by polystyrene it should be noted that weight average molecular weight refers to And calculated value.
The manufacture of such (methyl) acrylic polymer can suitably select the radiation such as polymerisation in solution, UV polymerization poly- Manufacturing method well known to conjunction, bulk polymerization, emulsion polymerization, various free radical polymerizations etc..In addition, obtained (methyl) acrylic compounds Polymer can be the arbitrary copolymers such as random copolymer, block copolymer, graft copolymer.
It should be noted that in polymerisation in solution, as polymer solvent, such as ethyl acetate, toluene can be used etc..As Specific polymerisation in solution example, polymerization initiator is added in reaction under the non-active gas air-flows such as nitrogen, usually on 50~70 DEG C of left sides It is carried out under the right side, 5~30 hours or so reaction conditions.
Polymerization initiator, chain-transferring agent used in free radical polymerization, emulsifier etc. are not particularly limited, it can be appropriate Selection uses.It should be noted that the weight average molecular weight of (methyl) acrylic polymer can pass through polymerization initiator, chain tra nsfer Dosage, reaction condition of agent etc. are controlled, and are suitable for their dosage etc. of adjustment according to their type.
It as radical polymerization initiator, can enumerate for example: 2,2 '-azodiisobutyronitriles, bis- (the 2- amidines of 2,2 '-azos Base propane) dihydrochloride, bis- [2- (5- methyl -2- imidazoline -2- base) propane] dihydrochlorides of 2,2 '-azos, 2,2 '-azos pair (2- methyl-prop amidine) dithionate, 2,2 '-azos bis- (N, N '-dimethyleneisobutylamidines), bis- [N- (the 2- carboxyls of 2,2 '-azos Ethyl) -2- methyl-prop amidine] azo-initiators, persulfuric acid such as hydrate (Wako Pure Chemical Industries, Ltd. manufacture, VA-057) The persulfates such as potassium, ammonium persulfate, dicetyl peroxydicarbonate two (2- ethylhexyl) ester, (the 4- tert-butyl ring of dicetyl peroxydicarbonate two Hexyl) ester, peroxide-butyl carbonate, new peroxide tert-butyl caprate, talkyl peropivalate, peroxidating spy penta Tert-butyl acrylate, dilauroyl peroxide, the positive decoyl of peroxidating two, peroxidating -2 ethyl hexanoic acid 1,1,3,3- tetramethyl butyl ester, mistake Aoxidize two (4- toluyls), dibenzoyl peroxide, peroxidating tert-butyl isobutyrate, 1,1- bis- (tert-hexyl peroxide) ring The peroxide type initiators such as hexane, tert-butyl hydroperoxide, hydrogen peroxide, the combination of persulfate and sodium hydrogensulfite, mistake The redox series initiators etc. that the peroxide such as the combination of oxide and sodium ascorbate and reducing agent are composed, but not It is defined in this.
Above-mentioned radical polymerization initiator can be used alone, and in addition can also mix two or more use, total content phase It is preferably 0.005~1 parts by weight or so for 100 parts by weight of monomer, more preferably 0.02~0.5 parts by weight or so.
As chain-transferring agent, it can be mentioned, for example: lauryl mercaptan, glycidyl mercaptan, thioacetic acid, 2- sulfydryl second Alcohol, thioglycolic acid, thioglycolic acid 2- ethylhexyl, 2,3- dimercapto -1- propyl alcohol etc..Chain-transferring agent can be used alone, In addition two or more use can also be mixed, total content is preferably 0.1 weight relative to 100 parts by weight of total amount of monomer component Part or so is following.
In addition, as the emulsifier used when carrying out emulsion polymerization, it can be mentioned, for example: lauryl sodium sulfate, 12 The yin such as alkylsurfuric acid ammonium, neopelex, polyoxyethylene alkyl ether ammonium sulfate, polyoxyethylene alkyl phenyl ether sodium sulphate Ionic emulsifying agent, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxy Nonionic emulsifier such as propylene block copolymer etc..These emulsifiers can be used alone, and can also be applied in combination 2 kinds More than.
In addition, having imported the cream of the free-radical polymerised functional groups such as acrylic, allyl ether as reactive emulsifier Agent specifically includes for example: AQUALON HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (are the first industry above Pharmaceutical Co., Ltd's manufacture), ADEKA REASOAP SE10N (manufacture of rising sun electrification work Co., Ltd.) etc..Reactive emulsifier exists Enter polymer chain after polymerization, thus improve water resistance, is preferred.Total amount of the dosage of emulsifier relative to monomer component 100 parts by weight are preferably 0.3~5 parts by weight, from polymerization stability, mechanical stability, more preferably 0.5~1 parts by weight.
<pigment>
Various pigments can be used in the pigment cooperated in adhesive composition of the invention.As pigment, example can be enumerated Such as: in tetraazatetradecane porphyrin class, porphyrin, cyanines class, azo, methylene pyrroles (pyrromethene) class, side are sour (squarylium) the various compounds such as class, xanthene class, oxonols class, sour cyanines (squaraine) class in side.From the sight of wide colour gamut Point set out, above-mentioned pigment be preferably tetraazatetradecane porphyrin class pigment, porphyrin pigment, cyanines class pigment, side acid inClass pigment, side Sour cyanines class pigment, particularly preferably tetraazatetradecane porphyrin class pigment.Above-mentioned pigment is specifically disclosed in Japanese Unexamined Patent Publication 2011-116818 Bulletin etc..Above-mentioned pigment can be used only a kind, two or more can also be applied in combination.
At least any wavelength of the above-mentioned pigment preferably in 570~610nm of 470~510nm of wave-length coverage and wave-length coverage Range has maximum absorption wavelength.In above-mentioned wave-length coverage there is the pigment of maximum absorption wavelength to can absorb color performance to be not required to Want it is luminous come inhibit this shine, be effective to wide colour gamut.There is maximum absorption wavelength as in above-mentioned wave-length coverage It is preferable to use tetraazatetradecane porphyrin class pigments for pigment.For example, showing absorption maximum as in 570~610nm of wave-length coverage The pigment of wavelength can be enumerated for example: the tetraazatetradecane porphyrin class compound (trade name: PD- of Yamamoto Chemicals Co., Ltd's manufacture 320, PD311), the tetraazatetradecane porphyrin class compound (trade name: FDG-007) etc. of hillside plot chemical industry Co., Ltd. manufacture.It needs It is noted that the measurement of the maximum absorption wavelength of pigment passes through the spectrophotometer (V- of Japan Spectroscopy Corporation's manufacture 570) Lai Jinhang.
