CN104046281A - Adhesive Agent For Optical Member And Active Energy Ray And/or Heat Hardening Adhesive Composite, Optical Member Having Adhesive Layer Attached Thereto, And Image Display Device - Google Patents

Adhesive Agent For Optical Member And Active Energy Ray And/or Heat Hardening Adhesive Composite, Optical Member Having Adhesive Layer Attached Thereto, And Image Display Device Download PDF

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Publication number
CN104046281A
CN104046281A CN201410291414.4A CN201410291414A CN104046281A CN 104046281 A CN104046281 A CN 104046281A CN 201410291414 A CN201410291414 A CN 201410291414A CN 104046281 A CN104046281 A CN 104046281A
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Prior art keywords
methyl
aromatics
ester
vinylformic acid
polarizer
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CN201410291414.4A
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CN104046281B (en
Inventor
铃木秀昭
高木圣子
三谷直也
堀家浩史
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Mitsubishi Kasei Corp
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Nippon Synthetic Chemical Industry Co Ltd
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Priority claimed from JP2010252719A external-priority patent/JP5729973B2/en
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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
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • C09J7/35—Heat-activated
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)
  • Adhesive Tapes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to adhesive agent for an optical member and active energy ray and/or heat hardening adhesive composite, the optical member having an adhesive layer attached thereto, and an image display device. The adhesive agent for the optical member is obtained by curing a self-adhesive composition [I] with active energy rays and/or heat, wherein the self-adhesive composition [I] contains an acrylic resin (A), an aromatic compound (B) containing one ethylenically unsaturated group, and an ethylenically unsaturated compound (C) containing at least two ethylenically unsaturated groups. The content of the aromatic compound (B) is 3-300 pts.wt. relative to 100 pts.wt. of the acrylic resin (A), and the content ratio (mol%) of the aromatic compound (B) to the total content of the aromatic compound (B) and the ethylenically unsaturated compound (C) is more than 50 mol%.

Description

Polarizer use tackiness agent and active energy beam/heat-curable adhesive composition, band binder layer Polarizer, image display device
The application is to be that on 01 20th, 2011, application number are PCT/JP2011/050916 the applying date, and denomination of invention is the dividing an application of application of tackiness agent, used for optical part tackiness agent, the optics with binder layer, image display device, active energy beam and/or Thermocurable binder composition, binder composition.
Technical field
The present invention relates to tackiness agent (pressure adhesive) and used for optical part tackiness agent, use it and the optics with binder layer, image display device, active energy ray-curable and/or the Thermocurable binder composition that obtain.Specifically, relate to and be suitable for liquid crystal indicator, organic EL display, optical thin film (the polarizing film of the image display devices such as PDP (plasma display panel), phase-contrast film, optical compensating film, film etc. adds lustre to) etc., more specifically, relate to the used for optical part tackiness agent for the glass substrate of the bonding optical laminate forming by protective film coating polarizing films such as triacetate fiber prime system films and liquid crystal cells, and be formed with the optics with binder layer of the binder layer being formed by this used for optical part tackiness agent, especially with the Polarizer of binder layer.
Background technology
Up to now, by on the surface of the liquid crystal cells of the stacked liquid crystal composition that is between two sheet glass clamping orientation of Polarizer, thereby formation LCD panel, cellulose-based film for described Polarizer, the two sides that the polyvinyl alcohol film etc. of polarity is given in coating such as cellulose triacetate film form, this liquid crystal cells lip-deep stacked conventionally by by the binder layer that is arranged at Polarizer surface with the surperficial butt of above-mentioned liquid crystal cells, press to carry out.
It is the 3-tier architecture that protective membrane is clipped in the two sides of polyethenol series polaroid that this Polarizer has with tri acetyl cellulose, but because these properties of materials lack dimensional stability.In addition, because polyethenol series polaroid is shaped by extending, therefore easily cause through time dimensional change.If the internal stress that the dimensional change due to such cannot be produced absorbs, relaxes, the residual stress distribution that acts on Polarizer can become inhomogeneous, and especially stress is concentrated in the circumference of Polarizer.Its result, the irregular colour light leakage phenomena that the circumference that liquid crystal indicator occurs in liquid crystal indicator is more brighter or more dim etc. than central authorities.
So, about various optical applications, Polarizer stickup tackiness agent especially, for the excellent in te pins of durability of not only bubbling, peeling off etc., and also excellent tackiness agent and being studied of the optical characteristics that is difficult to occur light leak etc.
For example, thereby in patent documentation 1, recorded a kind of use by the tackiness agent of the acrylic resin optical characteristics excellence of aromatic monomer copolymerization, thereby in patent documentation 2, recorded a kind of tackiness agent that the low-molecular weight compound that contains aromatic nucleus is compounded in to optical characteristics excellence in acrylic resin, in patent documentation 3, recorded a kind of will be used in combination acrylic resin ethylene unsaturated monomer (UV curing monomer) thus with active energy beam, irradiate the tackiness agent of the balance excellence that makes its crosslinking polymerization weather resistance and optical characteristics.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-53976 communique
Patent documentation 2:WO2007/072799 communique
Patent documentation 3: TOHKEMY 2009-132909 communique
Summary of the invention
the problem that invention will solve
Yet, although disclosed technology has shown certain optical characteristics in above-mentioned patent documentation 1, in order to meet in recent years for the requirements at the higher level of optical characteristics by this technology, must make a large amount of copolymerization of aromatic monomer.
But; while using a large amount of aromatic monomers to carry out polymerization; viscosity in reaction solution can rise; therefore (be for example difficult to be manufactured in the tackiness agent of optical applications normally used high molecular; weight-average molecular weight is more than 1,000,000) acrylic resin; in addition; common aromatic monomer; because the diacrylate body of the impurity producing when it is manufactured is difficult to be waited and removed by distillation; therefore often can contain the diacrylate body of impurity; due to the impact of this impurity, with the above-mentioned acrylic resin that is difficult to equally manufacture high molecular.
And then while using the low-molecular-weight aromatic monomers such as benzyl acrylate, vinylformic acid phenoxy ethyl be easier to carry out polymerization in polymerization, remaining monomer during polymerization may be still residual after binder layer forms, its stink also can become problem.
The disclosed technology of above-mentioned patent documentation 2 can obtain being difficult for occurring the result of irregular colour, light leak really, but, the low-molecular weight compound crystallinity with 2 above phenyl ring that patent documentation 2 is used is high or hydrophobic group is few, therefore poor to the consistency of acrylic resin, and be low molecular weight compositions, because force of cohesion is low, therefore the force of cohesion as acrylic adhesive cannot improve, and has the problem of the weather resistance variation of liquid crystal indicator.
In the disclosed technology of above-mentioned patent documentation 3, the balance of weather resistance and optical characteristics is really excellent, but because the main ethylene unsaturated monomer with 2 above olefinic unsaturated groups that uses is as UV curing monomer, therefore cross-linking density, the Young's modulus of the postradiation binder layer of UV are compared and are become very high with common tackiness agent, exist the viscosity of tackiness agent to reduce, the problem of tackiness agent adhesion sense difference while pasting to adherend.
Therefore, under such background, the object of the invention is to, the operability (viscosity) of binder layer, the tackiness agent that optical characteristics (mist degree (Haze)) is excellent are provided, even and the in the situation that of the laminating of the opticses such as Polarizer and glass substrate endurance quality and optical characteristics (resistance to light leak performance) also tackiness agent, especially the used for optical part tackiness agent of excellence.
for the scheme of dealing with problems
The inventor etc. have carried out repeatedly deep research for above-mentioned situation, found that: in the tackiness agent of active energy ray curable and/or thermohardening type, by take mode that monofunctional monomer is main body, using the polyfunctional monomer of monofunctional monomer that specified proportion contains 1 olefinic unsaturated group and olefinic unsaturated group containing more than 2 as the ethylene unsaturated monomer of solidified nature, and then use the monofunctional monomer with aromatic nucleus as monofunctional monomer, operability (viscosity), optical characteristics (mist degree) excellence, and the balance of endurance quality and resistance to light leak is excellent, thereby completed the present invention.
, main idea of the present invention relates to a kind of tackiness agent, it is characterized in that, it is for being cured by active energy beam and/or heat the tackiness agent forming by binder composition [I], described binder composition [I] contains acrylic resin (A), the alefinically unsaturated compounds (C) of olefinic unsaturated groups more than containing the aromatics (B) of 1 olefinic unsaturated group and containing 2, wherein the content of aromatics (B) is that resin (A) is 3～300 weight parts with respect to 100 parts by weight of acrylic acid, and aromatics (B) is greater than 50mol% with respect to aromatics (B) and the ratio (mol%) that contains of the total amount of alefinically unsaturated compounds (C).
In addition, main idea of the present invention relates to the used for optical part tackiness agent that uses above-mentioned tackiness agent to form, and the optics with binder layer of the stepped construction that comprises the binder layer that contains this used for optical part tackiness agent and optics, the image display device consisting of this optics.
In addition, main idea of the present invention relates to a kind of tackiness agent, it is characterized in that, it contains acrylic resin (A), containing the polymkeric substance of the aromatics (B) of 1 olefinic unsaturated group, containing the aromatics (B) of 1 olefinic unsaturated group, and organic solvent.
And then, main idea of the present invention relates to a kind of binder composition, it is characterized in that, it contains acrylic resin (A) and containing the aromatics (B) of 1 olefinic unsaturated group, form containing the alefinically unsaturated compounds (C) of 2 above olefinic unsaturated groups, wherein, the photoelastic coefficient of acrylic resin (A) is for negative, and the photoelastic coefficient of aromatics (B) and the cured article of alefinically unsaturated compounds (C) is for just.
In addition, the excellent performance of resistance to light leak of tackiness agent of the present invention, is presumed as follows about not there is the reason of light leak.
Generally speaking; the major cause that light leak occurs is speculated as: because Polarizer is exposed to the contraction in lower time of heat-resisting condition; stress is to concentrate and generation double refraction (having positive photoelastic coefficient) on protective film at the tri acetyl cellulose (TAC) of Polarizer; or the acrylate copolymer of tackiness agent is followed equally the contraction of Polarizer and is orientated, generation double refraction (generally speaking having negative photoelastic coefficient).
If be that the double refraction that protective film is originated compares to the acrylate copolymer with negative photoelastic coefficient in the past with the TAC with positive photoelastic coefficient, infer that the double refraction in acrylate copolymer source is larger.That is,, while producing tensile stress when Polarizer contraction (direction that produces stress is decided to be x direction of principal axis), it is that protective film reduces effect in the axial specific refractory power of y that the specific refractory power of the acrylate copolymer increasing at y direction of principal axis cannot be offset TAC.In order to eliminate (counteracting) this double refraction, must strengthen somewhere positive photoelastic coefficient.
Therefore in the present invention; by the negative birefringent acrylic resin (A) of the generation with respect in the past; evenly mix and produce positive birefringent aromatics (B) and the cured article of alefinically unsaturated compounds (C); can utilize aromatics (B) and the cured article of alefinically unsaturated compounds (C) to offset the double refraction of acrylic resin (A) and/or the birefringent generation that tri acetyl cellulose is film, thereby obtain the Polarizer that is provided with adhering agent layer of resistance to light leak excellence.
On the other hand, for the foregoing reasons, simple function and to produce positive birefringent aromatics (B) more than alefinically unsaturated compounds (C) importantly, aromatics (B) is brought into play degree of freedom with the cured article of alefinically unsaturated compounds (C) thus, when acrylic resin (A) is orientated, aromatics (B) is also and then orientated with the cured article of alefinically unsaturated compounds (C), infers and can reach effect of the present invention therefrom.
Otherwise, if the magnitude relation of aromatics (B) and alefinically unsaturated compounds (C) conversely, the branched structure of inferring its cured article can become very many and lose its structural degree of freedom, and becoming is difficult to orientation, thereby cannot reach effect of the present invention.
the effect of invention
Tackiness agent of the present invention especially can be applicable to optics purposes, operability (viscosity), optical characteristics (mist degree) excellence of the binder layer after solidifying by active energy beam and/or heat, even under the environment of high temperature, high humidity, optical laminate, especially the cementability of the optics such as Polarizer and glass substrate is also excellent, between binder layer and glass substrate, do not bubble, peel off, can obtain not producing the liquid crystal indicator of irregular colour, light leak.
Embodiment
The present invention is described in detail below, but an example of desirable embodiment is only shown here.
In addition, in the present invention, (methyl) vinylformic acid refers to acrylic or methacrylic acid, and (methyl) acryl refers to acryl or methacryloyl, and (methyl) acrylate refers to acrylate or methacrylic ester.
First, binder composition of the present invention [I] is described.
The composition that the alefinically unsaturated compounds (C) that binder composition of the present invention [I] is olefinic unsaturated groups more than containing acrylic resin (A), contain the aromatics (B) of 1 olefinic unsaturated group and containing 2 forms.
Acrylic resin used in the present invention (A) is that monomer (a1) is principal constituent for take (methyl) alkyl acrylate, as required the monomer that contains functional group (a2) is formed as copolymer composition copolymerization, and then monomer (a3) that also can copolymerization using other is as copolymer composition.Acrylic resin in the present invention (A) is used the monomer (a2) that contains functional group as copolymer composition, from becoming the cross-linking set of acrylic resin (A), make the further viewpoint rising of adaptation of base material, adherend consider it is preferred.
As this (methyl) alkyl acrylate, be monomer (a1), the carbonatoms of alkyl is preferably 1～20 conventionally, be particularly preferably 1～12, more preferably 1～8, especially be preferably 4～8, particularly can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-propyl, the just own ester of (methyl) vinylformic acid, (methyl) 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) vinylformic acid cetyl, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc.They can use separately a kind of or be used in combination of two or more.
