CN103497691B - Photo-cured adhesive composition, polarizing plate and producing method for the same, optical member and liquid crystal display device - Google Patents

Photo-cured adhesive composition, polarizing plate and producing method for the same, optical member and liquid crystal display device Download PDF

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Publication number
CN103497691B
CN103497691B CN201310346471.3A CN201310346471A CN103497691B CN 103497691 B CN103497691 B CN 103497691B CN 201310346471 A CN201310346471 A CN 201310346471A CN 103497691 B CN103497691 B CN 103497691B
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China
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compound
polaroid
methyl
adhesive agent
photocurable adhesive
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CN103497691A (en
Inventor
岩田智
竹内智康
藤田政大
稻田和正
佐内康之
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Toagosei Co Ltd
Sumitomo Chemical Co Ltd
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Toagosei Co Ltd
Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13356—Structural association of cells with optical devices, e.g. polarisers or reflectors characterised by the placement of the optical elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

Abstract

The present invention provides a photo-cured adhesive composition, and a polarizing plate having a protective film pasted on a polarizer using the adhesive, wherein the photo-cured adhesive composition allows a protective film to be adhered to a polarizer with sufficient adhesion strength within a short time even when a resin film having low moisture permeability selected from polyester resin, polycarbonate resin and acrylic resin is used as the protective film. When the polarizer uniaxially extended and consisted of a polyvinyl alcohol resin film in which a dichroic pigment is absorbed and orientated is adhered to the protective film consisted the resin film having low moisture permeability, the photo-cured adhesive composition includes (A) an epoxy compound having at least two epoxy groups in one molecule, (B) an oxetane compound having at least one oxetane group in one molecule, and (C) a photo cation polymerization initiator, wherein the weight ratio of the epoxy compound (A) to the oxetane compound (B) is 90/10 to 10/90, and the photo cation polymerization initiator (C) is 0.5 to 20% by weight in the composition.

Description

Photocurable adhesive agent composition, polarization plates and manufacturing process thereof, optics and liquid crystal indicator
The divisional application that the application is the applying date is on 03 04th, 2010, application number is 201010129028.7, denomination of invention is the application of " Photocurable adhesive agent composition, polarization plates and manufacturing process thereof, optics and liquid crystal indicator ".
Technical field
The present invention relates in polarization plates for polaroid and protective membrane are fitted Photocurable adhesive agent composition, use this adhesive composite to fit the polarization plates of protective membrane and the manufacture method of this polarization plates at polaroid.The invention still further relates to the optics and liquid crystal indicator that employ this polarization plates.
Background technology
Polarization plates can be used as a kind of optics forming liquid crystal indicator.Polarization plates is usually assembled in liquid crystal indicator with the structure being laminated with protective membrane on the two sides of polaroid and uses.Though known arranges the situation of protective membrane at the one side of polaroid, as a rule, not simple protective membrane but the layer with other optical functions is fitted in another side by doubling as protective membrane.In addition, as the manufacture method of polaroid, extensively known to utilizing the unilateral stretching polyvinyl alcohol resin film of dichroism pigment dyeing to implement boric acid process, method dry after washing.
Usually, after above-mentioned washing and drying, immediately protective membrane is fitted to polaroid.This is because the physical strength of dried polaroid is weak, if once be reeled, then there is the problems of crack of machine direction.Thus, usually, polaroid after the drying applies immediately the caking agent of water system, afterwards, by this caking agent simultaneously at the two sides of polaroid laminating protective membrane.Usually, as protective membrane, use the tri acetyl cellulose membrane of thick 30 ~ 120 μm.
Polaroid and the protective membrane that protective membrane is especially formed with by tri acetyl cellulose membrane bonding in, mostly use the caking agent of polyethenol series, also can attempt being replaced and use the caking agent of urethane system.Such as describe in Japanese Unexamined Patent Publication 7-120617 publication (patent documentation 1) and use urethane prepolymer as caking agent, polaroid high for water content is bonding with the acetate fiber prime system protective membrane of such as tri acetyl cellulose membrane.
But the rate of perviousness of triacetyl cellulose is high, under the condition of the polarization plates that this resin molding has been fitted to two sides as protective membrane such as temperature 70 C, relative humidity 90% and so under damp and hot, there is problems such as causing deterioration.Therefore, also proposed by using rate of perviousness lower than the resin molding of tri acetyl cellulose membrane as protective membrane, solve the method for this problem, such as known using noncrystalline polyolefin system resin as protective membrane.Specifically, in Japanese Unexamined Patent Publication 6-51117 publication (patent documentation 2), at least one laminating thermoplastic's saturated norbornene series resin sheet material at polaroid is described as the technical scheme of protective membrane.
With device in the past fit this Water Vapour Permeability low protective membrane time; there will be in wet type is stacked and can not obtain desirable bonding strength; or the problem such as bad order; so-called wet type is stacked is following method; that is: using with water is the caking agent such as polyvinyl alcohol water solution of primary solvent; after protective membrane being fitted to the polaroid of polyethenol series, make solvent seasoning.This causes due to following reason: compared with tri acetyl cellulose membrane, the film that Water Vapour Permeability is low is generally hydrophobicity; Water Vapour Permeability is low and can not the fully dry water as solvent.
Therefore, in Japanese Unexamined Patent Publication 2000-321432 publication (patent documentation 3), propose the scheme that the protective membrane that utilizes urethane adhesive to be formed with by thermoplasticity saturated norbornene system resin by the polaroid of polyethenol series is bonding.But there is the problem that solidification needs the long period in urethane adhesive, in addition, bonding force is also not necessarily abundant.
On the other hand, there will be a known the scheme of different types of protective membrane of fitting on the two sides of polaroid, such as propose in Japanese Unexamined Patent Publication 2002-174729 publication (patent documentation 4), to fit the protective membrane be made up of noncrystalline polyolefin system resin in the one side of the polaroid be made up of polyvinyl alcohol resin film, at another side, the scheme of the protective membrane that the laminating resin different from this noncrystalline polyolefin system resin is such as made up of triacetyl cellulose, following scheme is proposed: in the one side of the polarization film be made up of polyvinyl alcohol resin in Japanese Patent Laid-Open 2005-208456 publication (patent documentation 5), by the stacked cyclic olefine resin molding of water system first caking agent containing particular polyurethane resin, at the aqueous solution stacked cellulose acetate resin film of another side by the water system second caking agent such as polyvinyl alcohol resin different from the first caking agent.
The unit that the resin being called as cyclic olefine resin in noncrystalline polyolefin system resin, above-mentioned patent documentation 5 has the monomer of the polycycle cycloolefin comprising norbornylene or derivatives thereof, dimethylene eight hydroxyl naphthalene (dimethanooctahydronaphthalene) and so on is called as in above-mentioned patent documentation 4, when remaining double bond as ring-opening polymerization polymer, the thermoplastic resin that preferred double bond has been hydrogenated.
In addition; a kind of caking agent being principal constituent with the epoxy resin not containing aromatic nucleus is disclosed in Japanese Patent Laid-Open 2004-245925 publication (patent documentation 6); propose and make it cationic polymerization to this caking agent irradiation active energy beam, thus by method bonding with protective membrane for polaroid.Specify that; although the caking agent of epoxy disclosed in it is by noncrystalline polyolefin system resin and be that the various transparent resin films of representative fit in the process of polaroid effective especially with celluosic resin; but when taking acrylic resin as protective membrane, its bonding force may not be desirable.
Conventional art document
Patent documentation
[patent documentation 1] Japanese Patent Laid-Open 7-120617 publication
[patent documentation 2] Japanese Patent Laid-Open 6-51117 publication
[patent documentation 3] Japanese Patent Laid-Open 2000-321432 publication
[patent documentation 4] Japanese Patent Laid-Open 2002-174729 publication
[patent documentation 5] Japanese Patent Laid-Open 2005-208456 publication
[patent documentation 6] Japanese Patent Laid-Open 2004-245925 publication
In order to solve the problem when polaroid of polyethenol series and the low protective membrane of Water Vapour Permeability being fitted by wet type is stacked; consider the dry furnace superintendent after by laminating to lengthen with the scheme striving for time of drying; if but merely extended dry furnace superintendent, then there will be the problem easily causing variable color because of the thermal degradation when of polaroid.So, consider and reduce the scheme that drying temperature does not cause the thermal degradation when of polaroid.But during this situation, in order to the dry furnace superintendent of fully dry required lengthening further, there is the problem that facility investment is excessive.In addition; fit on the two sides of polaroid different types of protective membrane time; the shrinking percentage caused because of heat due to these protective membranes is different; therefore become with the state that the shrinkage of the protective membrane on two sides the is different situation bonding with polaroid, deposit and be back to normal temperature after the drying and retrodeviate vibration plate curling problem easily occurs.
In order to improve described problem, consider to adopt the applying method utilizing dry type stacked.But; because the viscosity of the caking agent with the stacked suitability of dry type is high; therefore there is the problem that the physical strength of polaroid is weak, due to this problem, the adhering method of polaroid and protective membrane is only limitted to the method being fitted to polaroid after protective membrane adhesive-applying again.In the method, when being attached with foreign matter in the applicator surface of caking agent before fitting, can not hidden foreign matter, be that starting point produces bubble between tack coat and polaroid with foreign matter after laminating, therefore become the reason of fleck defect.
Summary of the invention
Present inventor is in order to develop when the low resin molding of the Water Vapour Permeability that will be selected from vibrin, polycarbonate resin and acrylic resin is as the protective membrane of polaroid; just show the caking agent of the light solidified of good bonding power at short notice; carry out conscientious research; found that; by using specific Photocurable adhesive agent, can at short notice these protective membranes be fitted.So found; even if for the situation taking acrylic resin film as protective membrane; this caking agent also to giving high bonding force between itself and polaroid, and for using polyester resin film, polycarbonate resin adipose membrane as the situation of protective membrane, can play excellent bonding force too.
Therefore; the object of the invention is to; a kind of Photocurable adhesive agent is provided and uses this caking agent to fit the polarization plates of protective membrane at polaroid; even if wherein using the low resin molding of the Water Vapour Permeability being selected from vibrin, polycarbonate resin and acrylic resin as protective membrane; this protective membrane also can be adhered to polaroid with sufficient bonding strength by this light solidity caking agent at short notice, and does not cause the problems such as bad order.Another object of the present invention is to, a kind of optics using this polarization plates can form the excellent liquid crystal indicator of reliability is provided, and is applied to liquid crystal indicator.
That is, according to the invention provides a kind of Photocurable adhesive agent composition, it is the adhesive composite for protective membrane bonding on polaroid, this polaroid is by through unilateral stretching, be adsorbed with dichroism pigment and the polyvinyl alcohol resin film of dichroism pigment orientation is formed, this protective membrane is by being selected from vibrin, the transparent resin film of polycarbonate resin and acrylic resin is formed, described Photocurable adhesive agent composition contains the epoxy compounds in (A) molecule with at least 2 epoxy group(ing), (B) there is in molecule the oxetane compound of at least 1 oxetanylmethoxy, and (C) light cationic polymerization initiators, weight ratio (A)/(B) between above-mentioned epoxy compounds (A) and above-mentioned oxetane compound (B) is about 90/10 ~ 10/90, in composition, the amount of above-mentioned smooth cationic polymerization initiators (C) is about 0.5 ~ 20 % by weight.
In described Photocurable adhesive agent composition, preferably, epoxy compounds (A), containing the compound in molecule with at least 2 epoxy group(ing) and at least 1 aromatic nucleus, is specially in molecule the compound with at least 2 epoxy group(ing) and at least 1 aromatic nucleus; Or for there are at least 2 epoxy group(ing) in the compound in molecule with at least 2 epoxy group(ing) and at least 1 aromatic nucleus and molecule and not there is the mixture of the compound of aromatic nucleus.In addition, this epoxy compounds (A) more preferably containing more than one the epoxide be selected from the glycidyl ether of aromatics and glycidyl ester, is specially more than one epoxy compounds of glycidyl ether and the glycidyl ester being selected from aromatics; Or be the mixture of the epoxy compounds of more than a kind in the glycidyl ether compound that is selected from aromatics and epihydric alcohol ester compound and other epoxy compounds (A).