The content of pigment in adhesive composition of the invention can absorbing wavelength range according to pigment, light absorption system Number, (methyl) acrylic polymer type adjust, in general, relative to 100 parts by weight of (methyl) acrylic polymer, Preferably 0.01~5 parts by weight, more preferably 0.05~3 parts by weight, further preferably 0.1~1 parts by weight.Especially make In the case where with tetraazatetradecane porphyrin class pigment, preferably above range.
<free-radical generating agent>
As the free-radical generating agent cooperated in adhesive composition of the invention, it can exemplify and manufacture above-mentioned (methyl) The radical polymerization initiator used when acrylic polymer.In above-mentioned radical polymerization initiator, it is matched with bonding The free-radical generating agent of agent composition is preferably peroxide.
Free-radical generating agent, which can generate free radicals reactive species by heating or illumination, makes (first in adhesive composition Base) acrylic polymer is crosslinked.As free-radical generating agent, it is contemplated that operability, stability are, it is preferable to use 1 minute The peroxide that half life temperature is 80 DEG C~160 DEG C, the mistake for the use of 1 minute half life temperature being more preferably 90 DEG C~140 DEG C Oxide.
It as above-mentioned peroxide, can enumerate for example: dicetyl peroxydicarbonate two (4- tert-butylcyclohexyl) ester (1 minute Half life temperature: 92.1 DEG C), peroxide-butyl carbonate (1 minute half life temperature: 92.4 DEG C), peroxidating neodecanoic acid The tert-butyl ester (1 minute half life temperature: 103.5 DEG C), talkyl peropivalate (1 minute half life temperature: 109.1 DEG C), The peroxidating pivalic acid tert-butyl ester (1 minute half life temperature: 110.3 DEG C), dilauroyl peroxide (1 minute half life temperature: 116.4 DEG C), the positive decoyl of peroxidating two (1 minute half life temperature: 117.4 DEG C), peroxidating -2 ethyl hexanoic acid 1,1,3,3- tetra- Methylbutyl butenoate (1 minute half life temperature: 124.3 DEG C), peroxidating two (4- toluyl) (1 minute half life temperature: 128.2 DEG C), dibenzoyl peroxide (1 minute half life temperature: 130.0 DEG C), peroxidating tert-butyl isobutyrate (decline for 1 minute half Phase temperature: 136.1 DEG C), 1,1- bis- (tert-hexyl peroxide) hexamethylene (1 minute half life temperature: 149.2 DEG C) etc..Wherein, special Be not from cross-linking reaction efficiency it is excellent from the aspect of, it is preferable to use dicetyl peroxydicarbonate two (4- tert-butylcyclohexyl) ester (1 minute Half life temperature: 92.1 DEG C), dilauroyl peroxide (1 minute half life temperature: 116.4 DEG C), (1 point of dibenzoyl peroxide Clock half life temperature: 130.0 DEG C) etc..
The half-life period of above-mentioned peroxide is the index for characterizing the decomposition rate of peroxide, is referred to up to peroxide Residual quantity becomes the time until half.About the decomposition temperature for obtaining half-life period with any time or at ambient temperature Half-life, it is on the books in catalogue of manufacturer etc., such as in the " organic peroxide of NOF Corp Catalogue (organic peracid compound カ タ ロ グ) the 9th edition (in May, 2003) " etc. in it is on the books.
In order to adjust the processability of the adhesive phase formed by above-mentioned adhesive composition, re-workability, cross-linked stable, Fissility etc., the content of the free-radical generating agent (especially peroxide) in adhesive composition of the invention can be considered solidifying Glue rate etc. and determine.In general, relative to above-mentioned 100 parts by weight of (methyl) acrylic polymer, the content of free-radical generating agent Preferably 0.01~2 parts by weight, further preferably 0.04~1.5 parts by weight, further preferably 0.05~1 parts by weight.
It should be noted that residual preparation sometimes should (methyl) propylene in above-mentioned (methyl) acrylic polymer Not used radical polymerization initiator (free-radical generating agent) in the polymerization when acids polymers.The remaining free radical Producing agent can be used as the use of the free-radical generating agent in above-mentioned adhesive composition.In such a case it is possible to it is remaining from Dosage is generated by base to be quantified, and free-radical generating agent is suitably cooperated according to the content of remaining free-radical generating agent.
It should be noted that remaining peroxide decomposition amount can for example pass through HPLC (efficient liquid phase after reaction treatment Chromatography) it is measured.
More specifically, for example, the adhesive composition after reaction treatment can be taken out to about 0.2g respectively every time, dipping In ethyl acetate 10mL, using vibrating machine with 120rpm mechanical shaking extraction 3 hours at 25 DEG C, then 3 days are stood at room temperature. Next, addition acetonitrile 10mL will be filtered with 120rpm oscillation 30 minutes at 25 DEG C by molecular filter (0.45 μm) About 10 μ L of obtained extracting solution injects HPLC, is analyzed, as the amount of peroxides after reaction treatment.
<antioxidant>
As the antioxidant cooperated in adhesive composition of the invention, it can be mentioned, for example: phenols, Phosphorus, sulphur class and amine The antioxidant of class, using selected from it is therein at least any one.Wherein, preferably phenolic antioxidant.
As the specific example of phenolic antioxidant, can enumerate: as mononuclear phenolic compounds 2,6-di-tert-butyl p-cresol, 2,6- di-t-butyl -4- ethyl -phenol, 2,6- dicyclohexyl -4- methylphenol, 2,6- diisopropyl -4- ethyl -phenol, 2,6- Two tertiary pentyl -4- methylphenols, bis- t-octyl -4- n-propyl phenol of 2,6-, 2,6- dicyclohexyl -4- n-octyl phenol, 2- are different Propyl -4- methyl-6-tert-butylphenol, 2- tert-butyl -4- ethyl -6- tert-octyl phenol, 2- isobutyl group -4- ethyl -6- uncle oneself Base phenol, 2- cyclohexyl -4- normal-butyl -6- isopropyl-phenol, styrol cresols, DL- alpha-tocopherol, β-(3,5- bis- Tert-butyl-hydroxy phenyl) propionic acid stearyl ester etc.；2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butyl as two ring phenolic compounds Base phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol)s, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-thiobis (4- methyl-6-tert-butylphenol), 4,4 '-methylene-bis(2,6-di-t-butyl phenol)s, 2,2 '-methylene Bis- [6- (1- methylcyclohexyl) paracresol], 2,2 '-ethylenebis (4,6- DI-tert-butylphenol compounds), 2,2 '-butylidenebis (uncles 2- Butyl -4- methylphenol), eight di-2-ethylhexylphosphine oxide of 3,6- dioxa [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic ester], Triethylene glycol bis- [3- (3- tert-butyl -5- methyl -4- hydroxy phenyl) propionic esters], bis- [3- (the tertiary fourths of 3,5- bis- of 1,6-HD Base -4- hydroxy phenyl) propionic ester], 2,2 '-thiodiethylenes it is bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester] Deng；1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane, (2,6- bis- of 1,3,5- tri- as tricyclic phenolic compounds Methyl -3- hydroxyl -4- t-butylbenzyl) isocyanuric acid ester, [(3,5- di-tert-butyl-hydroxy phenyl) the propionyl oxygen of 1,3,5- tri- Base ethyl] isocyanuric acid ester, three (4- tert-butyl -2,6- dimethyl -3- hydroxybenzyl) isocyanuric acid esters, 1,3,5- trimethyl - 2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene etc.；Four [methylene -3- (bis- uncles of 3,5- as Fourth Ring phenolic compounds Butyl -4- hydroxy phenyl) propionic ester] methane etc.；Bis- (3,5- di-tert-butyl-4-hydroxyl benzyl phosphines as phosphorous phenolic compounds Acetoacetic ester) calcium, bis- (3,5- di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester) nickel etc..