Should (methyl) alkyl acrylate be in monomer (a1), from copolymerizable, bonding physical property, processing ease and raw material, obtaining the viewpoint of easiness considers, preferably use (methyl) n-butyl acrylate, (methyl) 2-EHA, more preferably from the viewpoint of excellent in te pins of durability, consider to use (methyl) n-butyl acrylate.
Content when making (methyl) alkyl acrylate be monomer (a1) copolymerization, overall with respect to copolymer composition, be preferably 10～100 % by weight, be particularly preferably 50～99 % by weight, 80～98 % by weight more preferably, when the content of (methyl) acrylic ester monomer (a1) is very few, adhesiveproperties has the tendency of reduction.
As the monomer that contains functional group (a2); can list that contain can be by reacting the monomer of the functional group that becomes cross-linking set with aftermentioned linking agent (E); such as can list hydroxyl monomer, containing carboxylic monomer, emulsion stability, containing acetoacetyl monomer, containing isocyanate group monomer, containing glycidyl monomer etc.; in these; from effectively carrying out the viewpoint of crosslinking reaction, preferably use hydroxyl monomer, contain carboxylic monomer.
As hydroxyl monomer, can list for example (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 5-hydroxyl pentyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, the vinylformic acid hydroxyalkyl acrylates such as (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the caprolactone modification monomers such as caprolactone modification (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid binaryglycol ester, alkylidene oxide (oxyalkylene) modified monomers such as (methyl) polyalkylene glycol acrylate ester, in addition can list for example 2-acrylyl oxy-ethyl 2-hydroxyethyl phthalic acid, the monomer that N-methylol (methyl) acrylamide etc. contains primary hydroxyl, the monomer that (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 3-chlorine-2-hydroxyl propyl ester etc. contain secondary hydroxyl, (methyl) vinylformic acid 2, the monomer that 2-dimethyl-2 hydroxy methacrylate etc. contains tert-hydroxyl.
In above-mentioned hydroxyl monomer, from the viewpoint of the reactivity excellence with linking agent (E), consider, the monomer that preferably contains primary hydroxyl, and then, preferably being used as the ratio that contains of impurity two (methyl) acrylate is the hydroxyl monomer below 0.5%, more preferably use below 0.2%, particularly the hydroxyl monomer below 0.1%.Particularly, preferred vinylformic acid 2-hydroxy methacrylate, vinylformic acid 4-hydroxyl butyl ester.
As containing carboxylic monomer, such as listing (methyl) vinylformic acid, acrylic acid dimer, β-crotonic acid, toxilic acid, maleic anhydride, fumaric acid, citraconic acid, propene dicarboxylic acid, methylene-succinic acid, acrylamide N-glycolic acid, TRANSCINNAMIC ACID etc., wherein preferably use (methyl) vinylformic acid.
As emulsion stability, such as listing (methyl) vinylformic acid tertiary butyl amino ethyl ester, (methyl) vinylformic acid ethylamino ethyl ester, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester etc.
As containing acetoacetyl monomer, such as listing (methyl) vinylformic acid 2-(acetoacetoxy groups) ethyl ester, acetoacetic acid allyl ester etc.
As containing isocyanate group monomer, such as listing 2-acrylyl oxy-ethyl isocyanic ester, 2-methylacryoyloxyethyl isocyanic ester, their alkylidene oxide affixture etc.
As containing glycidyl monomer, such as listing (methyl) glycidyl acrylate, (methyl) vinylformic acid allyl glycidyl etc.
These monomers that contain functional group (a2), can use separately also can be used in combination two or more.
As make to contain functional group monomer (a2) copolymerization time content, overall with respect to copolymer composition, be preferably 0～30 % by weight, be particularly preferably 0.1～10 % by weight, 0.2～3 % by weight more preferably, when the content of the monomer that contains functional group (a2) is too much, viscosity uprises, and the stability of resin has the tendency of reduction.
As other co-polymerized monomer (a3), such as the monomer that can list (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid phenoxy group binaryglycol ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, vinylbenzene, alpha-methyl styrene etc. and contain 1 aromatic nucleus, the monomer that biphenyl acrylate, (methyl) vinylformic acid biphenylyloxy ethyl ester, (methyl) vinylformic acid biphenyl oxyalkyl ester etc. contain xenyl, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 3-methoxyl group butyl ester, (methyl) vinylformic acid 2-butoxyethyl, (methyl) vinylformic acid 2-butoxy binaryglycol ester, (methyl) vinylformic acid methoxyl group binaryglycol ester, (methyl) vinylformic acid methoxyl group triglycol ester, (methyl) vinylformic acid oxyethyl group binaryglycol ester, (methyl) vinylformic acid methoxyl group dipropylene glycol ester, the monomer that (methyl) vinylformic acid methoxy poly (ethylene glycol) ester etc. contains alkoxyl group and alkylidene oxide, alkoxyalkyl (methyl) the acrylamide monomers such as methoxymethyl (methyl) acrylamide, ethoxyl methyl (methyl) acrylamide, propoxy-methyl (methyl) acrylamide, n-butoxy methyl (methyl) acrylamide, isobutoxy methyl (methyl) acrylamide, (methyl) acrylamide monomers such as (methyl) acryloyl morpholine, dimethyl (methyl) acrylamide, diethyl (methyl) acrylamide, (methyl) acrylamide N-methylol (methyl) acrylamide, vinyl cyanide, methacrylonitrile, vinyl acetate etc.
Content when making other co-polymerized monomer (a3) copolymerization, overall with respect to copolymer composition, be preferably 0～30 % by weight, be particularly preferably 1～20 % by weight, 2～10 % by weight more preferably, when the content of other co-polymerized monomer (a3) is too much, have to obtain effect of the present invention and become difficult tendency.
In addition, while turning to object with high molecular, can be used in combination the compound etc. that two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid binaryglycol ester, two (methyl) vinylformic acid triglycol ester, two (methyl) polyalkylene glycol acrylate ester, two (methyl) vinylformic acid propylene glycol ester, Vinylstyrene etc. have 2 above olefinic unsaturated groups.
By the monomer component polymerization of above-mentioned (a1)～(a3) is manufactured to acrylic resin (A), this polymerization can be undertaken by existing known methods such as solution free radical polymerization, suspension polymerization, mass polymerization, letex polymerizations.Such as mixing in organic solvent or dripping (methyl) alkyl acrylate, be monomer (a1), the monomer (a2) that contains functional group, other polymerization single polymerization monomer, the polymerization starters such as co-polymerized monomer (a3), and with reflux state or polymerization 2～20 hours at 50～90 ℃.
As the organic solvent for this polymerization, the ketones such as aliphatics alcohols, acetone, methylethylketone, mibk, pimelinketone such as ester class, n-propyl alcohol, Virahol such as toluene, dimethylbenzene etc. are aromatic hydrocarbon based such as listing, methyl acetate, ethyl acetate, butylacetate etc.
As the polymerization starter in this free-radical polymerized middle use, as concrete example, can list the azos such as the two methyl pentane nitriles of azobis isobutyronitrile, azo that belong to common radical polymerization initiator is the peroxidation system polymerization starters such as polymerization starter, benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, isopropyl benzene hydroperoxide etc.
The weight-average molecular weight of acrylic resin (A) is generally 100,000～3,000,000, is preferably 300,000～2,500,000, is particularly preferably 600,000～2,000,000, is especially preferably 1,000,000～1,800,000.When weight-average molecular weight is too small, endurance quality has the tendency of reduction, needs Macrodilution solvent when excessive, from the viewpoint of coating, cost, has not preferably tendency.
In addition, the dispersity (weight-average molecular weight/number-average molecular weight) of acrylic resin (A) is preferably below 20, is particularly preferably below 10, more preferably, below 7, is especially preferably below 4.When this dispersity is too high, the endurance quality of binder layer reduces, and has the tendency of easy foaming.Wherein, the lower limit of dispersity is considered from the viewpoint of manufacturing limit, is generally 2.
And then the second-order transition temperature of acrylic resin (A) is preferably-80～-20 ℃, be particularly preferably-75～-30 ℃, more preferably-60～-40 ℃, when second-order transition temperature is too high, there is the bonding force excessive tendency that rises, the tendency that has thermotolerance to reduce when too low.
In addition, above-mentioned weight-average molecular weight is the weight-average molecular weight converting based on polystyrene standard molecular weight, is at high performance liquid chromatography (Japanese Waters company's manufacture " Waters2695 (body) " and 3 root chromatogram columns that in " Waters2414 (detector) ", use is connected: Shodex GPC KF-806L (exclusion limit molecular weight: 2 * 10 7, separating ranges: 100～2 * 10 7, theoretical plate number: 10000 sections/, filler material: styrene diethylene benzene copoly mer, packing material size: 10 μ m) measure and the value that obtains, number-average molecular weight also can make to use the same method.Dispersity can be tried to achieve by weight-average molecular weight and number-average molecular weight in addition.In addition, second-order transition temperature is calculated by Fox formula.
[mathematical expression 1]
1 Tg = Wa Tga + Wb Tgb + . . . + Wn Tgn
Tg: the second-order transition temperature of multipolymer (K)
Tga: the second-order transition temperature of the homopolymer of monomer A (K) Wa: the weight fraction of monomer A
Tgb: the second-order transition temperature of the homopolymer of monomers B (K) Wb: the weight fraction of monomers B
Tgn: the second-order transition temperature of the homopolymer of monomer N (K) Wn: the weight fraction of monomer N
(Wa+Wb+…+Wn＝1)
In addition, in the present invention, by balance meeting well weather resistance and the viewpoint that suppresses light leak, the acrylic resin (A2) that the acrylic resin (A1) that preferably combination use side chain contains hydroxyl and side chain contain carboxyl is as acrylic resin (A).
On be set forth in the acrylic resin (A1) that side chain contains hydroxyl (being sometimes called for short below " acrylic resin (A1) "), so long as the acrylic resin that contains hydroxyl at side chain, such as can list method by making hydroxyl monomer copolymerization, the functional group of the acrylic resin that makes to contain functional group and having concurrently can react with the functional group of this functional group reactions and the compound of hydroxyl the material that the method etc. of (post-modification) is manufactured.
In the middle of them, while manufacturing from industry, can obtain easily the viewpoint of the acrylic resin (A1) that side chain contains hydroxyl, use is by the copolymer composition that contains hydroxyl monomer and other copolymer composition copolymerization and the resin obtaining is preferred, this acrylic resin (A1) can obtain as follows: as form aforesaid propylene acid be resin (A) containing monomer (a2), use hydroxyl monomer as neccessary composition.
In addition, acrylic resin (A1) does not preferably contain containing carboxylic monomer in fact as the copolymer composition beyond hydroxyl monomer, does not more preferably in fact contain the monomer containing other functional group beyond carboxyl yet." do not contain in fact " and refer to that the ratio that contains of above-mentioned monomer is below 1 % by weight, be preferably below 0.1 % by weight, be particularly preferably and do not contain.
The acrylic resin that above-mentioned side chain contains carboxyl (A2) (below sometimes referred to as " acrylic resin (A2) "), so long as the acrylic resin that side chain contains carboxyl, such as can list by making method containing carboxylic monomer copolymerization, the functional group and the material simultaneously with the manufactures such as method that can react with the functional group of this functional group reactions and the compound of carboxyl (post-modification) of the acrylic resin that makes to contain functional group.
In the middle of them, use will contain containing the copolymer composition of carboxylic monomer and the material of other copolymer composition copolymerization, the viewpoint that can obtain easily the acrylic resin (A2) that side chain contains carboxyl while manufacturing from industry is preferred, this acrylic resin (A2) can obtain as follows: as forming the monomer (a2) containing functional group that aforesaid propylene acid is resin (A), use containing carboxylic monomer as neccessary composition.
In addition, acrylic resin (A2) does not preferably contain in fact hydroxyl monomer as the copolymer composition beyond hydroxyl monomer, does not more preferably in fact contain the monomer of hydroxyl other functional group in addition yet." do not contain in fact " and refer to that the ratio that contains of above-mentioned monomer is below 1 % by weight, be preferably below 0.1 % by weight, be particularly preferably and do not contain.
When being used in combination acrylic resin (A1) and acrylic resin (A2), when acrylic resin (A1) lacks with the difference of the weight-average molecular weight of acrylic resin (A2), can improve the force of cohesion of the polymer network after being cross-linked and improve weather resistance, so preferably, particularly, the ratio of the weight-average molecular weight of acrylic resin (A1) and acrylic resin (A2) ((A1)/(A2)) is preferably (A1)/(A2)=0.5～1.5, more preferably (A1)/(A2)=0.8～1.2, more preferably (A1)/(A2)=0.9～1.1.
Acrylic resin (A1) is preferably (A1) with the compounding ratio (weight ratio) of acrylic resin (A2): (A2)=50:50～99:1, be particularly preferably (A1): (A2)=60:40～95:5, more preferably (A1): (A2)=70:30～90:10.
Acrylic resin (A1) with respect to acrylic resin (A2) containing proportional when too much, exist with ... linking agent addition, have gel fraction occurs significantly to rise, the tendency that weather resistance, resistance to light leak reduce, has the bonding force excessive tendency that rises when very few.
Herein, in binder composition [I] contained hydroxyl and carboxyl containing proportional (mol ratio), be preferably hydroxyl/carboxyl=0.15～20, be particularly preferably hydroxyl/carboxyl=0.5～10, more preferably hydroxyl/carboxyl=1.5～2.5.Hydroxyl when too much, exists with ... linking agent addition containing proportional to carboxyl, has the gel fraction of generation significantly to rise, and the tendency that causes weather resistance, resistance to light leak to reduce has the bonding force excessive tendency that rises when very few.