On the other hand, as the example of oxetane compound (B), there is in preferred molecule the compound of 1 oxetanylmethoxy and at least 1 aromatic nucleus, have in molecule in the compound of 1 oxetanylmethoxy and at least 1 aromatic nucleus and molecule and there is at least 1 oxetanylmethoxy and the mixture without the compound of aromatic nucleus, there is in molecule the compound of 2 oxetanylmethoxy, there is in molecule the compound of at least 2 oxetanylmethoxy, there is in molecule the mixture in the compound of 2 oxetanylmethoxy and molecule with the compound of 1 oxetanylmethoxy, there is in molecule the mixture etc. in the compound of at least 2 oxetanylmethoxy and molecule with the compound of 1 oxetanylmethoxy.
The unsaturated compound of at least 1 olefinic unsaturated link(age) can also be had as (D) composition containing in molecule in these Photocurable adhesive agent compositions, now, the amount of this unsaturated compound (D) is generally the ratio of less than 35 % by weight in the composition, is preferably 5 ~ 25 about % by weight.This unsaturated compound (D) is preferably (methyl) acrylic compounds in molecule with at least 1 (methyl) acryl and at least 1 alicyclic skeleton or aromatic nucleus skeleton, more preferably has two (methyl) acrylate of tricyclodecane skeleton.
Adhesive composite contain above-mentioned unsaturated compound (D) particularly (methyl) acrylic compounds time, preferably containing optical free radical polymerization starter as (E) composition.The amount of optical free radical polymerization starter (E) is preferably the ratio of about less than 10 % by weight in the composition.
This Photocurable adhesive agent composition can also containing not having other compositions of polymerizability as (F) composition, and now, the amount of other compositions (F) is preferably generally the ratio of about less than 10 % by weight in the composition.
In addition; according to the invention provides a kind of polarization plates; it is the polarization plates by caking agent, protective membrane being fitted in polaroid; wherein; polaroid by through unilateral stretching, be adsorbed with dichroism pigment and the polyvinyl alcohol resin film of dichroism pigment through orientation is formed; said protection film is made up of the transparent resin film being selected from vibrin, polycarbonate resin and acrylic resin, and this caking agent is formed by any one Photocurable adhesive agent composition above-mentioned.
Described polarization plates can be obtained by the method comprising following operation: adhesive applicating operation, at least one party of the binding face of polaroid and protective membrane, applies any one Photocurable adhesive agent composition above-mentioned; Bonding process, by the bond layer of gained, fits polaroid and protective membrane; Curing process, under the state of polaroid and protective membrane being fitted by described bond layer, makes Photocurable adhesive agent composition solidify.Specifically can adopt following method: after polaroid applies uncured above-mentioned Photocurable adhesive agent composition, at this adhesive composite applicator surface laminating protective membrane, then, make this adhesive composite solidify to form the method for bond layer; After protective membrane applies uncured above-mentioned Photocurable adhesive agent composition, polaroid is fitted to this adhesive composite applicator surface, then, make this adhesive composite solidify to form the method for bond layer; The above-mentioned Photocurable adhesive agent composition that curtain coating is uncured between polaroid and protective membrane; with the state of the laminating thing with the clamping polaroids such as roller and protective membrane, adhesive composite is extruded out equably; and make it crimping simultaneously, make this adhesive composite solidify to form the method etc. of bond layer afterwards again.
In addition, by the invention provides a kind of optics being laminated with the optical layers of above-mentioned polarization plates and other optical functions of display.Now, other optical layers preferably include polarizer.This optics is also provided to be configured in the liquid crystal indicator of the one-sided of liquid crystal cells or bilateral.
Photocurable adhesive agent composition of the present invention there is the irradiation through ultraviolet isoreactivity energy line and easily solidify, can the advantage of bonding polaroid and protective membrane securely at short notice.This adhesive composite is effective especially when protective membrane is made up of acrylic resin.Because this adhesive composite can solidify at short notice, therefore, productivity the polarization plates of polaroid and protective membrane being fitted and being obtained by this adhesive composite can be manufactured well.In addition, the optics being combined with this polarization plates and other optical layers can form the excellent liquid crystal indicator of reliability.
Embodiment
Below describe the present invention in detail.In the present invention; by through unilateral stretching, be adsorbed with dichroism pigment and in the process of the polaroid bonding protective membrane be made up of transparent resin film that forms of the polyvinyl alcohol resin film of dichroism pigment through orientation, use the Photocurable adhesive agent composition of specific composition.Like this, by polaroid and protective membrane being fitted by Photocurable adhesive agent composition, polarization plates can be obtained.This polarization plates is stacked with the optical layers with other optical functions, can optics be obtained.In addition, this optics is configured at least side of liquid crystal cells, can liquid crystal indicator be become.Below, successively Photocurable adhesive agent composition, polarization plates, the manufacture method of polarization plates, optics, liquid crystal indicator are described.
[Photocurable adhesive agent composition]
In the present invention, in the process of polaroid and protective membrane being fitted, employ the Photocurable adhesive agent composition of specific composition.Below, sometimes by this Photocurable adhesive agent composition referred to as " Photocurable adhesive agent ".Photocurable adhesive agent of the present invention is the caking agent that must contain following (A), (B) and (C) these three kinds of compositions.
(A) have in molecule the epoxy compounds of at least 2 epoxy group(ing),
(B) have in molecule at least 1 oxetanylmethoxy oxetane compound and
(C) light cationic polymerization initiators.
In this manual, sometimes by above-mentioned (A) epoxy compounds referred to as " (A) composition " or " epoxy compounds (A) ".Equally, in this manual, also (B) oxetane compound is called " (B) composition " or " oxetane compound (B) ", also (C) light cationic polymerization initiators is called " (C) composition " or " light cationic polymerization initiators (C) ".
(A) weight ratio of (A)/(B) between the epoxy compounds of composition and the oxetane compound of (B) composition is preferably about 90/10 ~ 10/90.In addition, the optical free radical polymerization starter of (C) composition is preferably the ratio of about 0.5 ~ 20 % by weight in the composition.
At random the unsaturated compound of at least 1 olefinic unsaturated link(age) can be had as (D) composition containing in molecule in described Photocurable adhesive agent, during containing this unsaturated compounds (D), preferably contain optical free radical polymerization starter as (E) composition.This Photocurable adhesive agent can also containing not having other compositions of polymerizability as (F) composition.
In this specification sheets, also by above-mentioned (D) unsaturated compound referred to as " (D) composition " or " unsaturated compound (D) ".Equally, in this manual, also be called " (E) composition " or " optical free radical polymerization starter (E) " by (E) optical free radical polymerization starter, other compositions (F) without polymerizability are called " (F) composition " or " not having other compositions (F) of polymerizability ".
< epoxy compounds (A))
In Photocurable adhesive agent of the present invention, as long as the epoxy compounds becoming (A) composition is the epoxide in molecule with at least 2 epoxy group(ing), just do not limit, usually known various solidified nature epoxy compoundss can be used.As the epoxy compounds preferably becoming (A) composition, can enumerate as: the compound in molecule with at least 2 epoxy group(ing) and at least 1 aromatic nucleus is (following, be called " fragrant family epoxy compounds "), or there are in molecule at least 2 epoxy group(ing) and wherein at least 1 forming the compound (hereinafter referred to as " cycloaliphatic epoxy ") etc. formed between adjacent 2 carbon atoms of ester ring type ring.
As fragrant family epoxy compounds, as long as do not hinder effect of the present invention, just there is no particular limitation, exemplarily can enumerate the bisphenol-type epoxy resin of the diglycidylether and so on as the diglycidylether of dihydroxyphenyl propane, the diglycidylether of Bisphenol F and brominated bisphenol A; The epoxy resin of the varnish type of phenolic resin varnish type epoxy resin and cresol novolacs type epoxy resin and so on; And the epoxide of hexichol type epoxy resin, quinhydrones diglycidylether, resorcinol diglycidyl ether, terephthalic acid diglycidyl ester, Diglycidyl M-phthalate, styrene-butadiene copolymer, the epoxide of styrene-isoprene copolymer, end have the polyhutadiene of carboxylic acid and the addition reaction etc. of bisphenol A type epoxy resin.
At this, epoxy resin refers in molecule the epoxy group(ing) with average more than 2 and the compound solidified through reaction or polymkeric substance.According to the convention of this area, in this specification sheets, as long as have the compound of the epoxy group(ing) of the solidified nature of more than 2 in molecule, even monomer is also sometimes referred to as epoxy resin.
As cycloaliphatic epoxy, as long as just there is no particular limitation not hinder effect of the present invention, exemplarily can enumerate as bicyclopentadiene dioxide, limonene dioxide, dioxidized 4-vinyl cyclohexene, 3,4-epoxycyclohexylmethyl 3, the compound etc. at least with 1 epoxidation cyclohexyl of 4-epoxycyclohexane carboxylate and two (3,4-epoxycyclohexylmethyl) adipic acid ester and so on.
Than that described above, the fatty family epoxy compounds of 1,6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, tetramethylolmethane four glycidyl ether and polytetramethylene glycol diglycidylether and so on, the epoxy compounds that the aromatic nucleus of the diglycidylether of Hydrogenated Bisphenol A and so on has been hydrogenated, two ends that two ends have a polyhutadiene of the hydroxyl compound by glycidyl ether, the inner loop oxide compound of polyhutadiene, the double bond of the styrene-butadiene copolymer compound by a part of epoxidation (such as, " エ Port Off レ Application De " that Daicel chemical industry (strain) is made), and the compound of the isoprene unit of the segmented copolymer of ethylene-butene copolymer and polyisoprene by a part of epoxidation (such as, " L-207 " of KRATON Inc.) and so on the epoxy compounds etc. of polymer system also can as the epoxy compounds of (A) composition.
In these, fragrant family epoxy compounds due to excellent, particularly excellent to the cementability of polaroid and protective membrane as weather resistance during polarization plates etc., therefore preferably.Moreover, as this fragrant family epoxy compounds, can enumerate if the glycidyl ether of aromatics or the glycidyl ester of aromatics etc. are as preferred exemplary.The concrete example preference of the glycidyl ether of aromatics is as the bisphenol-type epoxy resin of the diglycidylether of the diglycidylether of dihydroxyphenyl propane, the diglycidylether of Bisphenol F and brominated bisphenol A and so on; The type epoxy resin of phenolic resin varnish type epoxy resin and cresol novolacs type epoxy resin and so on; Hexichol type epoxy resin; Quinhydrones diglycidylether; Resorcinol diglycidyl ether etc.In addition, the concrete example of the glycidyl ester of aromatics preferably can enumerate terephthalic acid diglycidyl ester, phthalic acid 2-glycidyl ester etc.
Wherein, the glycidyl ether of aromatics due to the adhesion when polaroid is bonding with protective membrane, more excellent as weather resistance during polarization plates, therefore particularly preferably.As compound particularly preferred in the glycidyl ether of aromatics, can enumerate as the diglycidylether of dihydroxyphenyl propane, the diglycidylether of Bisphenol F and phenolic resin varnish type epoxy resin.
(A) epoxy compounds of composition can be used alone a kind, also can be used in combination by two or more.Such as, by used in combination for fragrant family epoxy compounds of more than two kinds, maybe using fragrant family epoxy compounds as main body, cycloaliphatic epoxy can be mixed.
< oxetane compound (B))
In Photocurable adhesive agent of the present invention, become (B) as long as composition oxetane compound molecule in there is the compound of at least 1 oxetanylmethoxy, be just not particularly limited, the various compounds with oxetanylmethoxy can be used.Oxetane compound (B) can enumerate the compound (hereinafter referred to as " multifunctional trimethylene oxide ") in compound (hereinafter referred to as " simple function trimethylene oxide ") as having 1 oxetanylmethoxy in molecule and molecule with more than 2 oxetanylmethoxy as preferred exemplary.