It as the specific example of Phosphorus antioxidant, can enumerate: three monooctyl ester of phosphorous acid, trilauryl phosphite, phosphorous acid Three (tridecyl) esters, triisodecyl phosphite ester, phenyl diisooctyl phosphite ester, phenyl diiso decyl phosphite ester, phenyl Two (tridecyl) phosphite esters, diphenyl iso-octyl phosphite ester, diphenyl isodecyl phosphite, diphenyl tridecane are sub- Phosphate, triphenyl phosphite, three (nonyl phenyl) phosphite esters, three (2,4- di-tert-butyl-phenyl) phosphite esters, three (fourth oxygen Base ethyl) phosphite ester, four (tridecyl) -4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl) diphosphites, 4, 4 '-isopropylidenediphenol alkyl phosphites (wherein, the carbon atom number of alkyl is 12~15 or so), 4,4 '-isopropylidenes Bis- (2- tert-butyl-phenyls) two (nonyl phenyl) phosphite ester, three (xenyl) phosphite esters, four (tridecyl) -1,1,3- three (2- methyl -5- tert-butyl-hydroxy phenyl) butane diphosphites, three (3,5- di-tert-butyl-hydroxy phenyl) phosphorous acid Ester, hydrogenation -4,4 '-isopropylidene diphenyl polyphosphite, bis- (octyl phenyls) bis- [4,4 '-butylidenebis (3- methyl -6- Tert-butyl-phenyl)] 1,6-HD diphosphites, six (tridecyl) -1,1,3-, three (2- methyl -4- hydroxyl -5- tert-butyl Phenyl) diphosphites, three [4,4 '-isopropylidenes are bis- (2- tert-butyl-phenyl)] phosphite esters, three (1,3- distearyl oxygroups Isopropyl) phosphite ester, 9,10- dihydro -9- phospho hetero phenanthrene -10- oxide, four (2,4- di-tert-butyl-phenyl) -4,4 '-Lian Ya benzene Two phosphinate of base, distearyl pentaerythrityl diphosphite, two (nonyl phenyl) pentaerythritol diphosphites, phenyl 4,4 '-isopropylidenediphenol pentaerythritol diphosphites, bis- (2,4- di-tert-butyl-phenyl) pentaerythrite diphosphorous acids Ester, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphites and phenyl bisphenol-A-pentaerythrite diphosphorous acid Ester etc..
As sulfur type antioxidant, it is preferable to use the polyol ester of dialkyl thiodipropionate and alkylthio propionic acid.Make For dialkyl thiodipropionate used herein, it is however preferred to have the thio-2 acid dioxane of the alkyl of carbon atom number 6~20 Base ester, in addition, the polyol ester as alkylthio propionic acid, it is however preferred to have the alkylthio of the alkyl of carbon atom number 4~20 The polyol ester of propionic acid.In this case, the example as the polyalcohol for the alcohol ester that comes from different backgrounds and possess different abilities, can enumerate: glycerol, trihydroxy methyl Ethane, trimethylolpropane, pentaerythrite and tris(2-hydroxy ethyl)isocyanurate etc..As such thio-2 acid dialkyl group Ester, it can be mentioned, for example: dilauryl thiodipropionate, two myristin of thio-2 acid and distearylthiodi-propionate etc.. On the other hand, the polyol ester as alkylthio propionic acid, it can be mentioned, for example: glycerol tributyl thiopropionate, glycerol three are pungent Base thiopropionate, three lauryl thiopropionate of glycerol, three stearyl-thio propionic ester of glycerol, trimethylolethane trimethacrylate butyl Thiopropionate, trimethylolethane trimethacrylate octylsulfo propionic ester, trimethylolethane trimethacrylate lauryl thiopropionate, three hydroxyl first Three stearyl-thio propionic ester of base ethane, pentaerythrite tetrabutyl thiopropionate, four octylsulfo propionic ester of pentaerythrite, season Penta tetrol, four lauryl thiopropionate, four stearyl-thio propionic ester of pentaerythrite etc..