In addition, hydroxyl, carboxyl in above-mentioned binder composition [I], be preferably the functional group that comes from fact acrylic resin (A1) and acrylic resin (A2), but also can be the hydroxyl, the carboxyl that come from other constituent, as long as be in above-mentioned scope in binder composition [I].
As the aromatics that contains 1 olefinic unsaturated group (B) using in the present invention (below sometimes referred to as " simple function aromatics (B) "; so long as there is the compound of aromatic nucleus and 1 olefinic unsaturated group in molecule; the functional group of containing olefinic unsaturated group as this, can list (methyl) acryl, crotonyl, vinyl, allyl group etc.
As simple function aromatics (B); in its structure; compound for containing (methyl) acryl among above-mentioned functional group; during single (methyl) acrylate based compound, the viewpoint of easily reacting when by active energy beam and/or thermofixation considers it is preferred.
The number of the aromatic nucleus containing as simple function aromatics (B), can contain 1 also can contain a plurality of, from obtaining the viewpoint of the balance of sticky object, consider, be preferably the compound that contains 1 aromatic nucleus, good from efficiency, can control the specific refractory power of adhesive linkage, birefringent viewpoint is considered, is preferably the compound that contains 2 aromatic nucleus.
As above-mentioned simple function aromatics (B), particularly, can list ether is that simple function aromatics (b1), ester are simple function aromatics (b2) etc., as ether, be simple function aromatics (b1), such as listing phenol, be the dihydroxy benzene derivatives such as derivative, pyrocatechol, Resorcinol, quinhydrones etc., as the simple function aromatics (b2) of ester system, such as listing benzoic acid derivative, phthalic acid derivatives etc.
As phenol derivatives; the derivative (b1-1) of the structure that the structure position that preferably hydrogen atom of the hydroxyl of phenol is contained (methyl) acryl replaces; as dihydroxy benzene derivatives, the derivative (b1-2) that the structure position that wherein one or two hydrogen atom of 2 hydroxyls that preferably Resorcinol has is contained (methyl) acryl replaces.
The structure position that contains (methyl) acryl as this, the preferred material representing with following general formula (1) that also contains alkylidene oxide structure.
[Chemical formula 1]
(in formula, R is hydrogen atom or methyl, and X is alkylidene group, and n is more than 1 integer.)
X in above-mentioned general formula (1) is alkylidene group, is wherein preferably the alkylidene group of carbonatoms 1～10, is particularly preferably the alkylidene group of the carbonatomss 1～4 such as ethylidene, propylidene, tetramethylene, is especially preferably ethylidene.
When n is more than 2 polyoxyalkylene chain positions, can be the homopolymer of same alkylidene oxide chain, also can be different alkylidene oxide chains with the multipolymer of random or block-wise.
In addition, above-mentioned alkylidene group also can have substituting group, as substituting group, conventionally can list halogen atom, hydroxyl, alkoxyl group, amino, sulfanyl (sulfanyl), aryl, heteroaryl etc., is wherein preferably hydroxyl.
N in above-mentioned general formula (1) is more than 1 integer, is preferably 1～10, is particularly preferably 1～2, more preferably 2.When this n value is excessive, the humidity resistance of acrylic resin has the tendency of reduction, and in addition, in order to control specific refractory power, double refraction, alkylidene group, alkylidene oxide structure are advisable with shorter one, and n is little is preferred.
Concrete example as above-mentioned (b1-1), for example can list (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid diethylamino phenyl diol ester, (methyl) vinylformic acid phenyl triglycol ester, (methyl) vinylformic acid phenyl TEG ester, the repeat number of the ethylene glycol structures such as (methyl) vinylformic acid phenyl eight glycol esters is (methyl) vinylformic acid phenyl macrogol ester of 2～8 (being preferably 2～4), (methyl) vinylformic acid phenoxy group propyl ester, (methyl) vinylformic acid phenyl dipropylene glycol ester, (methyl) vinylformic acid phenyl polypropylene glycol ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid ethoxyquin phenyl phenyl ester, (methyl) vinylformic acid Nonylphenoxy ethyl ester, the repeat number of the ethylene glycol structures such as (methyl) vinylformic acid nonyl phenyl binaryglycol ester is (methyl) vinylformic acid nonyl phenyl macrogol ester of 2～8 (being preferably 2～4), (methyl) vinylformic acid Nonylphenoxy propyl ester, the repeat number of the propylene glycol structures such as (methyl) vinylformic acid nonyl phenyl dipropylene glycol ester is (methyl) vinylformic acid nonyl phenyl polypropylene glycol ester of 2～8 (being preferably 2～4) etc., (OSAKA ORGANIC CHEMICAL INDUSTRY LTD. manufactures as commercially available product, can to list vinylformic acid phenoxy group macrogol ester, trade(brand)name " viscoat#193 "), (OSAKA ORGANIC CHEMICAL INDUSTRY LTD. manufactures vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, trade(brand)name " viscoat#220 ", vinylformic acid phenoxy group binaryglycol ester (kyoeisha Chemical Co., Ltd. manufacture, trade(brand)name " Light acrylate P2HA ", (Hitachi Chemical Co., Ltd. manufactures vinylformic acid phenyl triglycol ester, trade(brand)name " phenoxy triethyleneglycol acrylate "), (Hitachi Chemical Co., Ltd. manufactures vinylformic acid phenyl TEG ester, trade(brand)name " phenoxy tetraethyleneglycol acrylate "), (Hitachi Chemical Co., Ltd. manufactures vinylformic acid nonyl phenyl chlorocarbonate, trade(brand)name " nonyl phenoxy ethyl acrylate "), (Hitachi Chemical Co., Ltd. manufactures vinylformic acid nonyl phenyl binaryglycol ester, trade(brand)name " nonyl phenoxy diethylene glycol acrylate "), (Hitachi Chemical Co., Ltd. manufactures vinylformic acid nonyl phenyl TEG ester, trade(brand)name " nonyl phenoxy tetraethylene glycol acrylate "), (Hitachi Chemical Co., Ltd. manufactures vinylformic acid nonyl phenyl eight glycol esters, trade(brand)name " nonyl phenoxy octaethylene glycol acrylate "), (Hitachi Chemical Co., Ltd. manufactures (methyl) vinylformic acid nonyl phenyl polypropylene glycol ester, trade(brand)name " nonyl phenoxy plypropylene glycol (meta) acrylate "), the adjacent phenyl phenyl ester of vinylformic acid ethoxyquin (Shin Nakamura Chemical Co., Ltd. manufacture, trade(brand)name " NK ester A-LEN-10 ") etc.
As benzoic acid derivative; be preferably the derivative (b2-1) of the structure that structure position that the hydrogen atom of benzoic carboxyl contained (methyl) acryl replaces; as phthalic acid derivatives, be preferably the derivative (b2-2) of the structure that one of them of 2 carboxyls that phthalic acid has or structure position that two hydrogen atoms are contained (methyl) acryl replace.
The structure position that contains (methyl) acryl as this, is preferably the material that aforementioned formula (1) represents.
Concrete example as said derivative (b2-2) can list phthalic acid 2-acrylyl oxy-ethyl-2-hydroxy propyl ester (the OSAKA ORGANIC CHEMICAL INDUSTRY LTD. manufacture as commercially available product, trade(brand)name " viscoat#2311HP "), (OSAKA ORGANIC CHEMICAL INDUSTRY LTD. manufactures 2-acrylyl oxy-ethyl hydrogen phthalic ester, trade(brand)name " viscoat#2000 "), (OSAKA ORGANIC CHEMICAL INDUSTRY LTD. manufactures 2-acryloyl-oxy propyl group hydrogen phthalic ester, trade(brand)name " viscoat#2100 "), 2-methylacryoyloxyethyl phthalic acid (Shin Nakamura Chemical Co., Ltd. manufacture, trade(brand)name " CB-1 ") etc.
Simple function aromatics (B) used in the present invention, as previously mentioned, so long as there is the compound of aromatic nucleus and 1 olefinic unsaturated group in molecule, just have no particular limits, but be particularly preferably the material that molecule contains 2 above aromatic nucleus, sulphur atom or bromine atoms.
Aromatic nucleus, sulphur atom, bromine atoms are known as the high structure of specific refractory power and easily import the structure of Acrylic Acid Monomer, by these structures being imported to the side chain (being preferably on side chain the position away from main chain) of acrylic resins, the double refraction composition producing in the time of can making the whole stress application of acrylic adhesive layer rises very well in the specific refractory power efficiency of draw direction one side (x axle one side).
Result, in the tackiness agent that contains acrylic resin in (methyl) alkyl acrylate main body that makes to rise with respect to specific refractory power perpendicular to draw direction (y axle side), forms with the total of the polymkeric substance of above-mentioned simple function compound (B), the double refraction of binder layer is cancelled, and can become and is difficult for occurring birefringent binder layer and suppresses light leak with good efficiencies.
The structure position that meets " containing 2 above aromatic nucleus, sulphur atom or bromine atoms " condition containing as simple function aromatics (B), can list biphenyl structural, naphthalene structure, anthracene structure, benzene sulphur structure, bromobenzene structure etc., wherein biphenyl structural, benzene sulphur structure consider it is preferred from the viewpoint that effectively provides positive double refraction to improve effect.
For above-mentioned simple function aromatics (B), (methyl) acrylate based compound that particularly can list (methyl) acrylate based compound that contains biphenyl structural, (methyl) acrylate based compound that contains benzene sulphur structure, (methyl) acrylate based compound that contains naphthalene structure, contains bromobenzene structure etc.
(methyl) acrylate based compound that contains biphenyl structural as this, can list (methyl) biphenyl acrylate, (methyl) vinylformic acid biphenyl oxyalkyl ester, the poly-alkyl diol ester of stretching of (methyl) vinylformic acid biphenyl.
As this (methyl) vinylformic acid biphenyl oxyalkyl ester, (methyl) vinylformic acid biphenyl oxyalkyl ester that the carbonatoms that can list alkyl is 1～8, particularly can list (methyl) vinylformic acid biphenyl oxygen methyl esters, (methyl) vinylformic acid biphenyl 2-ethoxyethyl acetate, (methyl) vinylformic acid biphenyl oxygen propyl ester etc.
As this (methyl) vinylformic acid biphenyl polyalkylene glycol ester, the carbonatoms that can list alkylidene group is 1～8, the number of repeat unit of alkylene glycol chain is (methyl) vinylformic acid biphenyl polyalkylene glycol of 2～10, particularly can list (methyl) vinylformic acid biphenyl binaryglycol ester, (methyl) vinylformic acid biphenyl triglycol ester, (methyl) vinylformic acid biphenyl TEG ester, (methyl) vinylformic acid biphenyl dipropylene glycol ester, (methyl) vinylformic acid biphenyl macrogol ester, (methyl) vinylformic acid biphenyl polypropylene glycol ester etc.
In the middle of them, preferred (methyl) vinylformic acid biphenyl polyalkylene glycol ester, (methyl) vinylformic acid biphenyl macrogol ester from providing efficiently the viewpoint of positive photoelasticity effect to consider particularly preferably, (methyl) vinylformic acid biphenyl polyoxyethylene glycol that more preferably number of repeat unit of glycol chain is 1～4.
(methyl) acrylate based compound that contains benzene sulphur structure as this, can list (methyl) vinylformic acid benzene thioesters, (methyl) vinylformic acid benzene sulfanyl ester etc., as this (methyl) vinylformic acid phenyl sulfanyl ester, (methyl) vinylformic acid phenyl sulfanyl ester that the carbonatoms that can list alkyl is 1～12, particularly can list (methyl) vinylformic acid benzene sulphur methyl esters, (methyl) vinylformic acid benzene sulphur ethyl ester, (methyl) vinylformic acid benzene sulphur propyl ester, (methyl) vinylformic acid benzene sulphur butyl ester, (methyl) vinylformic acid benzene sulphur pentyl ester, the own ester of (methyl) vinylformic acid benzene sulphur, (methyl) vinylformic acid benzene sulphur heptyl ester, (methyl) vinylformic acid benzene sulphur monooctyl ester, (methyl) vinylformic acid benzene sulphur ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid benzene sulphur ester in the last of the ten Heavenly stems etc.
In the middle of them, preferred (methyl) vinylformic acid benzene sulfanyl ester, particularly preferably (methyl) vinylformic acid benzene sulphur ethyl ester from can effectively providing the viewpoint of positive photoelasticity effect to consider, more preferably vinylformic acid benzene sulphur ethyl ester.
(methyl) acrylic compound that contains naphthalene structure as this, can list (methyl) vinylformic acid naphthyloxy ester, (methyl) vinylformic acid naphthyloxy methyl esters, (methyl) vinylformic acid naphthyloxy ethyl ester, (methyl) vinylformic acid naphthyloxy propyl ester etc.
(methyl) acrylate that contains bromobenzene structure as this, can list (methyl) vinylformic acid bromine phenoxy group methyl esters, (methyl) vinylformic acid dibromo-phenoxy base methyl esters, (methyl) vinylformic acid tribromophenoxy methyl esters, (methyl) vinylformic acid tetrabromo phenoxy group methyl esters, (methyl) vinylformic acid pentabromo-phenoxy group methyl esters, (methyl) vinylformic acid bromine phenoxy ethyl, (methyl) vinylformic acid dibromo-phenoxy base ethyl ester, (methyl) vinylformic acid tribromophenoxy ethyl ester, (methyl) vinylformic acid tetrabromo phenoxy ethyl, (methyl) vinylformic acid pentabromo-phenoxy ethyl, (methyl) vinylformic acid bromine phenoxy group propyl ester, (methyl) vinylformic acid dibromo-phenoxy base propyl ester, (methyl) vinylformic acid tribromophenoxy propyl ester, (methyl) vinylformic acid tetrabromo phenoxy group propyl ester, (methyl) vinylformic acid phenoxyalkyl ester that the phenyl ring such as (methyl) vinylformic acid pentabromo-phenoxy group propyl ester replace through 1～5 bromine atoms.