As the preferred exemplary of simple function trimethylene oxide, can enumerate such as, the simple function trimethylene oxide etc. containing hydroxyl of the simple function trimethylene oxide, 3-ethyl-3-hydroxymethyl oxetane and so on containing aromatic series base of the simple function trimethylene oxide, 3-ethyl-3-phenoxymethyloxetane and so on containing alkoxyalkyl of 3-ethyl-3-(2-Ethylhexoxymethyl) trimethylene oxide and so on.
As multifunctional trimethylene oxide, include, for example as following compound.
3-ethyl-3-((3-Ethyloxetane-3-base) methoxymethyl) trimethylene oxide,
Isosorbide-5-Nitrae-bis-((3-Ethyloxetane-3-base) methoxymethyl) benzene,
Isosorbide-5-Nitrae-bis-((3-Ethyloxetane-3-base) methoxyl group) benzene,
Two ((3-Ethyloxetane-3-base) methoxyl group) benzene of 1,3-,
Two ((3-Ethyloxetane-3-base) methoxyl group) benzene of 1,2-,
4,4 '-bis-((3-Ethyloxetane-3-base) methoxyl group) biphenyl,
2,2 '-bis-((3-Ethyloxetane-3-base) methoxyl group) biphenyl,
3,3 ', 5,5 '-tetramethyl--4,4 '-bis-((3-Ethyloxetane-3-base) methoxyl group) biphenyl,
Two ((3-Ethyloxetane-3-base) methoxyl group) naphthalene of 2,7-,
Two (4-{ (3-Ethyloxetane-3-base) methoxyl group } phenyl) methane,
Two (2-{ (3-Ethyloxetane-3-base) methoxyl group } phenyl) methane,
2,2-pair (4-{ (3-Ethyloxetane-3-base) methoxyl group } phenyl propane,
The etherification modified thing through 3-chloromethyl-3-Ethyloxetane of varnish-type phenolic resin formaldehyde resin,
3 (4), 8 (9)-bis-((3-Ethyloxetane-3-base) methoxymethyl)-three ring [5.2.1.0 2,6] decane,
Two ((3-Ethyloxetane-3-base) methoxymethyl) norbornane of 2,3-,
1,1,1-tri-((3-Ethyloxetane-3-base) methoxymethyl) propane,
Two ((3-Ethyloxetane-3-base) methoxymethyl) butane of 1-butoxy-2,2-,
Two ({ 2-(3-Ethyloxetane-3-base) methoxyl group } ethylsulfanyl) ethane of 1,2-,
Two ({ 4-(3-Ethyloxetane-3-base) methylsulfany } phenyl) sulfide,
Two ((3-Ethyloxetane-3-base) methoxyl group)-2,2,3,3,4,4,5, the 5-octafluoro hexanes of 1,6-,
The hydrolytic condensate of 3-((3-Ethyloxetane-3-base) methoxyl group) propyl-triethoxysilicane,
The condenses etc. of four ((3-Ethyloxetane-3-base) methyl) silicon ester.
From screening characteristics, become polarization plates time viewpoint to the adhesion of protective membrane, be liquid compound under the oxetane compound of (B) composition is preferably the room temperature of molecular weight less than 500.Moreover, from the angle of the excellent durability of polarization plates, as during for simple function trimethylene oxide, more preferably there is in molecule the compound of aromatic nucleus, or multifunctional trimethylene oxide.As the example of this particularly preferred oxetane compound, can enumerate as 3-ethyl-3-phenoxymethyloxetane, 3-ethyl-3-((3-Ethyloxetane-3-base) methoxymethyl) trimethylene oxide and Isosorbide-5-Nitrae-bis-((3-Ethyloxetane-3-base) methoxymethyl) benzene etc.
(B) oxetane compound of composition is except being used alone a kind, also can be mixed with two or more.
The ratio > of < epoxy compounds (A) and oxetane compound (B)
(A) usage ratio of the epoxy compounds of composition and the oxetane compound of (B) composition with the mass ratio range of (A)/(B) for 90/10 ~ 10/90.As far away less than this ratio, then can not give full play to one of key property of Photocurable adhesive agent of the present invention, the effect of namely solidifying at short notice.When considering both for suitable part by weight, before curing for low viscosity and screening characteristics is excellent and can show sufficient adhesion and pliability after solidification, be therefore about 70/30 ~ 20/80, preferred part by weight is about 60/40 ~ 25/75.
< light cationic polymerization initiators (C) >
Photocurable adhesive agent of the present invention contains the epoxy compounds (A) and oxetane compound (B) that are explained above as cure component, any one in them is all solidified through cationic polymerization, is therefore combined with the light cationic polymerization initiators as (C) composition.This light cationic polymerization initiators, through the irradiation of visible ray, ultraviolet, X-ray, electron rays isoreactivity energy line, produces positively charged ion kind or Lewis acid, thus causes the polyreaction of epoxy group(ing), oxetanylmethoxy.
By coordinating as the light cationic polymerization initiators of (C) composition, can solidify at normal temperatures, considering the necessity minimizing of the distortion caused because of the thermotolerance of polaroid, expansion or contraction, can bonding protective membrane well.In addition, light cationic polymerization initiators through active energy ray irradiation and play the effect of catalyzer, therefore, even if be mixed in epoxy compounds (A) and oxetane compound (B), storage stability, workability are also excellent.Produce positively charged ion kind, lewis acidic compound as the irradiation through active energy ray, the salt as aromatic diazonium salt, aromatic iodonium salts, aromatic series sulfonium salt and so on can be enumerated, iron-allene complex thing etc.
As aromatic diazonium salt, the compound that can be listed below:
Benzene diazonium hexafluoro antimonate,
Benzene diazonium hexafluorophosphate,
Benzene diazonium hexafluoro borate etc.
As aromatic iodonium salts, the compound that can be listed below:
Phenylbenzene iodine four (pentafluorophenyl group) borate,
Diphenyl iodine hexafluorophosphate,
Phenylbenzene iodine hexafluoro antimonate,
Two (4-nonyl phenyl) iodine hexafluorophosphate etc.
As aromatic series sulfonium salt, the compound that can be listed below:
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoro antimonate,
Triphenylsulfonium four (pentafluorophenyl group) borate,
Phenylbenzene (4-(phenylsulfartyl) phenyl) sulfonium hexafluorophosphate,
Phenylbenzene (4-(phenylsulfartyl) phenyl) sulfonium hexafluoro antimonate,
The two hexafluorophosphate of 4,4 '-bis-(phenylbenzene sulfonium base (sulfonio)) diphenyl sulfide,
The two hexafluoro antimonate of 4,4 '-bis-(two (beta-hydroxy oxyethyl group) phenyl sulfonium base) diphenyl sulfide,
The two hexafluorophosphate of 4,4 '-bis-(two (beta-hydroxy oxyethyl group) phenyl sulfonium base) diphenyl sulfide,
7-(two (p-toluyl) sulfonium base)-ITX hexafluoro antimonate,
7-(two (p-toluyl) sulfonium base)-ITX four (pentafluorophenyl group) borate,
4-phenylcarbonyl group-4 '-phenylbenzene sulfonium base-diphenyl sulfide hexafluorophosphate,
4-(p-tert-butyl-phenyl carbonyl)-4 '-phenylbenzene sulfonium base-diphenyl sulfide hexafluoro antimonate,
4-(p-tert-butyl-phenyl carbonyl)-4 '-two (p-toluyl) sulfonium base-diphenyl sulfide four (pentafluorophenyl group) borate etc.
As iron-allene complex thing, the compound that can be listed below:
Dimethylbenzene-cyclopentadienyl iron (II) hexafluoro antimonate,
Cumene-cyclopentadienyl iron (II) hexafluorophosphate,
Dimethylbenzene-cyclopentadienyl iron (II)-three (trifluoromethyl sulfonyl) methanides etc.
These light cationic polymerization initiators can individually use a kind, also can be used in combination by two or more.Wherein, even if also there is Ultraviolet Light in the wavelength region may of more than 300nm due to aromatic series sulfonium salt, thus can provide the cured article that solidified nature is excellent, have good mechanical strength, bonding strength, therefore particularly preferably use aromatic series sulfonium salt.
Light cationic polymerization initiators easily can buy commercially available product, such as, can enumerate as " KAYARAD (カ ヤ ラ ッ De) PCI-220 " with trade(brand)name, " KAYARAD PCI-620 " (being Japanese chemical drug (strain) system above), " UVI-6992 " (Dow Chemical's system), " ア デ カ オ プ ト マ mono-SP-150 ", " ア デ カ オ プ ト マ mono-SP-170 " (being ADEKA Corp.'s system above), " CI-5102 ", " CIT-1370 ", " CIT-1682 ", " CIP-1866S ", " CIP-2048S ", " CIP-2064S " (being Japanese Cao Da (strain) system above), " DPI-101 ", " DPI-102 ", " DPI-103 ", " DPI-105 ", " MPI-103 ", " MPI-105 ", " BBI-101 ", " BBI-102 ", " BBI-103 ", " BBI-105 ", " TPS-101 ", " TPS-102 ", " TPS-103 ", " TPS-105 ", " MDS-103 ", " MDS-105 ", " DTS-102 ", " DTS-103 " (above is greening (strain) system), " PI-2074 " (Rhodia's system), " IRGACURE (イ Le ガ キ ュ ア) 250 ", " IRGACURE PAG103 ", IRGACUREPAG108 ", IRGACURE PAG121 ", IRGACURE PAG203 " (being Qi Ba Inc. above), " CPI-100P ", " CPI-101A ", " CPI-200K ", " CPI-210S " (being general sieve of China fir (strain) system above) etc., particularly preferably containing " UVI-6992 " of phenylbenzene (4-(phenylsulfartyl) phenyl) sulfonium as the Dow Chemical of cation constituent, " CPI-100P " that general sieve of China fir (strain) is made, " CPI-101A ", " CPI-200K ", " CPI-210S ".
(C) mixing ratio of the light cationic polymerization initiators of composition is with Photocurable adhesive agent totally for benchmark, is the scope of 0.5 ~ 20 % by weight.As its ratio is less than 0.5 % by weight, then the solidification of caking agent is insufficient, and physical strength, bonding strength decline, on the other hand, if its ratio is more than 20 % by weight, then the ionic substance in cured article increases, therefore the water absorbability of cured article increases, and weather resistance likely reduces.
< unsaturated compound (D) >
In Photocurable adhesive agent of the present invention, the unsaturated compound of at least 1 olefinic unsaturated link(age) can be had as (D) composition containing in molecule as required.As the typical case of described unsaturated compound (D), (methyl) acrylic compounds as having at least 1 (methyl) acryl in molecule can be enumerated.
Be not particularly limited as (methyl) acrylic compounds, can enumerate as (methyl) esters of acrylic acid, (methyl) acrylic amide, (methyl) vinylformic acid, (methyl) acryloyl morpholine, (methyl) propenal etc.