It as the specific example of amine antioxidants, can enumerate: bis- (2,2,6,6- tetramethyl -4- piperidyl) decanedioic acid Condensation polymer, N, the N ' of ester, dimethyl succinate and the formation of 1- (2- ethoxy) -4- hydroxyl -2,2,6,6- tetramethyl piperidine ethyl alcohol, N ", N " '-four-(bis- (butyl-(N- methyl -2,2,6,6- tetramethyl piperidine -4- base) amino)-triazine -2- bases of 4,6-) -4,7- Bis- (2,2,6,6- tetramethyl -4- piperidyl-the 1,6- of diaza decane -1,10- diamines, dibutyl amine 1,3,5- triazine N, N ' - The condensation polymer of hexamethylene diamine and N- (2,2,6,6- tetramethyl -4- piperidyl) butylamine, poly- [{ 6- (1,1,3,3- tetramethyl fourth Base) amino -1,3,5- triazine -2,4- diyl } { (2,2,6,6- tetramethyl -4- piperidyl) imino group } hexa-methylene (2,2,6, 6- tetramethyl -4- piperidyl) imino group], four (2,2,6,6- tetramethyl -4- piperidyl) -1,2,3,4- butane tetracarboxylic acid esters, 2,2,6,6- tetramethyl -4- piperidyl benzoic ether, bis- (1,2,6,6- pentamethyl -4- piperidyl) -2- (3,5- di-t-butyls - 4- hydroxybenzyl) -2- n-butylmalonic acid ester, bis- (N- methyl -2,2,6,6- tetramethyl -4- piperidyl) sebacates, 1,1 ' - (1,2- ethane diyl) bis- (3,3,5,5- tetramethyl piperazinones), (mixed 2,2,6,6- tetramethyl -4- piperidyl/tridecane Base) -1,2,3,4- butane tetracarboxylic acid esters, (mixed 1,2,2,6,6- pentamethyl -4- piperidyl/tridecyl) -1,2,3,4- Butane tetracarboxylic acid esters, [2,2,6,6- tetramethyl -4- piperidyl/β, β, β ', the β '-tetramethyl -3,9- [2,4,8,10- tetra- mixed Oxaspiro (5,5) hendecane] diethyl] -1,2,3,4- butane tetracarboxylic acid esters, mixing [1,2,2,6,6- pentamethyl -4- piperidines Base/β, β, β ', β '-tetramethyl -3,9- [tetra- oxaspiro of 2,4,8,10- (5,5) hendecane] diethyl] -1,2,3,4- butane four Carboxylate, N, the bis- [N- butyl-N- (1,2,2,6,6- pentamethyl -4- piperidyl) of bis- (3- aminopropyl) ethylenediamine -2,4- of N ' - Amino] the chloro- 1,3,5- triazine condensation product of -6-, poly- [6-N- morpholino -1,3,5- triazine -2,4- diyl] [(2,2,6,6- tetramethyl Base -4- piperidyl) imino group] hexa-methylene [(2,2,6,6- tetramethyl -4- piperidyl) acid imide], N, the bis- (2,2,6,6- of N ' - Tetramethyl -4- piperidyl) hexamethylene diamine and the glycol dibromide condensation product, the [N- (2,2,6,6- tetramethyl -4- that are formed Piperidyl) -2- methyl -2- (2,2,6,6- tetramethyl -4- piperidyl) imino group] propionamide etc..
The pigment caused by prevent from because of above-mentioned free-radical generating agent determines adhesive of the invention fading The content of antioxidant in composition.In general, relative to above-mentioned 100 parts by weight of (methyl) acrylic polymer, antioxidant Content is preferably set to the range of 0.1 parts by weight or more.On the other hand, it when the content of above-mentioned antioxidant is excessive, captures by free radical The increasing proportion for the free radical that producing agent generates.It is glued as a result, being easy to cause and harming by what above-mentioned adhesive composition was formed The gel fraction of the crosslinking of mixture layer, adhesive phase reduces, and there is the tendency that bad order occurs.From this viewpoint, relative to Above-mentioned 100 parts by weight of (methyl) acrylic polymer, the content of antioxidant are preferably set to 5 parts by weight hereinafter, further preferably It is set as 1.5 parts by weight range below.From the viewpoint of taking into account and ensuring above-mentioned gel fraction and prevent pigment from fading, relative to Above-mentioned 100 parts by weight of (methyl) acrylic polymer, the content of above-mentioned antioxidant is preferably 0.1~1.5 parts by weight, further Preferably 0.2~1.0 parts by weight, further preferably 0.3~0.8 parts by weight.
In addition, from the viewpoint of taking into account the gel fraction for ensuring above-mentioned adhesive phase and preventing pigment from fading, above-mentioned freedom The weight rate (A/B) of the dosage (B) of the dosage (A) and above-mentioned antioxidant of base producing agent is preferably generally 4 hereinafter, more preferably 2 hereinafter, further preferably 1.5 or less.On the other hand, above-mentioned weight rate (A/B) is preferably generally 0.01 or more, more preferably It is 0.05 or more, is further preferably designed as meeting 0.1 or more.
<crosslinking agent>
In addition, in the present invention, being formed in the adhesive composition of adhesive phase can be containing crosslinking agent (except above-mentioned freedom Other than base producing agent).As above-mentioned crosslinking agent, organic crosslinking agent, multifunctional metallo-chelate can be used.As organic Crosslinking agent can be enumerated: isocyanates crosslinking agent, epoxies crosslinking agent, imines crosslinking agent etc..Multifunctional metallo-chelate It is made of polyvalent metal and organic compound covalent bonding or coordination bonding.As polyvalent metal atom, can enumerate: Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti etc..As covalent bonding or match Atom in the organic compound of position bonding, can enumerate oxygen atom etc., as organic compound, can enumerate: Arrcostab, alcohol Compound, carboxylic acid compound, ether compound, ketone compound etc..
As crosslinking agent, preferably isocyanates crosslinking agent.As the compound of isocyanates crosslinking agent, Ke Yilie It illustrates such as: toluene di-isocyanate(TDI), chlorine phenylene vulcabond, tetramethylene diisocyanate, two isocyanide of phenylenedimethylidyne The isocyanate-monomers such as acid esters, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate and make these isocyanides Isocyanate compound obtained from the additions such as acid ester monomer and trimethylolpropane, isocyanuric acid carboxylate, biuret form Close object and polyether polyol, polyester polyol, acrylic acid multielement alcohol ester, polybutadiene polyol, polyisoprene polyol Etc. the isocyanates etc. for the carbamate prepolymer type that have passed through addition reaction.Particularly preferred polyisocyanate compound, such as Selected from hexamethylene diisocyanate, hydrogenation one of benzene dimethylene diisocyanate and isophorone diisocyanate or Polyisocyanate compound as derived from it.Here, selected from hexamethylene diisocyanate, hydrogenation phenylenedimethylidyne diisocyanate One of ester and isophorone diisocyanate or polyisocyanate compound as derived from it include two isocyanide of hexa-methylene Acid esters, hydrogenation benzene dimethylene diisocyanate, isophorone diisocyanate, polyalcohol modified hexa-methylene diisocyanate Ester, polyalcohol modified hydrogenation benzene dimethylene diisocyanate, trimer type hydrogenate benzene dimethylene diisocyanate, Yi Jiduo First alcohol modified isophorone diisocyanate etc..For the polyisocyanate compound that example goes out, especially by polymer In contain acid, alkali as catalyst, therefore the progress that is swift in response with hydroxyl is particularly helpful to accelerate crosslinking rate, because And it is preferred that.
It in the present invention, can be more effective by antioxidant when isocyanates crosslinking agent is applied in combination as crosslinking agent Ground inhibits the radical crosslinking as caused by oxygen to hinder, and can pass through free-radical generating agent (such as peroxide) efficient landform The three-dimensional crosslinked network of composite adhesives layer.Abnormal appearance occurs in polarizing coating end as a result, can more efficiently prevent from.