Wherein, the carbonatoms of alkyl is generally 1～12.
In addition, as simple function aromatics (B), during not containing easy functional group of reacting with acrylic resin (A), linking agent (E), from by containing the cross-linked network of acrylic resin (A), thereby causing the viewpoint that simple function aromatics (B) and the possibility that degree of freedom is lost, resistance to light leak improved effect reduces of the cured article of alefinically unsaturated compounds (C) are few to consider, is preferred.
In above-mentioned simple function aromatics (B), be particularly preferably vinylformic acid phenyl macrogol ester (number of repeat unit of polyoxyethylene glycol is 2～4), vinylformic acid Nonylphenoxy ethyl ester, vinylformic acid nonyl phenyl macrogol ester (number of repeat unit of polyoxyethylene glycol is 2～4), vinylformic acid Nonylphenoxy propylene glycol ester, vinylformic acid nonyl phenyl polypropylene glycol ester (number of repeat unit of polypropylene glycol is 2～4), vinylformic acid biphenyl 2-ethoxyethyl acetate, (methyl) vinylformic acid biphenyl macrogol ester (number of repeat unit of polyoxyethylene glycol is 2～4).
This functional group particularly, any one or more in isocyanate group, hydroxyl, carboxyl.
As the weight-average molecular weight of simple function aromatics (B), be generally 200～10000, be preferably 210～1000, be particularly preferably 220～500.This weight-average molecular weight has the minimizing due to aromatic nucleus concentration to become to be difficult for adjusting birefringent tendency, while having tackiness agent dry when too small, easily to volatilize, be difficult to obtain the tendency of invention effect when excessive.
As simple function aromatics (B), preferably its flash-point, more than 120 ℃, is particularly preferably 145～500 ℃, more preferably 150～400 ℃, is especially preferably 160～300 ℃.When this flash-point is too high, there is the tendency that double refraction adjustment capability reduces because molecular weight increases, when too small, have because volatility rises, easily volatilization and be difficult to obtain the tendency of invention effect when tackiness agent is dry.
As the simple function aromatics (B) that meets this flash-point, such as listing vinylformic acid diethylamino phenyl diol ester (flash-point: 165 ℃), ethoxyquin orthoxenol acrylate (flash-point: 170～199 ℃) etc.[< reference value >, vinylformic acid phenoxy ethyl (flash-point: 139～141 ℃), benzyl acrylate (flash-point: 107 ℃)].
The content of simple function aromatics (B), is resin (A) with respect to 100 parts by weight of acrylic acid, is required to be 3～300 weight parts, is preferably 5～100 weight parts, and more preferably 8～60 weight parts, are especially preferably 25～45 weight parts.When the content of simple function aromatics (B) is too much, the tendency that has weather resistance to worsen together with resistance to light leak, the tendency that has resistance to light leak to reduce when very few.
As the spendable ethene unsaturates (C) (below sometimes referred to as " multi-functional unsaturated compound (C) ") that contains 2 above olefinic unsaturated groups of the present invention, it is for example the ethylene unsaturated monomer that 1 molecule contains 2 above olefinic unsaturated groups, for example can use the monomer that 2 functional monomers, 3 officials can be above, or (methyl) propenoic methyl carbamate based compound, epoxy (methyl) acrylate based compound, polyester (methyl) acrylate based compound.Among these, use ethylene unsaturated monomer, (methyl) propenoic methyl carbamate based compound, from curing speed, the viewpoint that arrives the excellent in stability of physical property, consider it is preferred.
As above-mentioned 2 functional monomers, so long as the monomer that contains 2 olefinic unsaturated groups for example can list two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid binaryglycol ester, two (methyl) vinylformic acid TEG ester, two (methyl) polyalkylene glycol acrylate ester, two (methyl) vinylformic acid propylene glycol ester, two (methyl) vinylformic acid dipropylene glycol ester, two (methyl) vinylformic acid polypropylene glycol ester, two (methyl) vinylformic acid butanediol ester, two (methyl) vinylformic acid DOPCP, oxyethane modified bisphenol A type two (methyl) acrylate, epoxy pronane modification bisphenol A-type two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,6-hexylene glycol oxyethane modification two (methyl) acrylate, two (methyl) vinylformic acid glyceryl ester, two (methyl) vinylformic acid pentaerythritol ester, ethylene glycol diglycidylether two (methyl) acrylate, Diethylene Glycol diglycidylether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, hydroxyl trimethylacetic acid modification two (methyl) vinylformic acid DOPCP, isocyanuric acid oxyethane modification diacrylate, 2-(methyl) acryl oxygen ethyl phosphate ester acid etc.
Monomer that can be above as above-mentioned 3 officials, so long as the monomer that contains 3 above olefinic unsaturated groups, for example can list three (methyl) vinylformic acid TriMethylolPropane(TMP), three (methyl) vinylformic acid pentaerythritol ester, four (methyl) vinylformic acid pentaerythritol ester, three (methyl) vinylformic acid dipentaerythritol ester, four (methyl) vinylformic acid dipentaerythritol ester, five (methyl) vinylformic acid dipentaerythritol ester, six (methyl) vinylformic acid dipentaerythritol ester, three (methyl) acryloyl-oxy oxyethyl group TriMethylolPropane(TMP), poly-(methyl) acrylate of the poly-dehydration of glycerine glyceryl ether, isocyanuric acid oxyethane modification three (methyl) acrylate, oxyethane modification five (methyl) vinylformic acid dipentaerythritol ester, oxyethane modification six (methyl) vinylformic acid dipentaerythritol ester, oxyethane modification three (methyl) vinylformic acid pentaerythritol ester, oxyethane modification four (methyl) vinylformic acid pentaerythritol ester, succsinic acid modification three (methyl) vinylformic acid pentaerythritol ester etc.
As above-mentioned (methyl) propenoic methyl carbamate based compound, for thering is (methyl) acrylate based compound of amino-formate bond in molecule, use by (methyl) the acrylic acid series compound that contains hydroxyl and multicomponent isocyanate based compound (as required, polyvalent alcohol based compound) by the material of known general method reaction gained, as its weight-average molecular weight, conventionally use 300～4000 material.
The content of multi-functional unsaturated compound (C), is resin (A) with respect to 100 parts by weight of acrylic acid, and it is desirable to is 0.01～30 weight part, is preferably 0.5～10 weight part, more preferably 1～5 weight part.When the content of multi-functional unsaturated compound (C) is too much, the tendency that has weather resistance, resistance to light leak all to reduce, has the tendency of resistance to light leak deficiency when very few.
In the present invention, from can suitably adjusting cross-linking density, suitably adjustment adhesion sense, and then the viewpoint that can obtain the balance of weather resistance is considered, total amount with respect to above-mentioned simple function aromatics (B) with multi-functional unsaturated compound (C), the containing ratio (mol%) and need be greater than 50mol% of simple function aromatics (B), be preferably more than 50mol% and be less than 100mol%, be particularly preferably 55～99mol%, more preferably 60～98mol%, is especially preferably 65～97mol%.
Total amount with respect to simple function aromatics (B) with multi-functional unsaturated compound (C), simple function aromatics (B) containing proportional when too small, because the content of multi-functional unsaturated compound (C) is many with respect to simple function aromatics (B) change, there is cross-linking density to rise excessively, the tendency of shortcoming adhesion sense.In addition, simple function aromatics (B) with respect to the total amount of simple function aromatics (B) and multifunctional unsaturated compound (C) containing proportional when excessive, because the content of multi-functional unsaturated compound (C) tails off with respect to simple function aromatics (B), there is cross-linking density to rise few, the tendency of poor durability.
In addition, to (A) of the present invention～(C) composition, about the photoelastic coefficient of measuring by aftermentioned method, the photoelastic coefficient of acrylic resin (A) is for negative, and the aromatics that contains 1 olefinic unsaturated group (B) is timing with the photoelastic coefficient of the cured article of the alefinically unsaturated compounds (C) that contains 2 above olefinic unsaturated groups, from can effectively eliminating birefringent viewpoint, consider it is preferred.
The invention provides will contain aforesaid propylene acid be resin (A), simple function aromatics (B) and multi-functional unsaturated compound (C) as the binder composition [I] of neccessary composition, the tackiness agent being solidified into by active energy beam and/or heat (active energy beam irradiates and/or heating).Describedly be cured as the polymerization (high molecular) by active energy beam and/or heat of simple function aromatics (B) and multi-functional unsaturated compound (C), thereby solidify.
In addition, acrylic resin (A) is when relating to reaction, be not limited to by active energy beam and/or the simple function aromatics (B) of heat and the high molecular of multi-functional unsaturated compound (C), also can be along with acrylic resin (A) and simple function aromatics (B), and occur to solidify with the high molecular of multi-functional unsaturated compound (C) etc.
Above-mentioned while being cured by active energy beam and/or heat, the viewpoint of the stable reaction from can make active energy beam irradiate time and/or during heating considers, preferred adhesive composition [I] also contains polymerization starter (D).
In addition, in the present invention, as by the curing method of above-mentioned binder composition [I], also can list above-mentioned except containing (A)～(C) composition or (D) composition, also contain the material of linking agent (E) as binder composition [I], and the method that it is cured and is cured by linking agent by active energy beam and/or heat.Wherein, while using linking agent (E), acrylic resin (A) preferably has functional group, by this functional group, is reacted and can be cured (being cross-linked) with linking agent.
In the present invention, above-mentioned solidifying by active energy beam and/or heat (active energy beam irradiates and/or heating), from the active energy beam of ultraviolet ray that can be by the utmost point short period of time etc., irradiate that its curing viewpoint is considered is preferred, and then, solidify (be cross-linked) that be used in combination by linking agent is also preferred, can obtain to improve the cross-linking density, raising force of cohesion of tackiness agent and make the material that weather resistance is more excellent.
As above-mentioned polymerization starter (D), such as using the various polymerization starters such as Photoepolymerizationinitiater initiater (d1), thermal polymerization (d2), particularly use Photoepolymerizationinitiater initiater (d1), it is preferred from the irradiation of ultraviolet isoreactivity energy-ray that can be by the utmost point short period of time, its curing viewpoint being considered.
In addition, while using above-mentioned Photoepolymerizationinitiater initiater (d1), by active energy beam, irradiate binder composition [I] is solidified, while using thermal polymerization (d2), by heating, binder composition [I] is solidified, but also preferably both are used in combination as required.
As this Photoepolymerizationinitiater initiater (d1), so long as because light action produces the material of free radical, have no particular limits, can use the interior Photoepolymerizationinitiater initiater (d1-1) of autothermic cracking type of molecule, the Photoepolymerizationinitiater initiater (d1-2) of hydrogen-abstraction.
The Photoepolymerizationinitiater initiater (d1-1) of autothermic cracking type in molecule, for example can list 4-phenoxy group dichloroacetophenone, 4-tertiary butyl dichloroacetophenone, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropylidene phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone, 4-(2-hydroxyl-oxethyl)-phenyl (2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl propane-1-ketone, benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin ethyl isobutyl ether, benzyl dimethyl ketal, alpha-acyloxy oxime ester, acylphosphine oxide, aminomethyl phenyl glyoxylic ester, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 4-benzoyl-4 '-methyldiphenyl sulphur etc., preferred 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone wherein, 1-hydroxycyclohexylphenylketone.
In addition, Photoepolymerizationinitiater initiater (d1-2) as hydrogen-abstraction, for example can list benzophenone, benzoyl phenylformic acid, benzoyl methyl benzoate, 4-phenyl benzophenone, dihydroxy benaophenonel, 3, 3 '-dimethyl-4-methoxy benzophenone, 2, 4, 6-tri-methyl benzophenone, 4-methyldiphenyl ketone, thioxanthone (thioxanthone), CTX, 2-methyl thioxanthone, 2, 4-dimethyl thioxanthone, isopropyl thioxanthone, camphorquinone, dibenzosuberone (Dibenzosuberone), 2-ethyl-anthraquinone, 3, 3 ', 4, 4 '-tetra-(tert-butyl hydroperoxide carbonyl) benzophenone, benzyl, 9, 10-phenanthrenequione etc., preferred benzophenone wherein, methyldiphenyl ketone, 2, 4, 6-tri-methyl benzophenone.
The present invention, from the viewpoint of excellent in te pins of durability, preferably uses the Photoepolymerizationinitiater initiater (d1-2) of hydrogen-abstraction,, from making the photo-crosslinking of surface part and the balance of inner photo-crosslinking of binder layer good, and the viewpoint consideration that improves of overall performance.Particularly preferably by the Photoepolymerizationinitiater initiater (d1-2) of the Photoepolymerizationinitiater initiater (d1-1) of autothermic cracking type in molecule and hydrogen-abstraction, both are used in combination
Combination as the Photoepolymerizationinitiater initiater of autothermic cracking type and the Photoepolymerizationinitiater initiater of hydrogen-abstraction, be preferably the 1-hydroxycyclohexylphenylketone of autothermic cracking type or benzophenone, the methyldiphenyl ketone or 2 of 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone and hydrogen-abstraction, the combination of 4,6-tri-methyl benzophenone.