As (methyl) esters of acrylic acid (hereinafter referred to as simple function (methyl) acrylate) in molecule with 1 (methyl) acryl, there is no particular limitation, the compound that can be listed below:
(methyl) alkyl-acrylates of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, 2-ethylhexyl (methyl) acrylate, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate and (methyl) octadecyl acrylate and so on;
Hydroxyalkyl (methyl) esters of acrylic acid of 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate and 4-hydroxybutyl (methyl) acrylate and so on;
Ester ring type simple function (methyl) esters of acrylic acid of (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, Isosorbide-5-Nitrae-cyclohexane dimethylol list (methyl) acrylate, bicyclopentyl (methyl) acrylate, dicyclopentenyl (methyl) acrylate, dicyclopentenyl oxygen base ethyl (methyl) acrylate and so on;
Simple function (methyl) esters of acrylic acid with aromatic ring of (methyl) acrylate of (methyl) benzyl acrylate, p-cumyl phenol alkylene oxide adduct, (methyl) acrylate of o-phenylphenol alkylene oxide adduct, (methyl) acrylate of phenol alkylene oxide adduct and (methyl) acrylate of nonylphenol alkylene oxide adduct and so on is (at this, as alkylene oxide, can enumerate as ethylene oxy or propylene oxygen etc.);
Alkoxyalkyl (methyl) esters of acrylic acid of (methyl) acrylate of the alkylene oxide adduct of 2-methoxy ethyl (methyl) acrylate, ethoxyl methyl (methyl) acrylate and 2-ethylhexyl alcohol and so on;
List (methyl) esters of acrylic acid of the dibasic alcohol of ethylene glycol list (methyl) acrylate, propylene glycol list (methyl) acrylate, pentanediol list (methyl) acrylate and hexylene glycol list (methyl) acrylate and so on;
List (methyl) esters of acrylic acid of many alkane glycol of list (methyl) acrylate of list (methyl) acrylate of list (methyl) acrylate of glycol ether, list (methyl) acrylate of triglycol, Tetraglycol 99, list (methyl) acrylate of polyoxyethylene glycol, list (methyl) acrylate of dipropylene glycol, list (methyl) acrylate of tripropylene glycol and polypropylene glycol and so on;
(methyl) glycidyl acrylate;
(methyl) tetrahydrofurfuryl acrylate;
(methyl) tetrahydrofurfuryl acrylate class of caprolactone modification (methyl) tetrahydrofurfuryl acrylate and so on;
3,4-epoxycyclohexylmethyl (methyl) acrylate;
N, N-dimethyl aminoethyl (methyl) acrylate;
2-(methyl) acryloyloxyethyl isocyanate etc.
In addition, in molecule, having (methyl) esters of acrylic acid of more than 2 (methyl) acryls, there is no particular limitation, the compound that can be listed below:
Two (methyl) esters of acrylic acid with ester ring type ring of two (methyl) acrylate of tristane dihydroxymethyl two (methyl) acrylate, Isosorbide-5-Nitrae-cyclohexane dimethylol two (methyl) acrylate, norbornane dihydroxymethyl two (methyl) acrylate and Hydrogenated Bisphenol A and so on;
Two (methyl) esters of acrylic acid with aromatic ring of two (methyl) acrylate of the dihydroxyphenyl propane alkylene oxide adduct of two (methyl) acrylate of two (methyl) acrylate containing dihydroxyphenyl propane ethylene oxy affixture and dihydroxyphenyl propane propylene oxygen affixture and two (methyl) acrylate of bisphenol A diglycidyl ether and so on;
Two (methyl) esters of acrylic acid of the alkylene glycol of ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, pentanediol two (methyl) acrylate and hexylene glycol two (methyl) acrylate and so on;
Two (methyl) esters of acrylic acid of many alkylene glycols of glycol ether two (methyl) acrylate, triglycol two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate and polypropylene glycol two (methyl) acrylate and so on;
Two or three (methyl) esters of acrylic acid of the glycerols of two or three (methyl) acrylate of two of glycerine or three (methyl) acrylate and two glycerine and so on;
Two or three (methyl) esters of acrylic acid of the alkylene oxide adduct of glycerols;
Two (methyl) esters of acrylic acid of the bis-phenol alkylene oxide adduct of two (methyl) acrylate of dihydroxyphenyl propane alkylene oxide adduct and two (methyl) acrylate of Bisphenol F alkylene oxide adduct and so on;
Polyol many (methyl) esters of acrylic acid of trimethylolpropane tris (methyl) acrylate, ditrimethylolpropane three (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate and so on;
Many (methyl) esters of acrylic acid of the alkylene oxide adduct of these polyols;
Two of isocyanuric acid alkylene oxide adduct or three (methyl) esters of acrylic acid;
1,3,5-tri-(methyl) acryloyl six hydrogen-s-triazine etc.
As (methyl) acrylic amide, can enumerate as (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, two (methyl) acrylamides of N-diethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-(3-N, N-dimethylaminopropyl) (methyl) acrylamide, methylene-bis (methyl) acrylamide, ethene etc.
Also can use in addition (methyl) vinylformic acid urethane ester, polyester (methyl) acrylate and epoxy group(ing) (methyl) acrylate and so on oligopolymer as (methyl) acrylic compounds.
Moreover; also the compound with (methyl) acryl and olefinic unsaturated link(age) in addition can be used as (methyl) acrylic compounds; as its concrete example; can enumerate as (methyl) allyl acrylate, N, N-diallyl (methyl) acrylamide etc.
As (D) composition, there is no particular limitation, except above (methyl) acrylic compounds, also can use the vinyl compound of NVP, vinyl hexanediacetate and sebacic acid divinyl ester and so on; Cyanacrylate, triallylamine, tetraallyl pyromellitic ester, N, N, N ', the allylic cpd of N '-tetraallyl-1,4-Diaminobutane, tetraallyl ammonium salt and allyl amine and so on; The unsaturated carboxylic acid etc. of toxilic acid and methylene-succinic acid and so on.
In the unsaturated compound of these (D) compositions, preferably (methyl) acrylic compounds.In addition; by containing these compositions caking agent by bonding with protective membrane for polaroid make polarization plates time; from the viewpoint improving the weather resistance such as thermotolerance, there is in preferred molecule (methyl) acrylic compounds of at least 1 alicyclic skeleton or aromatic nucleus skeleton.As the concrete example of (methyl) acrylic compounds in described molecule with at least 1 alicyclic skeleton or aromatic nucleus skeleton, preference ester ring type simple function (methyl) described above esters of acrylic acid, have aromatic ring simple function (methyl) esters of acrylic acid, there are two (methyl) esters of acrylic acids of ester ring type ring and there is two (methyl) esters of acrylic acid of aromatic ring.Wherein, particularly preferably there is two (methyl) acrylate of tricyclodecane skeleton, as the concrete example of this particularly preferred (methyl) acrylic compounds, can enumerate as tristane dihydroxymethyl two (methyl) acrylate etc.
In order to regulate adhesion, the Young's modulus of adhesive linkage, the weather resistance etc. of sticky object of curing speed, polaroid and protective membrane, the unsaturated compound of (D) composition can be used.(D) unsaturated compound of composition can be used alone a kind, also can mix two or more and use.
When coordinating the unsaturated compound of (D) composition, its mixing ratio with composition totally for benchmark is preferably less than 35 % by weight.Like this, the adhesion of polaroid and protective membrane is excellent.If the amount of unsaturated compound (D) is more than 35 % by weight, then can not obtain with polaroid sufficient bonding strength.Therefore, the mixing ratio of unsaturated compound (D) is more preferably less than 30 % by weight, then is more preferably 5 ~ 25 about % by weight, and particularly preferably 10 ~ 20 about % by weight.
< optical free radical polymerization starter (E) >
When Photocurable adhesive agent of the present invention contains the unsaturated compound of (D) composition, in order to promote that it is free-radical polymerised, obtain the Photocurable adhesive agent that curing speed is desirable, preferably coordinate the optical free radical polymerization starter as (E) composition.
As the concrete example of optical free radical polymerization starter becoming (E) composition, there is no particular limitation, include, for example as following compound:
4 '-phenoxy group-2, 2-ω,ω-dichloroacetophenone, 4 '-tertiary butyl-2, 2-ω,ω-dichloroacetophenone, 2, 2-dimethoxy-2-phenyl acetophenone, 2-methyl isophthalic acid-(4-methylsulfanylphenyl)-2-morpholino propane-1-ketone, 1-hydroxycyclohexylphenylketone, α, α-diethoxy phenyl methyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone, the acetyl benzene series Photoepolymerizationinitiater initiater of 1-(4-(2-hydroxyl-oxethyl) phenyl)-2-hydroxy-2-methyl propane-1-ketone and 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone and so on,
The benzoin ether system Photoepolymerizationinitiater initiater of bitter almond oil camphor, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether and so on;
The benzophenone series Photoepolymerizationinitiater initiater of benzophenone, o-benzoyl M-nitro benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide and 2,4,6-tri-methyl benzophenone and so on;
The thioxanthone system Photoepolymerizationinitiater initiater of ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones and the chloro-4-propoxythioxanthone of 1-and so on;
2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide and two (2,4,6-trimethylbenzoyl) the acylphosphine oxide system Photoepolymerizationinitiater initiater of phenylphosphine oxide and so on;
1,2-acetyl caproyl, 1-(4-(phenylsulfartyl phenyl))-, the oxime ester system Photoepolymerizationinitiater initiater of 2-(O-benzoyl oxime) and so on;
Camphorquinone etc.
(E) the optical free radical polymerization starter of composition can be used alone a kind, also can performance desirably and coordinate two or more to use.When coordinating the optical free radical polymerization starter of (E) composition, its mixing ratio totally for benchmark with composition, is preferably less than 10 % by weight, is more preferably 0.1 ~ 3 about % by weight.Optical free radical polymerization starter (E) if amount too much, then can not obtain sufficient intensity, in addition, if its quantity not sufficient, then caking agent can not fully solidify sometimes.
Other compositions of < >
In addition, in the scope not damaging effect of the present invention, other compositions different from above-mentioned (A) ~ (E) composition in Photocurable adhesive agent of the present invention, can be coordinated arbitrarily.As the one belonged in other compositions described, the compound with cationic polymerization except as the oxetane compound except the epoxy compounds of (A) composition, (B) composition can be enumerated, being not particularly limited as its concrete example, the epoxy compounds etc. as having 1 epoxy group(ing) in molecule can being enumerated.In addition, as other kinds belonging to other compositions, other compositions (F) if not having polymerizability can be enumerated.Coordinate when not there is other compositions (F) of polymerizability, its mixing ratio with composition totally for benchmark is preferably about less than 10 % by weight.
As the example of other compositions (F) without polymerizability, there is no particular limitation, can enumerate as photosensitizing agent.By coordinating photosensitizing agent, can make reactive raising, physical strength, the bonding strength of cured article increase.As photosensitizing agent, can enumerate as carbonyl compound, organic sulfide, persulfide, redox based compound, azo and diazonium compound, halogenide, photoreduction pigment etc.
As concrete photosensitizing agent, there is no particular limitation, the compound that can be listed below:
Benzoin methyl ether, benzoin isopropyl ether and α, the benzoin derivatives of alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone and so on;
The benzophenone derivates of benzophenone, 2,4-dichloro benzophenones, o-benzoyl M-nitro benzoic acid methyl esters, 4,4 '-bis-(dimethylamino) benzophenone and 4,4 '-bis-(diethylamino) benzophenone and so on;
The thioxanthone derivates of CTX and ITX and so on;
The anthraquinone derivative of 2-chloroanthraquinone and 2-methylanthraquinone and so on;
The acridone derivatives of N-methylacridine ketone and N-butyl dihydroketoacridine and so on;
And, α, α-diethoxy phenyl methyl ketone, benzyl, Fluorenone, xanthone, uranyl (uranyl) compound, halogenide etc.
Wherein, there is the compound of the optical free radical polymerization starter being equivalent to above-mentioned (E) composition, but as long as the compound of sensitizer effect can be played to the light cationic polymerization initiators of (C) composition at this so-called photosensitizing agent, just there is no particular limitation.They can individually use, also can be used in combination by two or more.
Be 100 weight parts with the total amount of Photocurable adhesive agent cationic catalyzed polymerization monomer of the present invention (comprise containing above-mentioned epoxy compounds (A) and oxetane compound (B) and be combined with the situation that above-mentioned other have the compound of cationic polymerization), preferably in the scope of 0.1 ~ 20 weight part containing photosensitizing agent.
In addition, as other compositions (F) without polymerizability, hot cationic polymerization initiator can be used.As hot cationic polymerization initiator, can enumerate as benzylsulfonium, thiophene (thiophenium) salt, tetramethylene sulfide (thiolanium) salt, benzyl ammonium salt, pyridinium salt, salt, carboxylicesters, sulphonate, amine imide etc.These initiators easily obtain commercially available product, represent with trade(brand)name, such as " ADEKAOPTON (ア デ カ オ プ ト Application) CP77 " and " ADEKAOPTON CP66 " (above is (strain) ADEKA system), " CI-2639 " and " CI-2624 " (above is Japanese Cao Da (strain) system), " SUN-acid (サ Application エ イ De) SI-60L ", " SUN-acidSI-80L " and " SUN-acid SI-100L " (being three new chemical industry (strain) systems above) etc.