In adhesive composition, relative to 100 parts by weight of (methyl) acrylic polymer, the dosage of above-mentioned crosslinking agent Preferably 20 parts by weight are still more preferably 0.03~10 parts by weight hereinafter, further preferably 0.01~20 parts by weight.It needs It is noted that moisture-proof is insufficient when above-mentioned crosslinking agent is more than 20 parts by weight, peeling is easy to happen in reliability test etc..
In addition, silane coupling agent can be contained in adhesive composition of the invention.It, can by using silane coupling agent Improve durability.As silane coupling agent, it is specific enumerable for example: 3- glycidoxypropyltrime,hoxysilane, 3- epoxy Propoxypropyl triethoxysilane, 3- glycidoxypropyl diethoxy silane, 2- (3,4- epoxycyclohexyl) second Base trimethoxy silane etc. contains epoxy silane coupling, 3- TSL 8330, N-2- (amino-ethyl) -3- ammonia Base hydroxypropyl methyl dimethoxysilane, 3- triethoxysilyl-N- (1,3- dimethylbutylene) propylamine, N- phenyl-γ- TSL 8330 etc. contains amino silicane coupling agent, 3- acryloyloxypropyltrimethoxysilane, 3- methyl-prop Alkene acryloxypropylethoxysilane triethoxysilane etc. contains (methyl) acrylic silane coupling agent, 3- isocyanates propyl-triethoxysilicane Coupling agents containing isocyanato silanes such as alkane etc..
Above-mentioned silane coupling agent can be used alone, and in addition can also mix two or more use, for its total content Speech, relative to above-mentioned 100 parts by weight of (methyl) acrylic polymer, above-mentioned silane coupling agent is preferably 0.001~5 weight Part, more preferably 0.01~1 parts by weight, further preferably 0.02~1 parts by weight, further preferably 0.05~0.6 weight Part.This is to improve durability, the appropriate amount kept to the bonding force of the optical components such as liquid crystal cells.
Furthermore, in the present invention it is possible to cooperate organic silicon modified by polyether in the adhesive composition for forming adhesive phase. Compound disclosed in such as Japanese Unexamined Patent Publication 2010-275522 bulletin can be used in organic silicon modified by polyether.
Furthermore, in the present invention it is possible to contain other well known addition in the adhesive composition for forming adhesive phase Agent, can be properly added according to the purposes used the powder such as colorant, pigment, dyestuff, surfactant, plasticizer, Tackifier, surface lubricant, levelling agent, softening agent, age resister, light stabilizer, ultraviolet absorbing agent, polymerization inhibitor, it is inorganic or Organic filler, metal powder or granule, foil-like object etc..In addition, in controllable range, it can also be using addition reducing agent Redox class.
Adhesive phase is formed by above-mentioned adhesive composition, when forming adhesive phase, is preferably generated in adjustment free radical Agent (such as peroxide), crosslinking agent additive amount while, fully consider the shadow of crosslinking Treatment temperature, crosslinking Treatment time It rings.
Crosslinking Treatment temperature, crosslinking Treatment time can be adjusted according to the crosslinking agent used.Crosslinking Treatment temperature is preferably 170 DEG C or less.
In addition, above-mentioned crosslinking Treatment can carry out at the temperature at which the drying process of adhesive phase, it can also be in drying Otherwise designed crosslinking Treatment process carries out after process.
In addition, about the crosslinking Treatment time, it may be considered that productivity, operability are set, but usually 0.2~20 Minute or so, preferably 0.5~10 minute or so.
Generally preferably above-mentioned crosslinking is controlled, so that the gel fraction of above-mentioned adhesive phase is 50 weight % or more.From Outside, from the viewpoint of high temperature durability, the gel fraction of above-mentioned adhesive phase is preferably controlled to 60 weight % or more.Above-mentioned gel Rate is preferably 75 weight % or more, further preferably 80 weight % or more.On the other hand, it when gel fraction becomes excessive, is easy It is peeling-off in durability test, therefore, gel fraction be preferably 98 weight % hereinafter, further preferably 95 weight % with Under.The measurement of gel fraction is carried out according to the method recorded in embodiment.
In addition, for above-mentioned adhesive phase, with a thickness of 20 μm, saved at 85 DEG C 500 hours it The absolute value of the difference (T1-T2) of transmissivity (T2) after preceding transmissivity (T1) and preservation is preferably 50% hereinafter, further Preferably 40% hereinafter, further preferably 30% hereinafter, further preferably 10% hereinafter, most preferably 5% or less.It needs Illustrate, in general, the value of (T1-T2) due to pigment colour fading and become "-" value.It on the other hand, is "+" in above-mentioned value In the case where, expression is not faded substantially.
In addition, the ratio (T2/T1) of the above-mentioned transmissivity (T2) of above-mentioned adhesive phase and transmissivity (T1) be preferably 2 with Under, further preferably 1.5 hereinafter, further preferably 1.3 hereinafter, further preferably 1.2 hereinafter, further preferably 1.1 following.It should be noted that in general, the value of ratio (T2/T1) due to pigment colour fading and be 1 or more.On the other hand, exist In the case that above-mentioned value is less than 1, expression is not faded substantially.
Polarizing coating with adhesive phase of the invention is formd in at least side of polarizing coating by above-mentioned adhesive composition Adhesive phase.
As the method for forming adhesive phase, made using following method: for example, above-mentioned adhesive composition is applied It is distributed in the diaphragm etc. that have passed through lift-off processing, after drying and removing polymer solvent etc. and forming adhesive phase, is transferred to polarization The method of film；Alternatively, be coated with above-mentioned adhesive composition on polarizing coating, dry and remove polymer solvent etc. and on polarizing coating shape The method etc. of composite adhesives layer.It should be noted that suitably can also be newly added in addition to polymer solvent when coating adhesive More than one solvent.
As the diaphragm being release-treated, organosilicon peeling liner is preferably used.By adhesive composite of the invention It is coated on such liner above and makes it dry and formed in the process of adhesive phase, it, can as the method for keeping adhesive dry According to purpose suitably using suitable method.It is preferred that using the method being thermally dried to above-mentioned coated film.Heating is dry Dry temperature is preferably 40 DEG C~200 DEG C, more preferably 50 DEG C~180 DEG C, particularly preferably 70 DEG C~170 DEG C.By making to heat Temperature is in above-mentioned range, the available adhesive with excellent adhesion characteristic.