In addition, auxiliary agent as Photoepolymerizationinitiater initiater as required, also can be used in combination trolamine, tri-isopropanolamine, 4,4 '-dimethylamino benzophenone (Michler's keton), 2-dimethyl aminoethyl phenylformic acid, EDMAB, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,4-diethyl thioxanthone, 2,4-di-isopropyl thioxanthone etc.These can use a kind of or be used in combination two or more.
In addition, as above-mentioned thermal polymerization (d2), for example, can list methylethyl ketone peroxide, cyclohexanone peroxide, peroxidation methylcyclohexanone, methyl acetoacetate superoxide, diacetone peroxide, two (the tertiary hexyl peroxides)-3,3 of 1,1-, 5-trimethyl-cyclohexane, two (tertiary hexyl the peroxide)-hexanaphthenes of 1,1-, two (t-butyl peroxy)-3,3 of 1,1-, 5-trimethyl-cyclohexane, two (the t-butyl peroxy)-2-methylcyclohexanes of 1,1-, two (the t-butyl peroxy)-hexanaphthenes of 1,1-, two (t-butyl peroxy) cyclododecanes of 1,1-, two (t-butyl peroxy) butane of 1,1-, two (4, the 4-di-t-butyl peroxide cyclohexyl) propane of 2,2-, to menthane hydrogen peroxide, di-isopropylbenzene hydroperoxide, 1，1，3，3-tetramethylbutylhydro-peroxide, hydrogen phosphide cumene, tertiary hexyl hydrogen peroxide, tertbutyl peroxide, α, α '-bis-(t-butyl peroxy) diisopropylbenzene(DIPB), dicumyl peroxide, 2,5-dimethyl-2, two (t-butyl peroxy) hexanes of 5-, tert-butyl peroxide isopropyl benzene, ditertiary butyl peroxide, 2,5-dimethyl-2, two (the t-butyl peroxy)-3-hexins of 5-, peroxidation isobutyryl, peroxidation 3,5,5-trimethyl acetyl, peroxidation decoyl, lauroyl peroxide, stearoyl, peroxysuccinic acid, m-toluyl peroxide benzoyl, benzoyl peroxide, peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, two (4-tert-butylcyclohexyl) esters of peroxy dicarbonate, peroxy dicarbonate two-2-ethoxy ethyl ester, the own ester of peroxy dicarbonate two-2-oxyethyl group, peroxy dicarbonate two-3-methoxyl group butyl ester, peroxide-butyl carbonate, peroxy dicarbonate two (3-methyl-3-methoxyl group butyl) ester, α, α '-bis-(new decanoyl peroxide) diisopropylbenzene(DIPB), peroxidation neodecanoic acid isopropyl phenyl ester, peroxidation neodecanoic acid 1,1,3,3-tetramethyl-butyl ester, peroxidation neodecanoic acid 1-cyclohexyl-1-methyl ethyl ester, the tertiary own ester of peroxidation neodecanoic acid, new peroxide tert-butyl caprate, the tertiary own ester of peroxidation PIVALIC ACID CRUDE (25), tert-Butyl peroxypivalate, peroxidation-2 ethyl hexanoic acid 1,1,3,3-tetramethyl-butyl ester, 2,5-dimethyl-2, two (the 2-ethyl hexyl acyl group peroxide) capronates of 5-, peroxidation-2 ethyl hexanoic acid 1-cyclohexyl-1-methyl ethyl ester, the tertiary own ester of peroxidation-2 ethyl hexanoic acid, peroxide-2-ethyl hexanoic acid tert-butyl, the tertiary own ester of peroxidation sec.-propyl list carbonic acid, peroxidation tert-butyl isobutyrate, the peroxidation toxilic acid tert-butyl ester, peroxidation-3,5,5 Trimethylhexanoic acid tert-butyl ester, the peroxidation lauric acid tert-butyl ester, the peroxidation sec.-propyl list carbonic acid tert-butyl ester, peroxidation-2-ethylhexyl list carbonic acid tert-butyl ester, peroxide acetic acid butyl ester, peroxidation-toluoyl t-butyl perbenzoate, peroxidized t-butyl perbenzoate, two (t-butyl peroxy) isophthalic acid ester, 2,5-dimethyl-2, two (toluoyl peroxide) hexanes of 5-, the tertiary own ester of benzoyl peroxide formic acid, 2,5-dimethyl-2, two (benzoyl peroxide) hexanes of 5-, the peroxidation alkylene propyl group list carbonic acid tert-butyl ester, tertiary butyl trimethyl silyl superoxide, 3,3 ', 4,4 '-tetra-(t-butyl peroxy carbonyl) benzophenone, 2,3-dimethyl-2, the organo-peroxide series initiators such as 3-diphenyl butane, 2-phenylazo-4-methoxyl group-2,4-methyl pentane nitrile, 1-[(1-cyano group-1-methylethyl) azo] methane amide, 1,1 '-azo two (hexanaphthene-1-nitrile), 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile), 2, two (the 2-methyl-prop amidine) dihydrochlorides of 2 '-azo, 2, two (2-methyl-N-phenyl the third amidine) dihydrochlorides of 2 '-azo, 2, two [N-(4-the chloro-phenyl-)-2-methyl-prop amidine] dihydrochlorides of 2 '-azo, 2, two [N-(4-hydrogen the phenyl)-2-methyl-prop amidine] dihydrochlorides of 2 '-azo, 2, two [2-methyl-N-(phenyl methyl) the third amidine] dihydrochlorides of 2 '-azo, 2, two [2-methyl-N-(2-propenyl) the third amidine] dihydrochlorides of 2 '-azo, 2, two [N-(2-the hydroxyethyl)-2-methyl-prop amidine] dihydrochlorides of 2 '-azo, 2, two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane] dihydrochlorides of 2 '-azo, 2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochlorides of 2 '-azo, 2, two [2-(4,5,6,7-tetrahydrochysene-1H-1, the 3-diazepine-2-yl) propane] dihydrochlorides of 2 '-azo, 2, two [2-(3,4,5, the 6-tetrahydropyrimidine-2-yl) propane] dihydrochlorides of 2 '-azo, 2, two [2-(5-hydroxyl-3,4,5, the 6-tetrahydropyrimidine-2-yl) propane] dihydrochlorides of 2 '-azo, 2, two [2-[1-(2-the hydroxyethyl)-2-tetrahydroglyoxaline-2-yl] propane of 2 '-azo] dihydrochloride, 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane], 2,2 '-azo two [2-methyl-N-[1, two (the methylol)-2-hydroxyethyls of 1-] propionic acid amide], 2,2 '-azo two [2-methyl-N-[1, two (methylol) ethyls of 1-] propionic acid amide], 2,2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide], 2,2 '-azo two (2-methyl propanamide), 2,2 '-azo two (2,4,4-trimethylpentane), 2,2 '-azo two (2-methylpropane), dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), 4,4 '-azo two (4-cyanopentanoic acid), 2, the azo series initiators such as 2 '-azo two [2-(methylol) propionitrile], Deng.In addition, these thermal polymerizations can be used separately, also can be used in combination of two or more.
The content of above-mentioned polymerization starter (D), with respect to the aforementioned acrylic resin of 100 weight part (A), be preferably 0.01～20 weight part, be particularly preferably 0.1～10 weight part, 0.3～5 weight part more preferably, when the content of above-mentioned polymerization starter (D) is very few, the solidified nature that is weak and the physical property unsettled tendency that becomes, has the tendency that can not get better effect in the time of too much.In addition, total 100 weight parts with respect to simple function aromatics (B) with multi-functional unsaturated compound (C), are preferably 0.01～100 weight part, and more preferably 0.1～20 weight part, is particularly preferably 1～12 weight part.
In addition, as Photoepolymerizationinitiater initiater (d1), while being used in combination the interior Photoepolymerizationinitiater initiater (d1-1) of autothermic cracking type of molecule and the Photoepolymerizationinitiater initiater (d1-2) of hydrogen-abstraction, the ratio of the Photoepolymerizationinitiater initiater (d1-2) of the Photoepolymerizationinitiater initiater of autothermic cracking type (d1-1) and hydrogen-abstraction, be preferably (d1-1): (d1-2)=70:30～1:99 (weight ratio), be particularly preferably (d1-1): (d1-2)=55:45～5:95 (weight ratio), more preferably (d1-1): (d1-2)=45:55～10:90 (weight ratio), (d1-1) containing proportional too much or when very few, the tendency that all has the crosslinked balance collapse of binder layer integral body, there is the deteriorated possibility of bonding physical property.
When above-mentioned active energy beam irradiates, can pass through the light such as far ultraviolet rays yue, ultraviolet ray, near-ultraviolet ray, infrared rays, the hertzian wave such as X ray, gamma-rays, can pass through electron beam, proton beam, neutron beam etc. in addition, from considerations such as easily acquired, the prices of curing speed, irradiating unit, by the curing of uviolizing, be favourable.In addition, while carrying out electron beam irradiation, even if do not use above-mentioned Photoepolymerizationinitiater initiater (d1) also can solidify.
And the light source when carrying out above-mentioned uviolizing, can be used high voltage mercury lamp, electrodeless lamp, ultrahigh pressure mercury lamp, carbon arc lamp, xenon lamp, metal halide lamp, chemical lamp, black lamp etc.The in the situation that of above-mentioned high voltage mercury lamp, for example, at 5～3000mJ/cm 2, preferred 10～1000mJ/cm 2condition under carry out.In addition, the in the situation that of above-mentioned electrodeless lamp, for example, at 2～1500mJ/cm 2, preferred 5～500mJ/cm 2condition under carry out.And irradiation time is according to the distance of the kind of light source, light source and coated face, coating thickness, other conditions and different, can be conventionally several seconds～tens of seconds, according to circumstances, can be also part second.On the other hand, when above-mentioned electron beam irradiation, for example, can use the electron beam of the energy with 50～1000Kev scope, irradiation dose is 2～50Mrad.
In addition, as above-mentioned polymerization starter (D), when using thermal polymerization (d2), by adding thermal initiation, carrying out polyreaction.Treatment temp when being heating and curing, treatment time are according to the kind of used thermal polymerization (d2) and difference, conventionally, transformation period by initiator calculates, treatment temp is preferably 70 ℃～170 ℃ conventionally, treatment time is preferably 0.2～20 minute conventionally, is particularly preferably 0.5～10 minute.
As above-mentioned linking agent (E), for example can list isocyanate-based linking agent, epoxy and be linking agent, aziridine and be linking agent, melamine series linking agent, aldehyde is that linking agent, amine are linking agent, metal-chelating system linking agent.Among these, from can improve with the viewpoint of the adaptation of base material, with reactive viewpoint of base polymer, preferably use isocyanate-based linking agent.
As above-mentioned isocyanate-based linking agent, for example can list 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1, 3-xylylene diisocyanate, 1, 4-xylylene diisocyanate, hexamethylene diisocyanate, ditan-4, 4 '-vulcabond, isophorone diisocyanate, 1, two (isocyanato-methyl) hexanaphthenes of 3-, tetramethyl-xylylene diisocyanate, 1, 5-naphthalene diisocyanate, the adducts of the polyol crosslink agent such as triphenylmethane triisocyanate and these polyisocyanate crosslinkers and TriMethylolPropane(TMP), the biuret body of these polyisocyanate crosslinkers, isocyanuric acid ester body etc.
As above-mentioned epoxy, it is linking agent, for example can list epoxy resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, the T 55,1 of dihydroxyphenyl propane-Epicholorohydrin type, 6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, sorbyl alcohol polyglycidyl ether, Polyglycerine polyglycidyl ether, tetramethylolmethane polyglycidyl ether, two glycerine polyglycidyl ethers etc.
As above-mentioned aziridine, it is linking agent, for example can list tetramethylol methane-tri---'-aziridino propionic ester, TriMethylolPropane(TMP)-tri---'-aziridino propionic ester, N, N '-ditan-4,4 '-bis-(1-aziridine carboxylic acid amides), N, N '-hexa-methylene-1,6-two (1-aziridine carboxylic acid amides) etc.
As above-mentioned melamine series linking agent, such as listing HMMM, six ethoxyl methyl trimeric cyanamides, six propoxy-methyl melamines, six butoxymethyl trimeric cyanamides, six pentyloxy methyl melamines, six hexyloxy methyl melamines, melamine resin etc.
As above-mentioned aldehyde, be linking agent, such as can list oxalic dialdehyde, mda, suceinic aldehyde, maleic dialdehyde, glutaraldehyde, formaldehyde, acetaldehyde, phenyl aldehyde etc.
As above-mentioned amine, be linking agent, such as listing hexamethylene-diamine, triethyl diamines, polymine, vulkacit H, diethylenetriamine, trientine, isophorone diamine, aminoresin, polymeric amide etc.
As above-mentioned metal-chelating system linking agent, can list methyl ethyl diketone, acetylacetic ester coordination compound of the polyvalent metals such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium etc.
In addition, these linking agents (E) can be used separately, also can be used in combination of two or more.
The content of above-mentioned linking agent (E), is resin (A) with respect to 100 parts by weight of acrylic acid conventionally, is preferably 0.01～10 weight part, and more preferably 0.05～5 weight part, is particularly preferably 0.1～2 weight part.When linking agent (E) is very few, have force of cohesion not enough, cannot obtain the tendency of sufficient weather resistance, have flexibility and bonding force to reduce in the time of too much, weather resistance reduces, and becomes and easily peels off, and is therefore difficult to the tendency of using as optics.
In the present invention, also contain silane coupling agent (F) as the constituent of binder composition [I], from raising, for the viewpoint of the adaptation of optics, consider it is preferred.