Polyol class has the character promoting cationic polymerization, therefore also can use as other compositions (F) without polymerizability.As polyol class, preferably there is not the acidic groups beyond phenolic hydroxyl group, the polyol if not having the functional group beyond hydroxyl, polyester polyol, many caprolactones polyol, the polyol with phenolic hydroxyl group, many carbonic ethers polyol etc. can being enumerated.
Moreover, in the scope not damaging effect of the present invention, the silane coupling agent, ion trap agent, antioxidant, photostabilizer, chain-transfer agent, sensitizer, adhesion imparting agent, thermoplastic resin, weighting agent, flow modifier, softening agent, defoamer, flow agent, pigment, organic solvent etc. as other compositions (F) without polymerizability can be added.As other compositions (F) without polymerizability; to improve for the purpose of the adhesion with protective membrane further; thermoplastic resin is coordinated to be effective scheme; as thermoplastic resin; from the view point of the weather resistance improving polaroid; preferred glass temperature is the thermoplastic resin of more than 70 DEG C, as particularly preferred example, can enumerate as methyl methacrylate based polymer etc.
[polarization plates]
Photocurable adhesive agent described above be used for by through unilateral stretching, be adsorbed with dichroism pigment and the polaroid bonding protective membrane that forms of the polyvinyl alcohol resin film of dichroism pigment through orientation; like this, protective membrane is bonded to polaroid and becomes polarization plates.That is, as long as the polarization plates that the present invention relates to by through unilateral stretching, be adsorbed with dichroism pigment and the polaroid that the polyvinyl alcohol resin film of dichroism pigment through orientation is formed is fitted with the polarization plates of protective membrane, just there is no particular limitation.Protective membrane only can fit in the one side of polaroid, also can fit in the two sides of polaroid.When the two sides of polaroid laminating protective membrane, each protective membrane can be formed by homogenous resins, also can by different resin formation.
< polaroid >
The polyvinyl alcohol resin forming polaroid can by obtaining the resin saponification of polyvinyl acetate system.As polyvinyl acetate system resin, except the polyvinyl acetate of the homopolymer as vinyl acetate, also such as vinyl acetate and can with the multipolymer etc. of other monomers of its copolymerization.As other monomers with vinyl acetate copolymerization, can enumerate as unsaturated carboxylic acid class, olefines, ethene ethers, unsaturated sulfonic acid class etc.There is no particular limitation for the saponification deg of polyvinyl alcohol resin, is generally 85 ~ 100 % by mole, is preferably the scope of 98 ~ 100 % by mole.This polyvinyl alcohol resin can also be modified, the polyvinyl formal, polyvinylacetal etc. that such as can use by aldehydes modification.There is no particular limitation for the polymerization degree of polyvinyl alcohol resin, is generally 1000 ~ 10000, is preferably the scope of 1500 ~ 10000.
Polarization plates obtains by following operation: by the operation of this polyvinyl alcohol resin film unilateral stretching; By polyvinyl alcohol resin film dichroism pigment dyeing, make the operation that this dichroism pigment adsorbs; The polyvinyl alcohol resin film boric acid aqueous solution being adsorbed with dichroism pigment is carried out the operation processed; After boric acid aqueous solution process, carry out the operation of washing; And to implementing these operations, be adsorbed with dichroism pigment and the operation of the unilateral stretching polyvinyl alcohol resin film laminating protective membrane of dichroism pigment through orientation.
Unilateral stretching can utilize dichroism pigment dye before carry out, also can with utilize dichroism pigment to carry out dyeing to carry out simultaneously, also can utilize dichroism pigment dye after carry out.In addition, utilize dichroism pigment dye after carry out unilateral stretching time, this unilateral stretching can be carried out before boric acid process, also can carry out in boric acid process.In addition, certainly, also unilateral stretching can be carried out at this multiple Duan Bands.Can, to unilateral stretching between the roller that peripheral speed is different, hot-rolling also can be used to unilateral stretching to unilateral stretching.In addition, for carrying out the dry type stretching stretched in an atmosphere, also can stretch for the wet type of carrying out stretching under the state utilizing solvent-swollen.Stretching ratio is not particularly limited, and is generally about 4 ~ 8 times.
When dyeing to polyvinyl alcohol resin film with dichroism pigment, if such as by polyvinyl alcohol resin film immersion in the aqueous solution containing dichroism pigment.As dichroism pigment, can specifically use iodine or dichroic dye.
When dichroism pigment uses iodine, be typically employed in the aqueous solution containing iodine and potassiumiodide the method for flooding polyvinyl alcohol resin film and carrying out dyeing.There is no particular limitation for the content of the iodine in this aqueous solution, and every 100 weight parts waters are about 0.01 ~ 0.5 weight part usually, and there is no particular limitation for the content of potassiumiodide, and every 100 weight parts waters are about 0.5 ~ 10 weight part usually.There is no particular limitation for the temperature of this aqueous solution, is generally about 20 ~ 40 DEG C, and in addition, there is no particular limitation for the dipping time in this aqueous solution, is generally about 30 ~ 300 seconds.
On the other hand, when dichroism pigment uses dichroic dye, the method for to flood polyvinyl alcohol resin film and carrying out dyeing in the aqueous solution containing water-soluble dichroic dye can usually be adopted.There is no particular limitation for the content of the dichroic dye in this aqueous solution, and every 100 weight parts waters are 1 × 10 usually -3~ 1 × 10 -2about weight part.This aqueous solution also can containing inorganic salt such as sodium sulfate.There is no particular limitation for the temperature of this aqueous solution, is generally about 20 ~ 80 DEG C, and in addition, there is no particular limitation for the dipping time in this aqueous solution, is generally about 30 ~ 300 seconds.
Boric acid process after utilizing dichroism pigment to dye can be carried out in boric acid aqueous solution by the polyvinyl alcohol resin film immersion that will be colored.There is no particular limitation for the content of the boric acid in boric acid aqueous solution, about every 100 weight parts waters are 2 ~ 15 weight parts usually, be preferably 5 ~ 12 weight parts about.When dichroism pigment uses iodine, preferably this boric acid aqueous solution contains potassiumiodide.There is no particular limitation for the content of the potassiumiodide in boric acid aqueous solution, about every 100 weight parts waters are 2 ~ 20 weight parts usually, is preferably 5 ~ 15 weight parts.There is no particular limitation for dipping time in boric acid aqueous solution, is generally about 100 ~ 1200 seconds, preferably about 150 ~ 600 seconds and then preferably about 200 ~ 400 seconds.There is no particular limitation for the temperature of boric acid aqueous solution, is generally more than 50 DEG C, is preferably 50 ~ 85 DEG C.
Polyvinyl alcohol resin film after boric acid process will carry out washing process usually.Washing processing example is as by will be carried out in water by the acid-treated polyvinyl alcohol resin film immersion of boron.Implement drying treatment after washing, obtain polaroid.There is no particular limitation for the temperature of the water in washing process, and be generally about 5 ~ 40 DEG C, there is no particular limitation for dipping time, is generally about 2 ~ 120 seconds.The drying treatment of carrying out thereafter uses hot air dryer or far infra-red heater to carry out usually.There is no particular limitation for drying temperature, is generally 40 ~ 100 DEG C.Treatment time in drying treatment, there is no particular limitation, is generally about 120 ~ 600 seconds.
Like this, can obtain by being adsorbed with as the iodine of dichroism pigment or dichroic dye and the polaroid of this iodine as dichroism pigment or the dichroic dye polyvinyl alcohol resin film through orientation.
< protective membrane >
Then, the Photocurable adhesive agent illustrated before use, at the single or double laminating protective membrane of this polaroid.All the time, as polaroid protective membrane and the tri acetyl cellulose membrane extensively adopted has roughly 400g/m 2the Water Vapour Permeability of about/24hr, and in the present invention, as the protective membrane at least simultaneously fitting in polaroid, adopt the vibrin of the resin of display Water Vapour Permeability lower than described triacetyl cellulose, polycarbonate resin or acrylic resin.
There is no particular limitation for the kind of the vibrin used in protective membrane, from the viewpoint of mechanical properties, solvent resistance, scratch resistance, cost etc., and particularly preferably polyethylene terephthalate.Polyethylene terephthalate refers to more than the 80 % by mole resins be made up of ethylene glycol terephthalate of repeating unit, also can containing the Component units from other copolymer compositions.As other copolymer compositions, preferably can enumerate as different phthalic acid, the fragrant acid of p-beta-hydroxy ethoxy ethyl, 4,4 '-dicarboxyl hexichol, 4, the dicarboxylic acid component of 4 '-benzophenonedicarboxylic acid, two (4-carboxyl phenyl) ethane, hexanodioic acid, sebacic acid, 5-sodium sulfoisophthalic acid and Isosorbide-5-Nitrae-dicarboxyl hexanaphthene and so on; The diol component etc. of the ethylene oxy affixture of propylene glycol, butyleneglycol, neopentyl glycol, glycol ether, cyclohexanediol, dihydroxyphenyl propane, polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol and so on.These dicarboxylic acid component, diol component also can combine two or more as required respectively and use.In addition, can also also with the hydroxycarboxylic acid of p-Para Hydroxy Benzoic Acid and so on while using above-mentioned dicarboxylic acid component, diol component.As other copolymer compositions, the dicarboxylic acid component and/or diol component can with amido linkage, urethane bond, ehter bond, carbonic acid ester bond etc. also can be used on a small quantity.
As the manufacture method of vibrin, can adopt make terephthalic acid and ethylene glycol (moreover, other dicarboxylic acid as required and/or other glycol) the so-called direct polymerization method of direct reaction, the dimethyl ester of terephthalic acid and ethylene glycol (moreover, the methyl ester of other dicarboxylic acid as required and/or other glycol) is made to carry out the arbitrary methods such as the so-called transesterification reaction method of transesterification reaction.In addition, vibrin also can contain known additive as required.As the additive that can contain, there is no particular limitation, can enumerate as lubricant, anti-hard caking agent, thermo-stabilizer, antioxidant, antistatic agent, photostabilizer, shock-resistance modifying agent etc.The protective membrane being laminated in polarization film needs the transparency, and therefore the amount of these additives is preferably limited to irreducible minimum.
Be membranaceous by above-mentioned raw materials ester moulding, implement unilateral stretching or two-way stretch process, thus the protective membrane be made up of vibrin of drawn can be manufactured.By implementing stretch processing, the film that physical strength is high can be obtained.The manufacture method of the polyester resin film of drawn is arbitrary, and there is no particular limitation, can enumerate as: by above-mentioned raw materials resin melting, use tenter machine, at temperature more than second-order transition temperature, be after the horizontal stretching of No yield point film of sheet by extrusion moulding, implement the method for heat fixation process.
The polycarbonate resin used in protective membrane preferably can enumerate the polyester as formed by carbonic acid and glycol or bis-phenol.Wherein, the aromatic copolycarbonate in molecular chain with phenylbenzene alkane, due to thermotolerance, weathering resistance and acid-proof, therefore preferably uses.As this polycarbonate, can enumerate as by 2, two (4-hydroxy phenyl) propane (another name dihydroxyphenyl propane), 2 of 2-, two (4-hydroxy phenyl) butane, 1 of 2-, two (4-hydroxy phenyl) hexanaphthene, 1 of 1-, the polycarbonate that the bisphenols of two (4-hydroxy phenyl) Trimethylmethane of 1-or two (4-hydroxy phenyl) ethane of 1,1-and so on derives.
As the manufacture method of polycarbonate resin adipose membrane, the arbitrary method such as casting film method, extrusion by melting can be used.As concrete manufacture method, the method that can be listed below, that is: polycarbonate resin is dissolved in suitable organic solvent forms polycarbonate resin solution, base material (web) is formed by its curtain coating to metal support, after being peeled off from above-mentioned metal support by this base material, the base material warm air drying after stripping is obtained the method for film.