Drying time can be suitably using the suitable time.Above-mentioned drying time is preferably 5 seconds~20 minutes, further Preferably 5 seconds~10 minutes, particularly preferably 10 seconds~5 minutes.
Furthermore it is possible to the surface of polarizing coating formed adhesion promoting layer or implementing sided corona treatment, corona treatment etc. it is various Adhesive phase is formed after easy bonding processing.Easy bonding processing is carried out alternatively, it is also possible to the surface to adhesive phase.
As the forming method of above-mentioned adhesive phase, various methods can be used.It is specific enumerable for example: rolling method, roller are licked Rubbing method, gravure coating process, reversed rubbing method, roller brush method, spray coating method, dipping rolling method, stick coating method, knife coating, airblade coating Method, die lip rubbing method, utilizes the methods of extrusion coating methods of die coating machine etc. at curtain coating.
The thickness of adhesive phase is not particularly limited, for example, 1~100 μm or so, preferably 2~50 μm, more preferably 2 ~40 μm, further preferably 5~35 μm.
In the case where the exposure of above-mentioned adhesive phase, piece (diaphragm) the protection adhesive that have passed through lift-off processing can use Layer, until for actual use.
As the constituent material of diaphragm, it can be mentioned, for example: polyethylene, polypropylene, polyethylene terephthalate, polyester The suitable thin slice such as the porous materials such as the plastic foils such as film, paper, cloth, non-woven fabrics, net, foamed sheet, metal foil and their layered product Object etc., from the excellent aspect of surface smoothness, it is preferable to use plastic foil.
It as the plastic foil, as long as the film of above-mentioned adhesive phase can be protected, is not particularly limited, example can be enumerated Such as: polyethylene film, polypropylene screen, polybutene film, polybutadiene film, polymethylpentene film, polychloroethylene film, vinyl chloride copolymer Film, polyethylene terephthalate film, polybutylene terephthalate (PBT) film, polyurethane film, ethylene-vinyl acetate c Object film etc..
The thickness of above-mentioned diaphragm is usually 5~200 μm, and preferably 5~100 μm or so.It can also be as needed using having Machine silicon class, fluorinated, chain alkyl class or release agent, the silicon dioxide powder of fatty acid acyl amine etc. demould above-mentioned diaphragm And antifouling process or the antistatic treatment for being coated by type, is mixed into type, vapor deposition type for above-mentioned diaphragm etc..Especially it is possible to logical It crosses and is suitably carried out by the lift-off processings such as organosilicon processing, chain alkyl processing, fluorine processing and is further mentioned for the surface of above-mentioned diaphragm Fissility of the height relative to above-mentioned adhesive phase.
It should be noted that the piece being release-treated used when making the above-mentioned polarizing coating with adhesive phase can be with It uses directly as the diaphragm of the polarizing coating with adhesive phase, can simplify in terms of process.
The one or both sides that polarizing coating is generally used in polarizer have the polarizing coating of transparent protective film.
Polarizer is not particularly limited, and various polarizers can be used.As polarizer, it can be mentioned, for example make iodine, two colors Dichroic substance as property dyestuff is adsorbed in polyvinyl alcohol film, part formalizing polyvinyl alcohol film, ethylene-acetate second The hydrophilic macromolecule films such as the partly-hydrolysed film of enoate copolymer class and the dehydration for carrying out film obtained from simple tension, polyvinyl alcohol Polyenoid based oriented films such as processed material, the dehydrochlorinated products of polyvinyl chloride etc..Wherein, preferably by polyvinyl alcohol film and iodine etc. The polarizer that dichroic substance is formed.The thickness of these polarizers is not particularly limited, and usually 80 μm or so or less.
Above-mentioned polyvinyl alcohol film is dyed with iodine and carry out polarizer made of simple tension for example and can pass through by Polyvinyl alcohol film immersion dyes in the aqueous solution of iodine and is stretched to 3~7 times of former length and is made.It can also be impregnated in As needed in the aqueous solution of potassium iodide optionally comprising boric acid, zinc sulfate, zinc chloride etc. etc..Further, it is possible to as needed And polyvinyl alcohol film immersion is washed in water before dyeing.By being washed to polyvinyl alcohol film, in addition to can To wash away other than the dirt of polyvinyl alcohol film surface, antiblocking agent, also having makes polyvinyl alcohol membrane swelling to prevent from contaminating The unequal non-uniform effect of color.Stretching can carry out after being dyed using iodine, can also be stretched with Edge Coloring side, in addition It can also be dyed after being stretched using iodine.It can also be carried out in the aqueous solution of boric acid, potassium iodide etc. or water-bath It stretches.
In addition, can be used as polarizer with a thickness of 10 μm of slim polarizers below.It is examined from the viewpoint of slimming Consider, which is preferably 1~7 μm.The uneven thickness of such slim polarizer is small, and visibility is excellent, and size Change small, therefore excellent in te pins of durability, and then can also realize slimming as the thickness of polarizing coating, in terms of these preferably.
As representative slim polarizer, Japanese Unexamined Patent Application 51-069644 bulletin, Japanese Unexamined Patent Publication can be enumerated 2000-338329 bulletin, WO2010/100917 pamphlet, the specification of PCT/JP2010/001460 or Japanese Patent Application The slim polarizing coating recorded in 2010-269002 specification, Japanese Patent Application 2010-263692 specification.These are slim partially Vibrating diaphragm can be by including by polyvinyl alcohol resin (hereinafter also referred to PVA resinoid) layer and stretching resin base material with laminated body The state process stretched and the process dyed preparation method and obtain.If it is the preparation method, even if then PVA class tree Rouge layer is relatively thin, is supported by being stretched with resin base material, can also be stretched without generating fracture etc. caused by stretching Unfavorable condition.
It is including the process stretched with the state of laminated body and the work dyed as above-mentioned slim polarizing coating In the preparation method of sequence, from can with high magnification is stretched and from the aspect of improving polarizing properties, preferably No. WO2010/100917 Pamphlet, the specification of PCT/JP2010/001460 or Japanese Patent Application 2010-269002 specification, Japanese Patent Application 2010- As recording in No. 263692 specifications includes thin obtained from the preparation method of the process stretched in boric acid aqueous solution It is recorded in type polarizer, especially Japanese Patent Application 2010-269002 specification, Japanese Patent Application 2010-263692 specification Include secondarily carrying out the preparation method of the process stretched in atmosphere before being stretched in boric acid aqueous solution and obtaining Slim polarizer.