As above-mentioned silane coupling agent (F), such as listing containing epoxy silane coupling, containing acrylic silane coupling agent, containing mercaptosilane coupling agents, hydroxyl silane coupling agent, containing carboxyl silane coupling agent, containing amino silicane coupling agent, amide-containing silane coupling agent, containing isocyanato silanes coupling agent etc.These can use separately, also can be used in combination of two or more.Among these, preferably use containing epoxy silane coupling, contain mercaptosilane coupling agents, from improving damp and hot weather resistance and excessively not improving the viewpoint of bounding force, also preferably combination is used containing epoxy silane coupling and containing mercaptosilane coupling agents.
As the above-mentioned object lesson containing epoxy silane coupling, for example can list γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane, methyl three (glycidyl) silane, β-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane etc., wherein, γ-glycidoxypropyltrime,hoxysilane preferably, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group methyldiethoxysilane, β-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane.
As the above-mentioned concrete example containing mercaptosilane coupling agents, such as the silane coupling agent etc. that can list the oligomeric of γ mercaptopropyitrimethoxy silane, γ-sulfydryl propyl-triethoxysilicane, γ-sulfydryl propyl group dimethoxy-methyl silane or these compounds.
As the content of silane coupling agent (F), with respect to 100 parts by weight of acrylic acid, be resin (A), be generally 0.001～10 weight part, be preferably 0.01～1 weight part, be particularly preferably 0.03～0.8 weight part.When the content of this silane coupling agent (F) is very few, there is the tendency that can not get additive effect, in the time of too much, have with the mutual solubility of acrylic resin (A) and reduce, can not get the tendency of bonding force, force of cohesion.
In addition, in binder composition [I], in not undermining the scope of effect of the present invention, also further compounding static inhibitor, other acrylic adhesive, other tackiness agent, urethane resin, rosin, rosin ester, hydrogenated wood rosin glycerol ester, resol, aromatic series modified terpene resin, aliphatics through-stone oleo-resinous, alicyclic through-stone oleo-resinous, phenylethylene resin series, the tackifiers such as diformazan benzene series resin, tinting material, weighting agent, antiaging agent, UV light absorber, functional pigmented grade is known additive in the past, by ultraviolet ray or radiation exposure, develop the color or the compound of variable color.
In addition, beyond above-mentioned additive, also can contain on a small quantity contained impurity of the manufacture raw material etc. of constituent of binder composition [I] etc.
As above-mentioned static inhibitor, such as cationic static inhibitor, aliphatic sulfonate, higher alcohol sulfate salt, the higher alcohols that can list the quaternary ammonium salts such as imidazole salts, tetra-allkylammonium sulfonate, be oxidized an alkali metal salts such as anionic antistatic agent, two (fluorosulfonyl) imide potassium, two (three fluorosulfonyls) imide li, lithium chloride such as alkylene affixture sulfuric acid, high alcohol phosphate salt, higher alcohols alkylidene oxide affixture phosphate ester salt, alkali earth metal salt, higher alcohols oxidation alkylene affixture, polyalkylene glycol fatty acid ester etc.
Like this, the present invention obtains above-mentioned binder composition [I] to solidify the tackiness agent forming.
Herein, the adhesive sheet with the tackiness agent that binder composition of the present invention is solidified and obtain, when its tackiness agent (layer) is formed by the tackiness agent of the polymkeric substance of the aromatics (B) that contains acrylic resin (A), contains 1 olefinic unsaturated group, the aromatics (B) that contains 1 olefinic unsaturated group and organic solvent, from the viewpoint of easy performance effect of the present invention, consider it is preferred.
In this case, the content of the aromatics (B) containing 1 olefinic unsaturated group containing as the tackiness agent after solidifying, be preferably 0.1～10 % by weight, be particularly preferably 1～5 % by weight, content as organic solvent is 0.5 ppm by weight～5 % by weight, be preferably 1～1000 ppm by weight, be particularly preferably 10～100 ppm by weight.
And then above-mentioned tackiness agent, preferably containing alkyl acrylate is monomer (a1).For example,, for coming from the material of the manufacture of acrylic resin (A).
When containing alkyl acrylate and being monomer (a1), content is 1ppm～5%, is preferably 10ppm～1000ppm, is particularly preferably 50～100ppm.
And, by the binder layer stratification consisting of above-mentioned tackiness agent is upper at optics (optical laminate), can obtain the optics with binder layer.
In the above-mentioned optics with binder layer, preferably in the contrary one side of the optics face with binder layer, stripping film is also set.
Manufacture method as the above-mentioned optics with binder layer, binder composition [I] is when irradiating by active energy beam and adding at least one of hankering and be cured, there is following methods: [1] is coated with binder composition [I] on optics, after dry, laminating stripping film, by active energy beam, irradiate and add at least one method of processing of hankering, [2] binder composition [I] is coated with on stripping film, after dry, laminating optics, by active energy beam, irradiate and add at least one method of processing of hankering, [3] binder composition [I] is coated with on optics, dry, further by active energy beam, irradiate and add after at least one of hankering process, the method of laminating stripping film, [4] binder composition [I] is coated with on stripping film, dry, further by active energy beam, irradiate and add at least one of hankering and process, the method of optics etc. of fitting afterwards.Among these, never damage viewpoint, operability, the stable viewpoint of manufacturing of base material, the situation of carrying out active energy beam irradiation in the method for [2] is preferred.
In addition,, when binder composition [I] is used linking agent while solidifying (be cross-linked) (be also used in combination undertaken by linking agent), preferably implement maturation process after stating in the use the optics of method manufacture with binder layer.In this maturation process, take reaction times of the chemically crosslinked that time of carrying out in order to obtain the balance of bonding physical property is tackiness agent, condition as slaking, temperature is generally room temperature～70 ℃, time is generally 1～and 30 days, particularly, for example, can carry out 1～20 in 23 ℃, carry out 3～10 in 23 ℃, in 40 ℃, carry out 1～7 etc. implementing under condition.
While being coated with above-mentioned binder composition [I], preferably by this binder composition [I] to be coated with after solvent cut, to weaker concn, as heating residue concentration, be preferably 5～60 % by weight, be particularly preferably 10～30 % by weight.In addition, as long as can make binder composition [I] dissolve as above-mentioned solvent, just have no particular limits, such as using the alcohol series solvents such as aromatic series series solvent, methyl alcohol, ethanol, propyl alcohol such as ketone series solvent, toluene, dimethylbenzene such as ester series solvent, acetone, methylethylketone, mibk such as methyl acetate, ethyl acetate, methyl acetoacetate, methyl aceto acetate.Among these, from the viewpoint such as solvability, drying property, price, consider, can suitable use ethyl acetate, methylethylketone.
In addition, about the coating of above-mentioned binder composition [I], can be undertaken by customary ways such as rolling method, die head coating method, photogravure coating method, comma coating method, silk screen printings.
The gel fraction of the binder layer of manufacturing by aforesaid method, considers from the viewpoint of endurance quality and anti-leakage rotary light performance, is preferably 30～99%, is particularly preferably 60～90%, more preferably 70～85%.When gel fraction is too low, there is the tendency that becomes not enough because of force of cohesion deficiency weather resistance.In addition, have the rising due to force of cohesion to make viscosity become not enough when gel fraction is too high, tackiness agent is for the tendency of the adhesion sense reduction of to-be-adhered object.
The binder layer of manufacturing by aforesaid method, while using finger contact, has well attached sense person because actual water vapour permeability while being attached on to-be-adhered object is good, has the tendency that promotes workability, is preferred.
In addition, when adjusting the gel fraction of used for optical part tackiness agent and be above-mentioned scope, such as irradiation dose, exposure intensity, adjustment that can be by adjusting active energy beam containing the kind of the kind of the compound of unsaturated group and amount, adjustment polymerization starter and be used in combination ratio, adjust polymerization starter compounding amount, the kind of adjusting linking agent and amount etc. reach.In addition, the ratio of components of the irradiation dose of above-mentioned active energy beam or exposure intensity, polymerization starter, addition are by interaction separately, and gel fraction changes, and are therefore necessary to obtain balance separately.
Above-mentioned gel fraction forms degree of crosslinking, and (standard of state of cure is for example calculated by following method.; with 200 object SUS wire netting processed, be wrapped in and form that the high molecular sheet (such as pet film etc.) of base material is upper forms the adhesive sheet (barrier film is not set) that binder layer forms; in toluene, flood 23 ℃ * 24 hours, the weight percent of residual undissolved binder constituents in wire netting of take is gel fraction.Wherein, deduct in advance the weight of base material.
In addition, the specific refractory power of the binder layer of manufacturing by aforesaid method is preferably 1.470～1.575, is particularly preferably 1.475～1.550, and more preferably 1.475～1.520, be especially preferably 1.480～1.500.This specific refractory power has the birefringence-compensated tendency that becomes inadequate of optical laminate integral body when too low, have with the refringence of optical thin film and become large when too high, and the tendency of boundary reflection easily occurs.
This specific refractory power is for being used ATAGO company system " Abbe refractometer 1T ", the measured value with NaD line at 23 ℃.
In addition, in the optics with binder layer of acquisition, there is no particular limitation for the thickness of binder layer, is preferably 5～300 μ m, is particularly preferably 10～50 μ m, more preferably 12～30 μ m.The thickness of this binder layer has bonding physical property to be difficult for stable tendency when too thin, have the thickness of optics integral body to increase excessive tendency when blocked up.
Optics with binder layer of the present invention is directly fitted in tackiness agent aspect on glass substrate, or the optics with stripping film is after peeling off stripping film, and tackiness agent aspect is fitted on glass substrate, supplies with for example LCD panel.
The initial adhesion power of binder layer of the present invention is according to suitably decisions such as the materials of adherend.For example, in the time of on fitting in glass substrate, preferably there is the bounding force of 0.2N/25mm～20N/25mm, more preferably 0.5N/25mm～10N/25mm.
Above-mentioned initial adhesion power is calculated as follows.For the Polarizer with binder layer, be cut into width 25mm, stripping film is peeled off, binder layer side is pressed on non-alkali glass plate (Corning Incorporated manufactures, " Corning XG "), by Polarizer and sheet glass laminating.After this, carry out autoclave processing (50 ℃, 0.5MPa, 20 minutes) afterwards, under 23 ℃, 50%RH, place after 24 hours, carry out 180 ℃ of stripping tests.
Optics of the present invention is not particularly limited, can list the optical thin film of image display devices such as being applicable to liquid crystal indicator, organic EL display, PDP, such as Polarizer, polarizer, elliptical polarization plate, optical compensating film, brightness enhancement film and their duplexer etc.Wherein, Polarizer is effective especially in the present invention.
The Polarizer using in the present invention is normally laminated with the material as the triacetate fiber prime system film of protective film on the two sides of polarizing film; as above-mentioned polarizing film; the film that the polyvinyl alcohol resin that use is usingd by 85～100 % by mole of mean polymerisation degree 1500～10000, saponification deg forms is as material film, by the aqueous solution of IKI or the single axle drawn membrane of dichroic dye dyeing (common 2～10 times, preferably the stretching ratio of 3～7 times of left and right).
As above-mentioned polyvinyl alcohol resin, conventionally by the polyvinyl acetate (PVA) saponification that Polymerization of Vac is formed, manufacture, also can contain a small amount of unsaturated carboxylic acid (comprising salt, ester, acid amides, nitrile etc.), olefines, vinyl ethers, unsaturated sulfonic acid salt etc. can with vinyl acetate copolymerized composition.In addition, can list that polyvinyl alcohol reacts with aldehydes under sour existence and so-called polyvinyl acetal resin and the polyvinyl alcohol derivatives such as bunching butyral resin, the vinyl-formal resin that obtain.
In addition, in the present invention, also can use the aromatics (B) that contains acrylic resin (A) and contain 1 olefinic unsaturated group, and the alefinically unsaturated compounds (C) that contains 2 above olefinic unsaturated groups forms, the photoelastic coefficient of acrylic resin (A) is for negative, and the photoelastic coefficient of the cured article of aromatics (B) and alefinically unsaturated compounds (C) is positive binder composition.
Wherein, in the present invention, photoelastic coefficient positive and negative, is the result of measuring as follows.
The positive and negative condition determination > of < photoelastic coefficient
In photoelasticity measurement device (UNIOPT CORPORATION, LTD. system: the test film of film like is set PEL-3A-102R), measures the positive and negative of photoelastic coefficient.
The positive and negative of photoelastic coefficient be, in the face that comprises width and length, take bearing of trend as 0 °, perpendicular to the direction of bearing of trend during as 90 °, orientations of major is just decided to be when 0 ° of direction, orientations of major is decided to be negative when 90 ° of directions.
The thickness of the test film during about said determination, the positive and negative refringence depending in arbitrary face of photoelastic coefficient, the positive and negative thickness effect that is not subject to of photoelastic coefficient, therefore the thickness of test film can be any thickness, use the maneuverable thickness such as workability, conventionally the test film of used thickness 1～1000 μ m.
The size of the test film during about said determination, so long as in being arranged at the scope of testing apparatus, there is no particular limitation, conventionally uses length 20～50mm, the test film of width 10～20mm.
In addition, photoelasticity refers to that material is owing to being subject to stress, there is orientation and phenomenon that double refraction size changes in the molecule of constitute, during uniaxial extension because stress direction is consistent with bearing of trend, therefore measure the birefringent orientations of major representing when elongation test sheet, can judge the positive and negative of photoelastic coefficient.Therefore, the extension ratio of the test film during about said determination, as long as setting orientations of major is stable multiplying power, as the soft material of tackiness agent, owing to easily occurring, orientation relaxes, stress relaxes, extension ratio hour cannot stably be measured orientations of major sometimes, therefore 2～5 times of extensible approximately former test length of a film, if as the hard material of film, extend approximately 1.01～2 times of left and right of former test length of a film.