Also there is no particular limitation for the acrylic resin used in protective membrane, take methacrylic acid as the monomer of principal constituent and copolymerization wherein has the multipolymer of other comonomer compositions a small amount of by preferred.As the methacrylic ester preference of the principal constituent of acrylic resin as alkyl methacrylate, particularly preferably methyl methacrylate.In addition, as comonomer composition, there is no particular limitation, generally uses methyl acrylate, ethyl propenoate, butyl acrylate, 2-ethyl-hexyl acrylate ester etc.Moreover, alkene nitrile compound of the aromatic ethylene compound of vinylbenzene and so on, vinyl cyanide and so on etc. also can be used as comonomer composition.
As the manufacture method of acrylic resin, the arbitrary method such as common mass polymerization, suspension polymerization, letex polymerization can be adopted.Wherein, particularly preferably there is not the mass polymer of water soluble component in polymerization in being.In addition, in order to obtain preferred second-order transition temperature, or in order to obtain showing the viscosity of the plasticity becoming good membranes, the preferably usage chain transfer agent when being polymerized.The amount of chain-transfer agent suitably determines according to the kind of monomer and composition.In addition, acrylic resin also can add known additive as required.As known additive, can enumerate as lubricant, anti-hard caking agent, thermo-stabilizer, antioxidant, antistatic agent, photostabilizer, shock-resistance modifying agent, tensio-active agent etc.Owing to needing the transparency as the protective membrane being laminated in polarization film, therefore the amount of these additives is preferably limited to irreducible minimum.
As the manufacture method of acrylic resin film, what also can use melting casting method, T modulus method, inflation method and so on dissolves any one method such as extrusion molding, rolling process.Wherein, from the viewpoint that can obtain the good film of surface texture, preferably material resin is such as melt extruded from T mould, make at least one side of gained membranoid substance with roller or be with the method contacting and be filmed.
From viewpoint such as the formation masking of film, the shock-resistance of film etc., acrylic resin also can containing the acrylic rubber particle as impact modifying agent.At this, as long as so-called acrylic rubber particle is using the particle of the elastomeric polymer based on acrylate as required composition, just there is no particular limitation, can enumerate as the particle of the single layer structure in fact only formed by this elastomeric polymer, using the particle of this elastomeric polymer as the multilayered structure of 1 layer.As the example of described elastomeric polymer, can enumerate as being principal constituent with alkyl acrylate and making itself and the cross-linking elasticity multipolymer that can obtain with other vinyl monomer of its copolymerization and cross-linkable monomer copolymerization.As the alkyl acrylate of principal constituent becoming elastomeric polymer, the carbon number that preferably can use the alkyl such as such as methyl acrylate, ethyl propenoate, butyl acrylate, 2-ethylhexyl acrylate is the alkyl acrylate of about 1 ~ 8, particularly preferably uses the acrylate with the alkyl of carbon number more than 4.As can with other vinyl monomers of this alkyl acrylate copolymer, the compound as having 1 polymerizability carbon-to-carbon double bond in molecule can being enumerated, more specifically can enumerate the alkene nitrile compound etc. of the aromatic ethylene compound, vinyl cyanide and so on of the methacrylic ester, vinylbenzene and so on as methyl methacrylate and so on.In addition, as cross-linkable monomer, the cross-linked compound as having at least 2 polymerizability carbon-to-carbon double bonds in molecule can being enumerated, more specifically can enumerate (methyl) acrylic acid alkenyl esters, Vinylstyrene etc. of (methyl) esters of acrylic acid of the polyvalent alcohol as ethylene glycol bisthioglycolate (methyl) acrylate and butyleneglycol two (methyl) acrylate and so on, allyl group (methyl) acrylate and so on.
In addition, also can using by the sandwich of the film do not formed containing the acrylic resin of rubber particles and the film be made up of the acrylic resin containing rubber particles as protective membrane.
In the polarization plates of the viewable side for liquid crystal indicator, can be configured at its viewable side namely and the protective membrane of liquid crystal cells opposite side give anti-glare.Now; on the surface of viewable side becoming protective membrane; namely with the face of face opposite side being fitted with polaroid; the antiglare layer with concave-convex surface is set; antiglare layer is generally formed by the following method: utilize convex-concave to print normal direction active energy ray-curable resin and give concavo-convex, or has to active energy ray-curable resin complex and make it to solidify with the particulate of its different refractivity again thus give concavo-convex method.In addition; when protective membrane contains acrylic resin; following scheme is also effective; namely; protective membrane is formed by the stacked film of light diffusion layer and transparent layer; wherein, light diffusion layer coordinates the particulate with the specific refractory power different from it and the light diffusion layer obtain in as the acrylic resin of base-material, contains the acrylic resin not coordinating described particulate in transparent layer.Now can adopt following mode: the mode of polaroid will be fitted in this light diffusion layer side by above-mentioned light diffusion layer and these 2 layers of stacked films formed of above-mentioned transparent layer, the stacked film of seizing the 3-tier architecture on the two sides of above-mentioned light diffusion layer with above-mentioned transparent layer on both sides by the arms be fitted in the mode etc. of polaroid with the transparent layer of one side.Moreover, during using the stacked film of acrylic resin by imparting anti-glare containing light diffusion layer as protective membrane, on the surface becoming its viewable side; namely with the face of opposition side, face fitting in polaroid; arrange antiglare layer as above, improve anti-dazzle performance further, the program is also effective.
As mentioned above; particularly using acrylic resin film as protective membrane time; for the epoxy monomer not containing aromatic nucleus shown in patent documentation 6 (Japanese Patent Laid-Open 2004-245925 publication) in the past; cementability is not necessarily abundant, even and if Photocurable adhesive agent of the present invention also can give good bonding force for using acrylic resin film as the situation of protective membrane.Therefore, the present invention is for particularly useful as the situation of protective membrane using acrylic resin film.Now, the unsaturated compound containing (D) composition illustrated before in preferred Photocurable adhesive agent, especially acrylic compounds.
In the present invention, by the Photocurable adhesive agent illustrated before, the protective membrane be made up of the transparent resin film being selected from vibrin, polycarbonate resin and acrylic resin of above-mentioned explanation of fitting at least one side of polaroid.Only when the single-sided lamination protective membrane of polaroid, the mode that the adhering agent layer for the miscellaneous parts such as liquid crystal cells of fitting such as directly is set in other faces of polaroid can be adopted.
On the other hand, when the two sides of polaroid laminating protective membrane, each protective membrane can be class of the same race, also can be different sorts.Specifically can preferably adopt such as using under type: in the mode of laminating polyester resin film in the two sides of polaroid as protective membrane; In the mode of laminating polycarbonate resin in the two sides of polaroid as protective membrane; In the mode of laminating acrylic resin in the two sides of polaroid as protective membrane; In the one side of polaroid; laminating is selected from the transparent resin film of any one of vibrin, polycarbonate resin and acrylic resin as protective membrane; in other faces of polaroid, that laminating is selected from any one of vibrin, polycarbonate resin and acrylic resin and different from the protective membrane of above-mentioned one side transparent resin films is as the mode etc. of protective membrane.Moreover; also following mode can be adopted: in the one side of polaroid; laminating is selected from the transparent resin film of any one of vibrin, polycarbonate resin and acrylic resin as protective membrane; in other faces of polaroid, fit and any one different transparent resin film of vibrin, polycarbonate resin and acrylic resin mode as protective membrane.When the two sides of polaroid laminating protective membrane, 2 protective membranes of can simultaneously simultaneously fitting stage by stage, also can on a stage laminating two sides.
When the two sides laminating protective membrane of polaroid; when its one side is other resin moldings different from vibrin, polycarbonate resin and acrylic resin; as the preferred exemplary of other resins described, can enumerate as cellulose-based resin, noncrystalline polyolefin system resin.In addition; fit in the protective membrane be made up of vibrin, polycarbonate resin or acrylic resin of the one side of polaroid; according to the present invention, come bonding by the Photocurable adhesive agent illustrated before, the protective membrane fitting in other faces of polaroid also can come bonding by other caking agent.Such as, when the one side of polaroid arranges the protective membrane be made up of the resin molding that the Water Vapour Permeability of cellulose-based resin molding and so on is higher, also can use the caking agent beyond the epoxies such as polyethenol series caking agent at the binding face of the high resin molding of described Water Vapour Permeability.But because Photocurable adhesive agent of the present invention is relative to cellulose-based resin molding, the noncrystalline polyolefin resin film in this example, high bonding force can be given, therefore, use the scheme of identical caking agent simple to operate on the two sides of polaroid, because of but favourable.
As a side protective membrane and the cellulose-based resin used is cellulosic partially or completely carboxylate, can enumerate as cellulosic acetic ester, propionic ester, butyric ester, their mixed ester etc.Specifically, can enumerate as triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate etc.As the commercially available product of the film be made up of described cellulose ester system resin, there is no particular limitation, can enumerate " FUJITAC (the Off ジ タ ッ Network) TD80 ", " FUJITAC TD80UF " and " FUJITAC TD80UZ " that make as Fuji's film (strain), " KC8UX2M " and " KC8UY " that Konica Minolta Ao Putuo (strain) is made etc.In addition, the cellulose-based resin molding imparting optical compensation function can also be used.As described optical compensation films, there is no particular limitation, and the surface application can enumerated as the film after making cellulose-based resin contain the compound of adjusting offset function, cellulose-based resin molding has the film of the compound of adjusting offset function, the cellulose-based resin molding film etc. after unidirectional or two-way stretch.As the example of commercially available cellulose-based optical compensation films, preferably can enumerate " Wide View (ワ イ De PVC ュ mono-) the film WVBZ438 " and " Wide View film WV EA " that make as Fuji's film (strain), " KC4FR-1 " and " KC4HR-1 " of Konica Minolta Ao Putuo (strain) Inc. etc.
As other the resin different from vibrin, polycarbonate resin and acrylic resin and the example of the low transparent resin of the Water Vapour Permeability that can use as the protective membrane of a side; there is no particular limitation, can enumerate as noncrystalline polyolefin system resin, polysulfone resin, ester ring type polyimide resin etc.Wherein, because the film be made up of noncrystalline polyolefin system resin is the excellent film such as mechanical property, solvent resistance, scratch resistance, cost, therefore particularly preferably use.
Noncrystalline polyolefin system resin has the polymerized unit derived by the polycycle cyclic olefin of norbornylene or derivatives thereof, dimethylene eight hydroxyl naphthalene and so on usually, when remaining double bond as ring-opening polymerization polymer, preferably at the thermoplastic resin that this has been hydrogenated.Noncrystalline polyolefin system resin also can be the multipolymer of cyclic olefin and chain olefin, also can import polar group in addition.Wherein, example representatively, can enumerate as thermoplasticity saturated norbornene system resin.As enumerated the example of commercially available noncrystalline polyolefin system resin, there are " ARTON (the ア mono-ト Application) ", " ZEONEX " and " ZEONOR " of Japanese ZEO (strain) of JSR (strain), " APO " of Mitsui Chemicals (strain) and " APELLE (ア ペ Le) " etc.When noncrystalline polyolefin system resin masking is formed film, suitably can adopt the known method such as solvent casting method, extrusion by melting.
Protective membrane, before fitting in polaroid, can implement the easy bonding process such as saponification process, corona treatment, plasma treatment, thickening coating process at binding face.In addition, also can protective membrane with the surface of the binding face opposition side to polaroid, there is the various processing layers such as hard coat, anti-reflection layer, antiglare layer.There is no particular limitation for the thickness of protective membrane, usually the scope of about 5 ~ 200 μm, is preferably 10 ~ 120 μm, is more preferably 10 ~ 85 μm.
[manufacture method of polarization plates]
Polarization plates of the present invention can be obtained by the method comprising following operation: at least one party of the polaroid illustrated before with the binding face of the protective membrane be made up of the transparent resin film being selected from vibrin, polycarbonate resin and acrylic resin, the operation of the Photocurable adhesive agent illustrated before coating; By the bond layer of gained, by the bonding process that polaroid and protective membrane are fitted; With the state of polaroid and protective membrane being fitted by this bond layer, make the curing process that Photocurable adhesive agent solidifies.