As the material for constituting transparent protective film, such as transparency, mechanical strength, thermal stability, moisture barrier can be used The excellent thermoplastic resins such as property, isotropism.As the concrete example of such thermoplastic resin, cellulose triacetate can be enumerated Equal celluosic resins, polyester resin, polyethersulfone resin, polysulfone resin, polycarbonate resin, polyamide, polyimides tree Rouge, polyolefin resin, (methyl) acrylic resin, cyclic polyolefin resin (norbornene resin), polyarylate resin, polyphenyl Vinyl, polyvinyl alcohol resin and their mixture.It should be noted that bonding can be passed through in the side of polarizer Oxidant layer is bonded transparent protective film, uses (methyl) acrylic compounds, carbamates, propenoic methyl carbamate in the other side The thermosetting resins such as class, epoxies, organic silicon or ultraviolet curing resin are as transparent protective film.It can also be in transparent guarantor The additive for being suitable for containing a kind of any of the above in cuticula.As additive, it can be mentioned, for example ultraviolet absorbing agent, antioxidant, profits Lubrication prescription, plasticizer, release agent, anti-coloring agent, fire retardant, nucleating agent, antistatic agent, pigment, colorant etc..In transparent protective film The content of above-mentioned thermoplastic resin be preferably 50~100 weight %, more preferably 50~99 weight %, further preferably 60 ~98 weight %, particularly preferably 70~97 weight %.The content of above-mentioned thermoplastic resin in transparent protective film is 50 weights When measuring % or less, it is possible to be unable to fully show the high transparency etc. that thermoplastic resin has originally.
For the thickness of transparent protective film, as long as the overall thickness of polarizing coating becomes 100 μm or less, without special Limitation, for example, 10~90 μm or so, preferably 15~60 μm, more preferably 20~50 μm.
Hard conating, anti-reflection layer, adherent layer, diffusion can be set in the face for not being bonded polarizer of above-mentioned transparent protective film The functional layers (superficial layer) such as layer or antiglare layer.
As long as not limited especially for by the bonding agent optical clear of above-mentioned polarizer and transparent protective film fitting The bonding agent of aqueous, solvent, hot melt class, the various forms of radical-curable, cationic curing type can be used, preferably in system For aqueous adhesive or radical-curable bonding agent.
<liquid crystal display panel>
Polarizing coating with adhesive phase of the invention fits in liquid by the adhesive phase of the polarizing coating with adhesive phase At least one side in brilliant unit, to form liquid crystal display panel.Polarizing coating with adhesive phase of the invention can be preferred for liquid The visible side of brilliant unit.
Any type of liquid crystal cells such as TN type, STN type, π type, VA type, IPS type can be used in liquid crystal cells, this The preferably middle liquid crystal cells using IPS mode of the liquid crystal display panel of invention.
In the formation of liquid crystal display panel other than above-mentioned polarizing coating, other optical layers can also be used.For the optical layer Be not particularly limited, for example, liquid crystal cells visible side and/or back side can be used 1 layer or 2 layers or more reflector plate, Half transmitting piece, phase difference film (including the wave plates such as 1/2,1/4), vision compensation film, brightness improve in the formation of liquid crystal display panels such as film The optical layer used.
<liquid crystal display device>
Liquid crystal display device can be by using the structures such as above-mentioned liquid crystal display panel and the lighting system used as needed It is suitable for assembling and importing driving circuit etc. and formed at component.In addition, when forming liquid crystal display device, for example, can be suitable When position configure 1 layer or 2 layers or more diffusion sheet, antiglare layer, antireflection film, screening glass, prism array, lens array sheet, The suitable component such as light diffusing sheet, backlight.Furthermore it is possible to form the liquid for having used backlight or reflector plate in the illumination system The suitable liquid crystal display device such as crystal device.
Embodiment
Hereinafter, the present invention is concretely demonstrated by embodiment, but the present invention is not limited to the examples.It needs It is noted that part and % in each example are weight basis.Hereinafter, the condition that is placed at room temperature for being not particularly limited is 23 DEG C, 65%RH.
<measurement of the weight average molecular weight of (methyl) acrylic polymer>
The weight average molecular weight (Mw) of (methyl) acrylic polymer is measured by GPC (gel permeation chromatography).For Mw/Mn is similarly determined.
Analytical equipment: TOSOH Co., Ltd's manufacture, HLC-8120GPC
Column: TOSOH Co., Ltd's manufacture, G7000HXL+GMHXL+GMHXL
Column dimension: each 7.8mm φ × 30cm amounts to 90cm
Column temperature: 40 DEG C
Flow: 0.8mL/min
Injection rate: 100 μ L
Eluent: tetrahydrofuran
Detector: differential refractometer (RI)
Standard sample: polystyrene
<production of polarizing coating>
By 80 μm of thickness of polyvinyl alcohol film in 30 DEG C, the iodine solution of 0.3% concentration in speed than one between different rollers It is stretched to 3 times on one side within Edge Coloring 1 minute.Then, the boric acid comprising 4% concentration, 60 DEG C of the potassium iodide of 10% concentration it is water-soluble Being stretched to total stretching ratio in liquid while impregnating 0.5 minute is 6 times.Next, by the iodate containing 1.5% concentration It impregnates 10 seconds and is cleaned in 30 DEG C of aqueous solutions of potassium, drying in 4 minutes is then carried out at 50 DEG C, has obtained thickness 30 μm of polarizer.Passing through the fitting of polyvinyl alcohol bonding agent on the two sides of the polarizer have passed through 80 μm of thickness of saponification process Tri cellulose acetate membrane, made polarizing coating.
<preparation of (methyl) acrylic polymer>
In the reaction vessel for having condenser, nitrogen ingress pipe, thermometer and agitating device, it is added and contains acrylic acid fourth 100 parts of ester, 0.01 part of acrylic acid 2- hydroxy methacrylate and 5 parts of acrylic acid of monomer mixture.Further, relative to above-mentioned monomer 100 parts of mixture, it is added 0.1 part of 2, the 2 '-azodiisobutyronitriles as polymerization initiator together with 100 parts of ethyl acetate, one It is then maintained at the liquid temperature in flask near 55 DEG C while being slowly stirred and importing nitrogen progress nitrogen displacement on one side, has carried out 8 Hour polymerization reaction, be prepared for weight average molecular weight (Mw) 1,800,000, Mw/Mn=4.1 acrylic polymer solution (solid 30 weight % of constituent concentration).