Embodiment
Be described more specifically by the following examples the present invention, as long as but the present invention is no more than its main idea, be not limited to following examples.Wherein, " part " in example, " % ", all represent weight basis in case of no particular description.
First, prepare in the following manner various acrylic resins (A).Wherein, about the mensuration of the weight-average molecular weight of acrylic resin (A), dispersity, second-order transition temperature, according to preceding method, measure.
Wherein, about the mensuration of the viscosity of acrylic resin (A), according to the 4.5.3 rotational viscosimeter method of JISK5400 (1990), measure.
In addition, the positive and negative mensuration of the photoelastic coefficient of acrylic resin (A), carries out in such a way.
The positive and negative mensuration 1> of < photoelastic coefficient
Acrylic resin (A) is coated on to SP-01 (gently peeling off PET) upper, dry after 3 minutes at 100 ℃, lamination SP-003 (heavily peeling off PET).By the sheet material obtaining slaking 1 week at 40 ℃, the thickness that obtains adhesive linkage is the adhesive sheet of 25 μ m.This adhesive sheet is cut into after 3cm * 2cm, and (Uniopt Corporation, Ltd. manufactures: in " PEL-3A-102R " only binder layer to be arranged to photoelasticity measurement device.The orientations of major while making it extend 2 times is also measured in the two ends of stretched bonded agent layer, judges the positive and negative of photoelastic coefficient.
With main shaft (slow axis) orientation, be positioned at 0 ° of direction person for just, take main shaft (slow axis) orientation and be positioned at 90 ° of direction persons as negative.
[preparation of acrylic resin (A)] (with reference to table 1)
[acrylic resin (A-1)]
Possessing condensation reflux device, agitator, nitrogen be blown into mouthful and the four-hole round-bottomed flask of thermometer in drop into 98.5 parts of butyl acrylates (a1), 1 part of vinylformic acid 2-hydroxy methacrylate (a2), 0.5 part of vinylformic acid (a2) and 75 parts of ethyl acetate, 45 parts of acetone, start after reflux, add 0.03 part of azobis isobutyronitrile as polymerization starter (AIBN), at ethyl acetate backflow temperature, react after 3 hours, by ethyl acetate, dilute, obtain acrylic resin (A-1) solution (weight-average molecular weight (Mw) 2,000,000, dispersity (Mw/Mn) 3.1, second-order transition temperature-54 ℃, solids component 16%, viscosity 8000mPas (25 ℃)).
[acrylic resin (A-2)]
Possessing condensation reflux device, agitator, nitrogen be blown into mouthful and the four-hole round-bottomed flask of thermometer in drop into 97 parts of butyl acrylates (a1), 3 parts of vinylformic acid (a2) and 100 parts of ethyl acetate, 45 parts of acetone, start after reflux, add 0.03 part of azobis isobutyronitrile as polymerization starter (AIBN), at ethyl acetate backflow temperature, react after 3 hours, by ethyl acetate, dilute, obtain acrylic resin (A-2) solution (weight-average molecular weight (Mw) 1,800,000, dispersity (Mw/Mn) 3.2, second-order transition temperature-53 ℃, solids component 18%, viscosity 8000mPas (25 ℃)).
[acrylic resin (A-3)]
Possessing condensation reflux device, agitator, nitrogen be blown into mouthful and the four-hole round-bottomed flask of thermometer in drop into 98.5 parts of butyl acrylates (a1), 1.5 parts of vinylformic acid 2-hydroxy methacrylates (a2) and 120 parts of ethyl acetate, 45 parts of acetone, start after reflux, add 0.03 part of azobis isobutyronitrile as polymerization starter (AIBN), at ethyl acetate backflow temperature, react after 3 hours, with ethyl acetate, dilute, obtain acrylic resin (A-3) solution (weight-average molecular weight (Mw) 1,500,000, dispersity (Mw/Mn) 3.4, second-order transition temperature-53 ℃, solids component 23%, viscosity 8000mPas (25 ℃)).
[acrylic resin (A-4)]
Condensation reflux device is being equipped with, agitator, nitrogen be blown into mouthful and the four-hole round-bottomed flask of thermometer in drop into 95 parts of butyl acrylates (a1), 5 parts of vinylformic acid (a2) and 120 parts of ethyl acetate, 45 parts of acetone, start after reflux, add 0.03 part of azobis isobutyronitrile as polymerization starter (AIBN), at ethyl acetate backflow temperature, react after 3 hours, by ethyl acetate, dilute, obtain acrylic resin (A-4) solution (weight-average molecular weight (Mw) 1,500,000, dispersity (Mw/Mn) 3.4, second-order transition temperature-51 ℃, solids component 23%, viscosity 8000mPas (25 ℃)).
[acrylic resin (A-5)]
Possessing condensation reflux device, agitator, nitrogen is blown in the four-hole round-bottomed flask of mouth and thermometer, drop into 95 parts of butyl acrylates (a1), 5 parts of vinylformic acid (a2) and 100 parts of ethyl acetate, 45 parts of acetone, start after reflux, add 0.03 part of azobis isobutyronitrile as polymerization starter (AIBN), at ethyl acetate backflow temperature, react after 3 hours, by ethyl acetate, dilute, obtain acrylic resin (A-5) solution (weight-average molecular weight (Mw) 1,700,000, dispersity (Mw/Mn) 3.2, second-order transition temperature-51 ℃, solids component 18%, viscosity 8000mPas (25 ℃)).
[acrylic resin (A-6)]
Possessing condensation reflux device, agitator, nitrogen be blown into mouthful and the four-hole round-bottomed flask of thermometer in drop into 61.3 parts of butyl acrylates (a1), 35 parts of benzyl acrylates, 3.5 parts of vinylformic acid 2-hydroxy methacrylates (a2), 150 parts, 0.2 part of vinylformic acid (a2) and ethyl acetate, 45 parts of acetone, start after reflux, add 0.03 part of azobis isobutyronitrile as polymerization starter (AIBN), at ethyl acetate backflow temperature, react after 3 hours, by ethyl acetate, dilute, obtain acrylic resin (A-6) solution (weight-average molecular weight (Mw) 1,500,000, dispersity (Mw/Mn) 3.5, second-order transition temperature-36 ℃, solids component 20%, viscosity 8000mPas (25 ℃)).
[acrylic resin (A-7)]
Possessing condensation reflux device, agitator, nitrogen is blown in the four-hole round-bottomed flask of mouth and thermometer, drop into 94.8 parts of butyl acrylates (a1), 0.2 part of vinylformic acid 2-hydroxy methacrylate (a2), 5 parts of vinylformic acid (a2) and 120 parts of ethyl acetate, 45 parts of acetone, start after reflux, add 0.03 part of azobis isobutyronitrile as polymerization starter (AIBN), at ethyl acetate backflow temperature, react after 3 hours, by ethyl acetate, dilute, obtain acrylic resin (A-7) solution (weight-average molecular weight (Mw) 1,500,000, dispersity (Mw/Mn) 3.4, second-order transition temperature-51 ℃, solids component 23%, viscosity 8000mPas (25 ℃)).
[table 1]
Note: BA: butyl acrylate
HEA: vinylformic acid 2-hydroxy methacrylate
AAc: vinylformic acid
BzA: benzyl acrylate
[simple function aromatics (B)]
Prepare following material as simple function aromatics (B-1).
(kyoeisha Chemical Co., Ltd. manufactures vinylformic acid diethylamino phenyl diol ester, trade(brand)name " Light acrylate P2HA ": molecular weight 236.3)
Prepare following material as simple function aromatics (B-2).
Ethoxyquin orthoxenol acrylate (Hitachi Chemical Co., Ltd. manufactures, trade(brand)name " FA-301A ": molecular weight 268, flash-point 170-199 ℃, volatilize residual part 100%)
Prepare following material as simple function aromatics (B-3).
(Shin Nakamura Chemical Co., Ltd. manufactures the adjacent biphenyl 2-ethoxyethyl acetate of vinylformic acid, trade(brand)name " A-LEN-10T ": molecular weight 268)
Prepare following material as simple function aromatics (B-4).
(OSAKA ORGANIC CHEMICAL INDUSTRY LTD. manufactures vinylformic acid benzene sulphur ethyl ester, trade(brand)name " PhSEA ": molecular weight 207)
[multifunctional unsaturated compound (C)]
Prepare following material as multifunctional unsaturated compound (C-1).
Viscoat 295 (molecular weight 296.3)
[polymerization starter (D)]
Prepare following material as Photoepolymerizationinitiater initiater (D-1).
The mixture of the mass ratio 1:1 of benzophenone and 1-hydroxycyclohexylphenylketone (Ciba Specialty Chemicals Inc. manufactures, " Irgacure500 ")
[linking agent (E)]
Prepare following material as linking agent (E-1).
55% ethyl acetate solution of the tolylene diisocyanate affixture of TriMethylolPropane(TMP) (Nippon Polyurethane Industry Co., Ltd. manufactures, " Coronate L-55E ")
[silane coupling agent (F)]
Prepare following material as silane based compound (F-1).
γ-glycidoxypropyltrime,hoxysilane (Shin-Etsu Chemial Co., Ltd manufactures, " KBM403 ")
Prepare following material as silane based compound (F-2).
γ mercaptopropyitrimethoxy silane (Shin-Etsu Chemial Co., Ltd manufactures, " KBM803 ")
Prepare following material as silane based compound (F-3).
Sulfydryl is silane coupling agent (oligomer type) (Shin-Etsu Chemial Co., Ltd manufactures, " X-41-1805 ")
[embodiment 1～13, comparative example 1～6]
By each compounding composition of preparing in a manner described, preparing, by ratio compounding shown in following table 2, thereby preparation becomes the binder composition that used for optical part tackiness agent forms material, by ethyl acetate, diluted (viscosity [500～10000mPas (25 ℃)]), made binder composition solution.
Then, by binder composition solution coat obtained above, at polyester, be on release sheet, making dried thickness is 25 μ m, dry after 3 minutes at 90 ℃, formed adhesive composition layer is transferred on polyethylene terephthalate (PET) film (thickness 38 μ m), the electrodeless lamp [the H bulb of LH6UV lamp] of manufacturing with Fusion company, with peak illumination: 600mW/cm 2, cumulative exposure amount: 240mJ/cm 2carry out uviolizing (120mJ/cm 2, 2 subpulses), under 23 ℃, the condition of 65%R.H., slaking is 10, obtains the PET film with binder layer.
Use the PET film with binder layer obtaining like this, according to each method evaluation of measuring operability shown below, resistance to smelly property, gel fraction, mist degree, specific refractory power.These the results are shown in following table 2.
[operability]
PET film by gained with binder layer is cut into after 25mm * 40mm, peels off release sheet, uses finger contact binder layer, by its adhesion sense of following benchmark evaluation.
Zero: have good adherence sense
*: not too there is adhesion sense
[resistance to smelly property]
Gained is placed after 3 hours under 23 ℃, the temperature and humidity control condition of 50%R.H. with the PET film of binder layer, peeled off release sheet, smell its taste and with following benchmark evaluation.
Zero: imperceptible monomer smell
*: feel to obtain monomer smell
[gel fraction]
PET film by gained with binder layer is cut into after 40mm * 40mm, peel off release sheet, and a side of binder layer is fitted on the SUS net sheet (200 order) of 50mm * 100mm, then, with respect to SUS net sheet longitudinally, from central part is folding, wrap into sample the weight change determination gel fraction when flooding 24 hours at 23 ℃ in the sealed vessel that 250g toluene is housed.
[mist degree]
The manufacture of mist degree test sample
Above-mentioned binder composition solution coat is gently peeled off on release sheet in polyester system, making dried thickness is 25 μ m, dry after 3 minutes at 90 ℃, with polyester system, heavily peel off a side of the adhesive composition layer of release sheet laminating formation, the electrodeless lamp [the H bulb of LH6UV lamp] of manufacturing with Fusion company, with peak illumination: 600mW/cm 2, cumulative exposure amount: 240mJ/cm 2carry out uviolizing (120mJ/cm 2, 2 subpulses), then slaking 10 days under 23 ℃, the condition of 50%R.H., obtains the binder layer without base material.The binder layer without base material of gained is cut away to 3cm * 4cm, divest and gently peel off release sheet, by a side of binder layer, by being pressed in non-alkali glass plate, (Corning Incorporated manufactures, EagleXG) upper, and then peels off and heavily peel off release sheet, obtains mist degree test sample.
The mensuration of haze value
Use HAZE MATER NDH2000 (Japanese electricity Se Industrial Co., Ltd manufacture) to measure diffusion transmissivity and the full light transmittance of above-mentioned mist degree test sample.Wherein, the machine is according to JIS K7361-1.
Value substitution following formula by the diffusion transmissivity obtaining and full light transmittance, calculates haze value.
Haze value (%)=(diffusion transmissivity/full light transmittance) * 100
[specific refractory power]
Use above-mentioned mist degree test sample, " the Abbe refractometer 1T " that uses Atago company to manufacture, the value at measuring 23 ℃ with NaD ray.
[table 2]
Note: (A)～(F) in, the numerical value in table is compounding weight part.
In table, "-" represents not compounding.
In comparative example 5,15 parts of fluorenes of compounding, in comparative example 6,30 parts of fluorenes of compounding.
In addition, in embodiment 13, use the above-mentioned PET film with binder layer to measure remaining simple function aromatics (B) and ethyl acetate concentration in tackiness agent (layer), the concentration of result simple function aromatics (B) is 4 % by weight, and ethyl acetate concentration is 25 ppm by weight.
Wherein, measuring method is as follows.