< adhesive applicating operation >
In adhesive applicating operation, at least one party in the binding face of polaroid and protective membrane, the Photocurable adhesive agent illustrated before coating.When the direct Photocurable adhesive agent of the surface application of polaroid or protective membrane, to its coating method, there is no particular limitation.Such as can utilize the various application pattern such as scraper applies, wire bar is coated with method, mould painting method, comma coating process (comma coat), intaglio printing coating.In addition, the Photocurable adhesive agent curtain coating illustrated before making it also can be adopted between polaroid and protective membrane, pressurize thus the method evenly spread out with roller etc. afterwards.
< bonding process >
After being coated with Photocurable adhesive agent like this, be supplied to bonding process.Such as, in this bonding process, in the surface application of polaroid during Photocurable adhesive agent in working procedure of coating before, by overlapping for protective membrane to polaroid; In working procedure of coating before, during Photocurable adhesive agent, polaroid is overlapped onto protective membrane in the surface application of protective membrane.In addition, make Photocurable adhesive agent curtain coating between polaroid and protective membrane time, with this state, polaroid is overlapping with protective membrane.At the two sides of polaroid laminating protective membrane and when all using Photocurable adhesive agent of the present invention on two sides, respectively on the two sides of polaroid by Photocurable adhesive agent overlapping protection film.Afterwards, be generally and seize on both sides by the arms with this state roller etc. pressurize from two sides (when the one side overlapping protection film of polaroid, being polaroid side and protective membrane side, or when the two sides overlapping protection film of polaroid, the protective membrane side for this two sides).At this, the material of roller can use metal, rubber etc.The roller being configured at two sides can, for identical material, also can be different materials.
< curing process >
As mentioned above, by the feeding sheet materials of fitted by uncured Photocurable adhesive agent polaroid and protective membrane to follow-up curing process.In this curing process, active energy ray is irradiated to Photocurable adhesive agent, the bond layer containing epoxy compounds, oxetane compound is solidified, makes polaroid bonding with protective membrane.When the single-sided lamination protective membrane of polaroid, active energy ray can from polaroid side, any side of protective membrane side irradiates.In addition; when the two sides of polaroid laminating protective membrane, following scheme is effective, that is: be fitted with the state of protective membrane respectively by Photocurable adhesive agent with the two sides of polaroid; irradiate active energy ray from the protective membrane side of either party, make the scheme that the Photocurable adhesive agent on two sides solidifies simultaneously.When the protective membrane of either party is combined with UV light absorber (such as; to the situation of cellulose-based resin molding as the protective membrane of a side of UV light absorber be combined with) and active energy ray is ultraviolet time, usually from the protective membrane side irradiation ultraviolet radiation not having combined with ultraviolet radiation absorption agent of the opposing party.
As active energy ray, visible ray, ultraviolet, X-ray, electron rays etc. can be used, due to easily process and curing speed is also desirable, therefore general preferred use ultraviolet.For the light source of active energy ray, there is no particular limitation, the active energy ray that below wavelength 400nm has luminescence distribution can be used in, such as low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, chemical lamp, black lamp, microwave-excited mercury lamp, metal halide lamp, LED etc.
The photo-irradiation intensity irradiated to Photocurable adhesive agent decides according to each object composition, still there is no particular limitation, to the exposure intensity in the effective wavelength field of the activation of polymerization starter preferably with the form of UV-B (the medium wavelength territory ultraviolet of 280 ~ 320nm) for 1 ~ 3000mW/cm 2.Exposure intensity is as being less than 1mW/cm 2, then the reaction times is long, on the other hand, if this exposure intensity is more than 3000mW/cm 2, then due to the heating when being polymerized from the heat of lamp radiation and Photocurable adhesive agent, likely there is the xanthochromia of Photocurable adhesive agent, the deterioration of polaroid.
The rayed time to Photocurable adhesive agent regulates according to each curing composition, and still there is no particular limitation, is preferably set to 10 ~ 5000mJ/cm with the integrating light quantity of the product representation of exposure intensity and irradiation time 2.Integrating light quantity is less than 10mJ/cm 2time, the generation from the spike of polymerization starter is insufficient, and being solidified with of bond layer may be insufficient, and on the other hand, this integrating light quantity is as more than 5000mJ/cm 2, then irradiation time is very long, unfavorable for raising productivity.
Irradiate active energy ray when Photocurable adhesive agent solidify, make it to solidify under the condition preferably do not declined in each performance of the polarization plates of the transparency of the degree of polarization of polaroid, transmitance and form and aspect or protective membrane.
In the polarization plates of such gained, for the thickness of bond layer, there is no particular limitation, is generally less than 50 μm, is preferably less than 20 μm, is more preferably less than 10 μm again.
[optics]
Polarization plates also can be used as the optics of the optical layers of the optical function beyond the stacked display in its side polarized light function.As to form optical layers stacked in polarization plates for the purpose of optics, there is no particular limitation, can enumerate the optical layers used in the formation as the liquid crystal indicators such as reflecting layer, semi-transmission type reflecting layer, light diffusion layer, polarizer, light collecting plate, brightness improving film etc.Above-mentioned reflecting layer, semi-transmission type reflecting layer and light diffusion layer can when formed comprise reflection-type, semi-transmission type or dispersion pattern, their dual-purpose types wherein the optics of polarization plates use.
The polarization plates of reflection-type is used to make the reflected incident light from viewable side carry out the liquid crystal indicator of the type shown, owing to omitting the light sources such as backlight, therefore easy by liquid crystal indicator slimming.In addition, the polarization plates of semi-transmission type is used at bright place as reflection-type display, the liquid crystal indicator in the dark carrying out the type shown by light sources such as backlights.As the optics of reflection type polarizer, such as can the protective membrane on polaroid set up be made up of metals such as aluminium paper tinsel, vapor-deposited film to be to form reflecting layer.As the polarization plates of semi-transmission type optics can by using above-mentioned reflecting layer as semi-transparent semi-reflecting lens (half mirror) or the reflector including the display light perviousnesies such as pearl (pearl) pigment is adhered to polarization plates to be formed.On the other hand; in optics as dispersion pattern polarization plates; the method that such as can be processed protective membrane enforcement delustring (matte) in polarization plates by use, coating contain the various methods such as the method for fine-grained resin, the bonding method containing fine-grained film, thus at surface formation minute concave-convex structure.
And then, spread the formation of the optics of dual-purpose polarization plates as reflection, such as, by the minute concave-convex structure face of dispersion pattern polarization plates, the methods such as the reflecting layer of this concaveconvex structure of reflection can be set and carry out.The reflecting layer of minute concave-convex structure has and utilizes diffuse-reflectance that incident light is spread, prevents the advantage etc. of directive property or dazzle, suppression light and shade inequality.In addition, also have when incident light and its reflected light suppress the unequal advantage of light and shade further through containing it being made to spread during fine-grained layer containing fine-grained resin layer, film.Reflect that the schematic design making of metal by such as using the methods such as evaporation or plating such as vacuum evaporation, ion plating, sputtering, can directly be set up in the reflecting layer of surperficial minute concave-convex structure on the surface of minute concave-convex structure.As the particulate coordinated for the formation of surperficial minute concave-convex structure, the inorganic system particulate comprising silicon-dioxide, aluminum oxide, titanium oxide, zirconium white, stannic oxide, Indium sesquioxide, Cadmium oxide, weisspiessglanz etc. enumerated as median size 0.1 ~ 30 μm can be utilized, comprise the organic system particulate etc. of crosslinked or uncrosslinked polymkeric substance etc.
On the other hand, the polarizer as above-mentioned optical layers uses in order to the phase differential compensating liquid crystal cells and cause.As its example, there is no particular limitation, can enumerate birefringence film, disc-like liquid crystal or the nematic liquid crystals such as the stretched film as comprised various plastics and be oriented the film secured, the component etc. being formed with above-mentioned liquid crystal layer on film base material.Now, as the film base material supporting aligned liquid-crystal layer, there is no particular limitation, preferably uses the Mierocrystalline cellulose mesenterys such as triacetyl cellulose.
As the plastics of form dielectric grid film, there is no particular limitation, such as, can enumerate the polyolefine of polycarbonate, polyvinyl alcohol, polystyrene, polymethylmethacrylate, polypropylene and so on, multi arylate, polymeric amide, noncrystalline polyolefin system resin etc.Stretched film can form with suitable mode process such as unidirectional or two-way stretches.In addition, also can for controlling the birefringence film of the specific refractory power of the thickness direction of film by applying convergent force and/or drawing force under the state bonding with heat-shrinkable film.In addition, phase retardation film also can in order to control the optical characteristics such as broadband and combinationally use more than 2.
Light collecting plate, in order to control light path etc. and use, can set up the formation such as sheet as prism array sheet (prism array sheet), lens array sheet (lens array sheet) or point (dot).
Brightness improving film uses in order to the brightness improved in liquid crystal indicator etc.As its example, the mutually different film of anisotropy as stacked multi-disc specific refractory power can be enumerated and be designed to the circularly polarizing separation sheet etc. of the aligned liquid-crystal layer producing anisotropic reflection-type rectilinearly polarized light separate sheet, the alignment films that film base material supports cholesteric liquid crystal polymer or cholesteric liquid crystal in reflectivity.
Optics can be polarization plates and the optical layers of more than 1 layer or 2 layers selected according to application target from described reflecting layer or semi-transmission type reflecting layer, light diffusion layer, polarizer, light collecting plate, brightness improving film etc. are carried out combining thus the duplexer of more than become 2 layers or 3 layers.In this case, the optical layers such as light diffusion layer, polarizer, light collecting plate, brightness improving film also can configure more than 2 layers respectively.In addition, there is no particular limitation in the configuration of each optical layers.
Use caking agent by integrated with polarization plates for the various optical layers forming optics, as long as the caking agent used can form the caking agent of bonding side well for this reason, there is no particular limitation.From the simplicity of bonding operation or prevent the viewpoints such as optical skew, preferably use tackiness agent (being also referred to as pressure-sensitive caking agent).Tackiness agent can use the tackiness agent as matrix polymer (base polymer) such as acrylic acid polymer, silicone-based polymer, polyester, urethane, polyethers.Wherein, the optical transparence of preferred use acrylic acid series tackiness agent and so on is outstanding, keep suitable wettability or cohesive force, also excellent and then there is weathering resistance and thermotolerance etc. with the cementability of base material, the tackiness agent of problem of peeling off such as can not float or strip off under the condition of heating, humidification.In acrylic acid series tackiness agent, be preferably less than 25 DEG C with second-order transition temperature, be more preferably the mode of less than 0 DEG C, coordinate comprise there is methyl, the acrylic monomer containing functional group of (methyl) acrylic acid alkyl ester that the carbon number of ethyl or butyl and so on is the alkyl of less than 20 and (methyl) vinylformic acid, hydroxyethyl (methyl) acrylate etc., and the acrylic copolymer that the weight-average molecular weight making it to be polymerized is more than 100,000 uses as matrix polymer.
Can utilize such as under type is carried out the formation of the adhering agent layer of polarization plates: in the organic solvent of toluene, ethyl acetate and so on, make adhesion agent composition dissolve or dispersion, prepare the liquid that solid component concentration is 10 ~ 40 % by weight, it is directly coated in mode polarization plates being formed adhering agent layer; In advance on barrier film, form adhering agent layer, then moved in polarization plates, thus form the mode etc. of adhering agent layer.The thickness of adhering agent layer is determined according to its bonding force etc., and the scope of about 1 ~ 50 μm is suitable.
In addition, as required, the weighting agent, pigment, tinting material, antioxidant, UV light absorber etc. that comprise glass fibre, granulated glass sphere, resin bead, metal powder, other inorganic powders etc. can also be coordinated in adhesive coating.As UV light absorber, there is no particular limitation, can enumerate as salicylate based compound, benzophenone based compound, benzotriazole based compound, cyanoacrylate based compound, nickel complex based compound etc.