Embodiment 1
(preparation of adhesive composition)
100 parts of the solid component of acrylic polymer solution relative to above-mentioned manufacture cooperates free-radical generating agent (mistake Benzoyl Oxide, the trade name NYPER BMT of NOF Corp's manufacture) 0.23 part, isocyanates crosslinking agent (Tosoh The trade name Coronate L of Co., Ltd.'s manufacture) 1 part, the tetraazatetradecane porphyrin class pigment (quotient of Yamamoto Chemicals Co., Ltd's manufacture Name of an article PD-320: there is maximum absorption wavelength in wavelength 595nm) 0.25 part and phenolic antioxidant (BASF JAPAN corporation The trade name IRGANOX 1010 made) 0.25 part, obtain adhesive composition.
(production of adhesive phase)
Above-mentioned adhesive composition is evenly coated at by organic with jetting type spreader (fountain coater) The surface of silicon class remover treated polyethylene terephthalate film (PET base material), it is permanent in 155 DEG C of air circulating types It is 2 minutes dry in warm baking oven, 20 μm of thickness of adhesive phase is formd on the surface of PET base material, it then, will be above-mentioned identical PET base material fits in the adhesive phase, has obtained the bonding film for having PET base material on the two sides of adhesive phase.
Embodiment 2~12, comparative example 1~3
In embodiment 1, when preparing adhesive composition, by pigment, free-radical generating agent, the dosage of antioxidant such as table 1 It is shown to be changed, in addition to this, bonding film has been made similarly to Example 1.
Evaluation below has been carried out for bonding film obtained in above-described embodiment and comparative example (adhesive phase).It will evaluation As a result shown in table 1.
<measurement of gel fraction>
Each adhesive composition before making bonding film in Examples and Comparative Examples is coated on and is removed with organic silicon Agent implements the polyethylene terephthalate film of processing so that after dry with a thickness of 20 μm, after coating, with each example phase Curing process is carried out under same drying condition (temperature, time), adhesive phase is formed, further in 23 DEG C of temperature, humidity 65% After placing 1 hour under conditions of RH, gel fraction is determined to the adhesive phase.
For gel fraction, above-mentioned adhesive phase 0.2g is taken, is wrapped in the fluororesin (TEMISH of measured in advance weight The manufacture of NTF-1122 Nitto Denko Corp) in (Wa) and bundled, so that optics adhesive does not leak, so Weight (Wb) is measured afterwards, is put into sample bottle.Ethyl acetate 40cc is added, is placed 1 hour or 7 days.Then, fluororesin is taken Out, 2 hours dry with 130 DEG C on aluminium cup, weight (Wc) of the measurement comprising the fluororesin including sample is asked by lower formula (I) Gel fraction out.
Formula (I): gel fraction=(Wc-Wa)/(Wb-Wa) × 100 (weight %)
<measurement of transmissivity>
After removing the PET base material of side on the bonding film obtained in the Examples and Comparative Examples, adhesive phase side is pasted Together in alkali-free glass.Then, another PET is removed, in 60 μm of adhesive phase coating thickness of acrylic film of exposing, as Sample.The sample is put into 85 DEG C of baking oven 1000 hours, has carried out durability test, be then taken out.To the sample It determines the transmissivity (T1) before carrying out durability test and carries out the transmissivity (T2) after durability test.Transmissivity Measurement carries out in the state that sample is 23 DEG C.The measurement of transmissivity has been carried out to above-mentioned sample.Acrylic film to transmissivity not It impacts.
Show the result in table 1.Together illustrated in table 1 transmissivity (T1) and transmissivity (T2) difference (T1-T2), they Ratio (T2/T1).The measurement of transmissivity uses spectral transmission analyzer (the color technical research institute in village with integrating sphere Dot-3c it) measures.

Claims (17)

1. a kind of polarizing coating adhesive composition, contain (methyl) acrylic polymer, pigment, free-radical generating agent and Antioxidant.
2. polarizing coating adhesive composition according to claim 1, wherein the pigment wave-length coverage 470~ At least any wave-length coverage in 570~610nm of 510nm and wave-length coverage has maximum absorption wavelength.
3. polarizing coating adhesive composition according to claim 1 or 2, wherein the pigment is tetraazatetradecane porphyrin class Pigment.
4. the polarizing coating described in any one of claim 1 to 3 with adhesive phase, wherein relative to (methyl) 100 parts by weight of acrylic polymer contain 0.01~5 parts by weight of pigment.
5. polarizing coating adhesive composition according to any one of claims 1 to 4, wherein the free radical generates Agent is peroxide.
6. polarizing coating adhesive composition according to any one of claims 1 to 5, wherein relative to (the first Base) 100 parts by weight of acrylic polymer, contain 0.01~2 parts by weight of free-radical generating agent.
7. polarizing coating adhesive composition described according to claim 1~any one of 6, wherein the antioxidant is phenol Kind antioxidant.
8. polarizing coating adhesive composition according to any one of claims 1 to 7, wherein relative to (the first Base) 100 parts by weight of acrylic polymer, contain 0.1~5 parts by weight of antioxidant.
9. polarizing coating adhesive composition described according to claim 1~any one of 8, wherein the free radical generates The weight rate (A/B) of the dosage (B) of the dosage (A) and the antioxidant of agent is 4 or less.
10. polarizing coating adhesive composition, also contains crosslinking agent described according to claim 1~any one of 9.
11. a kind of polarizing coating adhesive phase is combined by polarizing coating according to any one of claims 1 to 10 with adhesive Object is formed.
12. polarizing coating adhesive phase according to claim 11, gel fraction is 50~98 weight %.
13. polarizing coating adhesive phase according to claim 11 or 12, wherein described adhesive layer is with a thickness of 20 μm In the case where, the difference (T1-T2) of the transmissivity (T2) after transmissivity (T1) and preservation before being saved 500 hours at 85 DEG C Absolute value be 50% or less.
14. polarizing coating adhesive phase described in any one of 1~13 according to claim 1, wherein described adhesive layer is in thickness In the case that degree is 20 μm, the transmissivity (T2) after being saved 500 hours at 85 DEG C and the transmissivity (T1) before saving Ratio (T2/T1) is 2 or less.
15. a kind of polarizing coating with adhesive phase is formed with any in claim 12~14 in at least side of polarizing coating Polarizing coating adhesive phase described in.
16. a kind of liquid crystal display panel, wherein the polarizing coating with adhesive phase described in liquid crystal cells and claim 15 passes through the band The adhesive phase of the polarizing coating of adhesive phase fits in at least any surface of the liquid crystal cells.
17. a kind of liquid crystal display device, with the liquid crystal display panel described in claim 16.
CN201880011246.5A 2017-03-06 2018-03-05 Adhesive composition for polarizing film, adhesive layer for polarizing film, polarizing film with adhesive layer, liquid crystal panel, and liquid crystal display device Active CN110291167B (en)

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