[measuring method of the concentration of simple function aromatics (B)]
The above-mentioned PET film with binder layer is cut into after 40mm * 40mm, divest release sheet, one side of binder layer is fitted on the SUS net sheet (200 order) of 50mm * 100mm, afterwards, with respect to SUS net sheet longitudinally, folding from central part, wrap into after sample, at 23 ℃, be equipped with in the sealed vessel of 250g acetone and soaking after 24 hours, the acetone soln of gained is injected to 1 μ L (Injector:Agilent Technologies company manufactures 7683B series) with liquid automatic sampler, (GC:Agilent Technologies company manufactures to use gas chromatograph/mass fragments detector, 6890NNetwork GCsystem, MSD:Agilent Technologies company manufactures 5973inert), measure the concentration of the simple function aromatics (B) in solution.The chromatographic column of using is the DB-17MS (μ m φ * 0.25,30m * 250 μ m) that Agilent company manufactures, and current-carrying gas is He, and flow is 1.0ml/min, and pressure is 7.0psi (40 ℃ time).In addition, splitting ratio is 30:1, and injector temperature is 220 ℃.The temperature condition of post case is at 40 ℃ after 5 minutes, with 10 ℃/min, heats up, and after arriving 220 ℃, maintains 10 minutes.Transmission line temperature to MSD is 220 ℃, and scan pattern (mass range: 10～600, scanning times: 2.52/sec).The weight of the weight of the concentration of the simple function aromatics (B) in the acetone soln that in addition, the concentration of simple function aromatics (B) obtains by said determination, the PET film with binder layer of above-mentioned 40mm * 40mm, the PET film of 40mm * 40mm is calculated and is tried to achieve.
[measuring method of ethyl acetate concentration]
The PET film with binder layer of gained is cut into 25mm * 25mm, weighs after divesting demoulding PET.This sample is put into the sample vial of capacity 20mL and covered tightly.This bottle is heated 30 minutes with head-space sampler (Agilent Technologies company manufactures headspace sampler G1888) at 120 ℃, the gas of heated condition is taken out with the condition of (15psi * 4 minute), and (GC:Agilent Technologies company manufactures to use gas chromatograph/mass fragments detector, 6890N Network GC system, MSD:Agilent Technologies company manufactures 5973inert) measure ethyl acetate concentration contained in this gas.The chromatographic column of using is the DB-17MS (μ m φ * 0.25,30m * 250 μ m) that Agilent company manufactures, and current-carrying gas is He, and flow is 1.0ml/min, and pressure is 7.0psi (40 ℃ time).In addition, splitting ratio is 30:1, and injector temperature is 220 ℃.The temperature condition of post case is at 40 ℃ 5 minutes, then with 10 ℃/min, heats up, and after arriving 220 ℃, places 10 minutes.To 220 ℃ of the transmission line temperature of MSD, and scan pattern (mass range: 10～600, scanning times: 2.52/sec).
In addition, this only measures ethyl acetate is general, and represents that by take in this embodiment the ethyl acetate of using is that representative is measured.
The positive and negative mensuration 2> of < photoelastic coefficient
In addition, the photoelastic coefficient of mensuration simple function aromatics (B-1～B-4) is positive and negative.The in the situation that of independent simple function aromatics, cured article can not be cross-linked, therefore operational difficulty, the multi-functional unsaturated compound that compounding is a small amount of is also judged the positive and negative photoelastic coefficient as simple function aromatics positive and negative of the photoelastic coefficient of its cured article.; 100 parts of simple function aromatics of compounding (B-1～B-4), 10 parts of multi-functional unsaturated compounds (C-1) and 10 parts of Photoepolymerizationinitiater initiaters (D-1); be coated on the sheet glass that is provided with spacer of thick 400 μ m; from upper layers laminated glass; the electrodeless lamp [the H bulb of LH6UV lamp] of manufacturing with Fusion company, with peak illumination: 600mW/cm 2, cumulative exposure amount: 240mJ/cm 2carry out uviolizing (120mJ/cm 2, 2 subpulses) it is solidified.The thickness of the cured article obtaining is about 300 μ m.This cured article is cut into 3cm * 2cm, (longitudinal end clamps with fixture) is set on photoelasticity measurement device (Uniopt Corporation, Ltd. manufactures: " PEL-3A-102R ").The two ends of stretching cured article, measure the orientations of major while making it be out of shape 2%, similarly judge the positive and negative of photoelastic coefficient with aforementioned.
Its result, the photoelastic coefficient of each cured article of simple function aromatics (B-1～B-4) is just.
Then, by the binder composition solution coat of embodiment 1～13, comparative example 1～6, at polyester, be on stripping film, making dried thickness is 25 μ m, dry after 3 minutes at 90 ℃, formed adhesive composition layer (thickness 190 μ m) is transferred on Polarizer, the electrodeless lamp [the H bulb of LH6UV lamp] of manufacturing with Fusion company, with peak illumination: 600mW/cm 2, cumulative exposure amount: 240mJ/cm 2carry out uviolizing (120mJ/cm 2, 2 subpulses), under 23 ℃, the condition of 65%R.H., slaking is 10, obtains the Polarizer with binder layer.
Wherein, above-mentioned Polarizer be take relative outrigger shaft with " MLP38U " that MeCan Imaging Inc manufactures and is cut use as the mode of 45 °.
Use the Polarizer with binder layer obtaining in this way, according to each method evaluation of measuring weather resistance (hot resistance test, thermal cycling test, oven test) shown below, bonding force.These the results are shown in aftermentioned table 3.
[weather resistance]
Peel off the release sheet of the Polarizer with binder layer of gained, by a side of binder layer, by being pressed in non-alkali glass plate, (Corning Incorporated manufactures, Eagle XG) on, after laminating Polarizer and sheet glass, carry out autoclave processing (50 ℃, 0.5MPa, 20 minutes), the evaluation of afterwards, bubbling, peeling off in the long duration test (hot resistance test, thermal cycling test, oven test) of following (1)～(4).And then, below in the oven test of (4), except above-mentioned foaming, the evaluation of peeling off, also make so that Polarizer be the mode of crossed nicols (crossed Nicol) on surface the light leak observation sample with two sides, back side laminating same sample, carry out the evaluation of light leakage phenomena.
The size of the test film using in addition, is punched to 20cm * 15cm and uses.
[long duration test]
(1) hot resistance test
The long duration test of 60 ℃, 90%R.H.150 hour
(2) thermal cycling test
To at-35 ℃, place after 60 minutes, 70 ℃ of operations of placing 60 minutes, as 1 circulation, carry out the long duration test of 75 circulations
(3) oven test (A)
The long duration test of 90 ℃, 150 hours
(4) oven test (B)
Long duration test and the light leak of 80 ℃, 150 hours
[metewand]
(foaming)
Zero ... almost do not observe foaming
△ ... observe slightly and bubble
* ... observe a lot of foamings
(peeling off)
Zero ... occur being less than peeling off of 0.5mm, or be less than the vestige that floats of 0.5mm
△ ... occur that 0.5mm is above and be less than peeling off of 10mm, or 0.5mm is above and be less than the vestige that floats of 10mm
* ... there is more than 10mm peeling off, or more than 10mm float vestige
(light leak)
◎ ... substantially there is no light leak
Zero ... there is light leak slightly
△ ... there is a small amount of light leak
* ... there are a large amount of light leaks in four limits
[bonding force]
The Polarizer with binder layer of preparation is cut into width 25mm, divests mould release film, by a side of binder layer by being pressed in non-alkali glass plate (Corning Incorporated manufacture, " Corning1737 "), and fit Polarizer and sheet glass.Afterwards, carry out autoclave processing (50 ℃, 0.5MPa, 20 minutes), under 23 ℃, the condition of 50%R.H., place after 24 hours, carry out 180 ℃ of stripping tests.About separability, bonding force is little is desirable, and target is that after 1 day, bonding force is below 10N/25mm.
[table 3]
※: the tackiness agent of comparative example 6, the fluorenes using as uncured property aromatic series based compound and the consistency of acrylic resin are poor, and fluorenes oozes out and albefaction, and then also cannot fit to sheet glass, cannot carry out above-mentioned endurance test.
The tackiness agent of embodiment, weather resistance, resistance to light leak, the bonding force when laminating Polarizer and sheet glass is that very high level and balance is very excellent, and also excellence of the adhesion sense while making binder layer, mist degree, resistance to smelly property.On the other hand, comparative example 1～6 is failed the performance meeting the demands in the following areas.
Not in the comparative example 1 of compounding simple function aromatics (B-1), although the physical property of binder layer itself is excellent, but poor performance when laminating Polarizer and sheet glass, compounding simple function aromatics (B-1) and increasing in the comparative example 2 of compounding amount of multi-functional unsaturated compound (C-1) not, although performance when laminating Polarizer and sheet glass is excellent, the poor properties of binder layer itself.
With respect to (B-1) and total amount (C-1), only in the comparative example 3 of compounding simple function aromatics (B-1) 15.7mol%, although performance when laminating Polarizer and sheet glass is excellent, the poor properties of binder layer itself (operability is poor).
The comparative example 4 of the acrylic resin that use forms aromatic monomer copolymerization, result has occurred that aromatic monomer by not copolymerization causes allows the uncomfortable monomer smell of people, and due to the impact of remaining monomer, there is foaming slightly in result in oven test.
Be mixed with in the comparative example 5,6 of the fluorenes containing aromatic nucleus low molecular compound that belongs to uncured property, the stink that not only comes from fluorenes, and while increasing combined amount and the consistency of acrylic resin poor, therefore the mist degree of filming significantly worsens, and then, low molecular compound seepage, has not given play to the function as adhesive linkage completely.
In addition, the specific embodiment of the present invention has been shown in above-described embodiment, but above-described embodiment is only illustration, does not do the explanation limiting.In addition, belong to the change of the impartial scope of claim, all within the scope of the invention.
utilizability in industry
Tackiness agent of the present invention, binder layer after being cured by active energy beam and/or heat, its operability (viscosity), optical characteristics (mist degree) excellence, even under the environment of high temperature, high humidity, the cementability of the opticses such as optical laminate, especially Polarizer and glass substrate is still excellent, can obtain between binder layer and glass substrate and not bubble, peel off, the liquid crystal indicator of irregular colour or light leak does not occur.Therefore, for used for optical part tackiness agent, be especially effectively, and then, as using them and what obtain is very useful with the optics of binder layer and the tackiness agent of image display device for obtaining.

Claims (12)

1. a Polarizer tackiness agent, it is characterized in that, it is that to contain weight-average molecular weight be 600,000～3,000,000 acrylic resin (A), aromatics (B) containing 1 olefinic unsaturated group, containing 2 above alefinically unsaturated compounds (C) of olefinic unsaturated group and the binder composition [I] of solvent, by active energy beam and/or heat, be cured the tackiness agent forming, wherein, the content of aromatics (B) is that resin (A) is 3～300 weight parts with respect to 100 parts by weight of acrylic acid, and aromatics (B) is greater than 50mol% with respect to aromatics (B) and the ratio (mol%) that contains of the total amount of alefinically unsaturated compounds (C).
2. Polarizer tackiness agent according to claim 1, is characterized in that, the acrylic resin (A1) that acrylic resin (A) contains side chain hydroxyl and the carboxylic acrylic resin of side chain (A2).
3. Polarizer tackiness agent according to claim 1, is characterized in that, aromatics (B) contains 2 above aromatic nucleus, sulphur atom or bromine atoms.
4. Polarizer tackiness agent according to claim 1, is characterized in that, binder composition [I] contains polymerization starter (D).
5. according to the Polarizer tackiness agent described in any one in claim 1～4, it is characterized in that, binder composition [I] contains linking agent (E), and is cross-linked and is formed by linking agent.
6. with the Polarizer of binder layer, the stepped construction that it comprises binder layer and Polarizer, described binder layer contains the Polarizer tackiness agent described in any one in claim 1～5.
7. the Polarizer with binder layer according to claim 6, is characterized in that, its mode coating adhesive composition [I] that heats residue concentration 5～60 % by weight obtains.
8. the Polarizer with binder layer according to claim 6, is characterized in that, the gel fraction of binder layer is 30～99%.
9. according to the Polarizer with binder layer described in claim 7 or 8, it is characterized in that, the thickness of binder layer is 10～50 μ m.
10. an image display device, is characterized in that, its right to use requires the Polarizer with binder layer described in any one in 6～9.
11. 1 kinds of Polarizers active energy ray-curable and/or Thermocurable binder compositions, it is characterized in that, it contains weight-average molecular weight is 600,000～3,000,000 acrylic resin (A), aromatics (B) containing 1 olefinic unsaturated group, alefinically unsaturated compounds (C) and solvent containing 2 above olefinic unsaturated groups, wherein, the content of aromatics (B) is that resin (A) is 3～300 weight parts with respect to 100 parts by weight of acrylic acid, and aromatics (B) is greater than 50mol% with respect to aromatics (B) and the ratio (mol%) that contains of the total amount of alefinically unsaturated compounds (C).
12. 1 kinds of Polarizer binder compositions, it is characterized in that, it is that to contain weight-average molecular weight be 600,000～3,000,000 acrylic resin (A), containing the aromatics (B) of 1 olefinic unsaturated group, form containing alefinically unsaturated compounds (C) and the solvent of 2 above olefinic unsaturated groups, wherein, the photoelastic coefficient of acrylic resin (A) is for negative, and the photoelastic coefficient of aromatics (B) and the cured article of alefinically unsaturated compounds (C) is for just.
CN201410291414.4A 2010-01-21 2011-01-20 Polarizer binding agent and active energy beam/heat-curable adhesive composition, band adhesive phase Polarizer, image display device Active CN104046281B (en)

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KR20120124394A (en) 2012-11-13

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