[liquid crystal indicator]
Optics as above is configured at the one-sided of liquid crystal cells or both sides, can liquid crystal indicator be become.The liquid crystal cells used is any kind, such as, can use with film transistor type the liquid crystal cells of the active matrix drive-type being representative, be that the various liquid crystal cells such as the driving liquid crystal cells of the simple matrix of representative are to form liquid crystal indicator with super-twist nematic.The optics being configured at the both sides of liquid crystal cells can be the same or different.
[embodiment]
Below enumerate embodiment and comparative example, in further detail the present invention is described, but the invention is not restricted to these examples.In example, represent that the % of usage quantity or content is weight basis unless otherwise specified.
In embodiment and comparative example, the various compositions used in the preparation of adhesive composite are as follows, represent below with each symbol (trade(brand)name itself or its a part of).
(A) composition: epoxy compounds
JER-828: " jER-828 " that bisphenol A type epoxy resin, japan epoxy resin (strain) are made.
JER-152: " jER-152 " that phenolic resin varnish type epoxy resin, japan epoxy resin (strain) are made.
ECC:3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate.
(B) composition: oxetane compound
" ア ロ Application オ キ セ タ Application OXT-211 " that OXT-211:3-ethyl-3-phenoxymethyloxetane, East Asia synthesis (strain) are made.
" ア ロ Application オ キ セ タ Application OXT-221 " that OXT-221:3-ethyl-3-((3-Ethyloxetane-3-base) methoxymethyl) trimethylene oxide, East Asia synthesis (strain) are made.
OXT-121: with 1, two ((3-Ethyloxetane-3-base) methoxymethyl) benzene of 4-is the principal constituent of main component and has two sense oxetane compounds of xylylene skeleton, " ア ロ Application オ キ セ タ Application OXT-121 " that East Asia synthesis (strain) is made.
Below show the structure of these oxetane compounds.
(C) composition: light cationic polymerization initiators
UVI-6992: the carbonic allyl ester solution of the effective constituent 50% being main component with triaryl matte hexafluorophosphate, " UVI-6992 " of Dow Chemical.
d) composition: acrylic acid series unsaturated compound
M-203S: " ア ロ ニ ッ Network ス M-203S " that tristane dihydroxymethyl diacrylate, East Asia synthesis (strain) are made.
e) composition: optical free radical polymerization starter
Irg184:1-hydroxycyclohexylphenylketone, " IRGACURE184 " of Qi Ba Inc..
(F) composition: other compositions without polymerizability
BR-60: " ダ イ ヤ Na one Le BR-60 " that methyl methacrylate based copolymer, Mitsubishi's beautiful sun (strain) make.
[preparation of adhesive composite]
Each composition shown in table 1 and table 2 is coordinated with each ratio, is uniformly mixed according to usual method, prepared Photocurable adhesive agent composition.In addition, " UVI-6992 " that use as (C) composition is the carbonic allyl ester solution containing 50% effective constituent, therefore, is separated by (C) composition represent in table with propylene carbonate.That is, the use level of " UVI-6992 " in table represents the ratio of solid state component, and " UVI-6992 " use level itself is the amount shown in (C) composition one hurdle and the amount sum shown in propylene carbonate one hurdle, namely 6%.
[manufacture of polarization plates (1)]
At this, use 2 kinds of following films as protective membrane.
Stretching norbornene resin film: thickness 70 μm, trade(brand)name " ZEONOR film ", Japanese ZEO (strain) make.Corona discharge Treatment is carried out to this film, afterwards for the laminating with polaroid.
Two-way stretch polyethylene terephthalate film: thickness 50 μm, trade(brand)name " E5001 ", Japan's weaving (strain) system.This film also implement Corona discharge Treatment after for the laminating with polaroid.
By bar coater with the thickness of 3 μm, at the adhesive composite of the Corona discharge Treatment face of above-mentioned stretching norbornene resin film coating preparation, then fit thereon and be adsorbed with iodine in polyvinyl alcohol and the polaroid of iodine through orientation.Use bar coater separately at above-mentioned two-way stretch polyethylene terephthalate film with the thickness of 3 μm, apply same caking agent, then the side contrary with norbornene resin film of the polaroid of norbornene resin film of having fitted before being fitted in.Like this, utilize the UV irradiation equipment (lamp uses " the FusionH バ Le Block " of Fusion Inc.) of being furnished with belt conveyor, since two sides being fitted with to the polaroid of protective membrane, the integrating light quantity on My World surface is 300mJ/cm 2mode irradiation ultraviolet radiation after, place 1 hour in room temperature, manufacture and be fitted with in one side the protective membrane that is made up of polyethylene terephthalate film and be fitted with the polarization plates (1) of stretching norbornene resin film at another side.
[manufacturing of polarization plates (2)]
Two-way stretch polyethylene terephthalate film is transformed to acrylic resin film (thick 80 μm, trade(brand)name " テ Network ノ ロ イ S001 ", Sumitomo Chemical Zhu Shihui Inc.); other manufacture same carrying out with polarization plates (1), manufacture and are fitted with in one side the protective membrane that is made up of acrylic resin film and are fitted with the polarization plates (2) of stretching norbornene resin film at another side.
[evaluation test]
By following method, to each polarization plates evaluate cure of gained, cementability and weather resistance, show the result in table 1 and table 2.
< solidified nature >
Trial hand is peeled off between polaroid and polyethylene terephthalate film or acrylic resin film, although can not peel off by solidifying completely or peel off but this part does not have the sample of removing residual glue viscosity (tackiness caused by uncured caking agent) to be evaluated as "○", will to peel off and the sample of this part removing residual glue viscosity is evaluated as "×".
< cementability >
Following sample is evaluated as the poorest "×", that is: when the blade of shear knife is inserted from the inclined upward of polyethylene terephthalate film or acrylic resin film, film is peeled off from polaroid, and blade is inserted into polyethylene terephthalate film or the sample between acrylic resin film and polaroid.To situation about not peeling off in this experiment, then carry out following evaluation.Namely, by polarization plates with draw direction for long limit, be cut into the strip of wide 1cm, with shear knife, cut from the surface of polyethylene terephthalate film or acrylic resin film to the direction perpendicular with draw direction simplely, turned to by this cut channel outside to be bent to form " く " font, observe the situation now peeled off from end.Now, when end is peeled off, attempt peeling off from released part with hand, evaluate whether smoothly peel off, whether film there is material damage.According to evaluation result, judge as follows.
△: time bending, the stripping of end increases, and easily peels off with hand.
Zero: time bending, the stripping of about 1mm appears in end, but when attempting peeling off with hand further, there is material damage in film.
◎: peel off hardly time bending, when attempting peeling off with hand further, there is material damage in film.
< weather resistance >
For the good sample that cementability is more than "○", with 2 kinds of sample sizes of diagonal angle 15 inches (about 38cm) and diagonal angle 5 inches (about 13cm), implement to place in-35 DEG C 60 minutes the place 60 minutes again circulation thermal shock round-robin test of 300 times repeatedly in+70 DEG C, evaluate as follows.
Zero: in 15 inches, there is not bad order.
△: there is a bad order at 15 inches, but do not have bad order in 5 inches.
×: even if also there is bad order in 5 inches.
[table 1]
[table 2]
As shown in table 1, in the polarization plates of the embodiment 1 ~ 7 using Photocurable adhesive agent composition of the present invention to obtain, the cementability of polaroid and protective membrane is good, and solidified nature is also good.Wherein, even if as the oxetane compound of (B) composition, employ in the embodiment 1 ~ 3 of " OXT-211 " in molecule with 1 oxetanylmethoxy and 1 aromatic nucleus, cementability is also good especially.Containing 18% as (D) composition has in the embodiment 3 of acrylic acid series unsaturated compound " M-203S " of alicyclic skeleton, and except cementability is good, weather resistance is also good.In addition, employ in molecule and have under 2 oxetanylmethoxy, room temperature for aqueous and molecular weight is that the embodiment 4 ~ 7 (in embodiment 4, and with " OXT-121 ") of the oxetane compound " OXT-221 " of less than 500 is excellent in the balance of cementability and weather resistance.Wherein, in the embodiment 4 and 5 containing 18% acrylic acid series unsaturated compound " M-203S ", cementability is good especially.
On the other hand, as shown in table 2, in the comparative example 1 and 2 not containing the oxetane compound of (B) composition, lack cementability.Particularly, be combined with comparative example 2 pairs of polyethylene terephthalate films of the acrylic acid series unsaturated compound of 43% (D) composition, acrylic resin film cementability all bad.In addition, in the comparative example 3 not containing the epoxy compounds of (A) composition, solidified nature, cementability are all bad.
The possibility of industrial utilization
Photocurable adhesive agent composition of the present invention is easily solidified by the irradiation of ultraviolet isoreactivity energy line, and will be just effective in polaroid and protective membrane strong bond at short notice.

Claims (20)

1. a Photocurable adhesive agent composition; it is characterized in that; it is the adhesive composite for protective membrane being adhered to polaroid; wherein said polaroid by through unilateral stretching, be adsorbed with dichroism pigment and the polyvinyl alcohol resin film of dichroism pigment through orientation is formed; described protective membrane is made up of the transparent resin film being selected from vibrin, polycarbonate resin and acrylic resin
Described Photocurable adhesive agent composition contains:
(A) have in molecule the epoxy compounds of at least 2 epoxy group(ing),
(B) have in molecule the oxetane compound of at least 1 oxetanylmethoxy,
(C) light cationic polymerization initiators and
(F) second-order transition temperature is the methyl methacrylate based polymer of more than 70 DEG C,
Described epoxy compounds (A) is 90/10 ~ 10/90 with weight ratio (A)/(B) of above-mentioned oxetane compound (B),
The amount of the cationic polymerization initiators of light described in composition (C) is 0.5 ~ 20 % by weight.
2. Photocurable adhesive agent composition according to claim 1, wherein, epoxy compounds (A) is containing the compound in molecule with at least 2 epoxy group(ing) and at least 1 aromatic nucleus.
3. Photocurable adhesive agent composition according to claim 2, wherein, epoxy compounds (A) is selected from glycidyl ether and the glycidyl ester of aromatics.
4. Photocurable adhesive agent composition according to claim 1 and 2, wherein, oxetane compound (B) is containing the compound in molecule with 1 oxetanylmethoxy and at least 1 aromatic nucleus.
5. Photocurable adhesive agent composition according to claim 1 and 2, wherein, oxetane compound (B) is containing the compound in molecule with 2 oxetanylmethoxy.
6. Photocurable adhesive agent composition according to claim 1, wherein,
Epoxy compounds (A) is for having the compound of at least 2 epoxy group(ing) and at least 1 aromatic nucleus in molecule; Or for there are at least 2 epoxy group(ing) in the compound in molecule with at least 2 epoxy group(ing) and at least 1 aromatic nucleus and molecule and not there is the mixture of the compound of aromatic nucleus.
7. Photocurable adhesive agent composition according to claim 6, wherein,
The epoxide of more than a kind that epoxy compounds (A) is the glycidyl ether and glycidyl ester that are selected from aromatics; Or be the epoxy compounds of more than a kind of glycidyl ether compound and epihydric alcohol ester compound that is selected from aromatics and the mixture of other epoxy compounds (A).
8. the Photocurable adhesive agent composition according to claim 1 or 6, wherein,
Oxetane compound (B) is for having the compound of 1 oxetanylmethoxy and at least 1 aromatic nucleus in molecule; Or for there is at least 1 oxetanylmethoxy in the compound in molecule with 1 oxetanylmethoxy and at least 1 aromatic nucleus and molecule and not there is the mixture of the compound of aromatic nucleus.
9. the Photocurable adhesive agent composition according to claim 1 or 6, wherein,
Oxetane compound (B) is for having the compound of at least 2 oxetanylmethoxy in molecule; Or for having the mixture of the compound of 1 oxetanylmethoxy in the compound in molecule with at least 2 oxetanylmethoxy and molecule.
10. the Photocurable adhesive agent composition according to claim 1,2 or 6, wherein,
Contain the unsaturated compound in (D) molecule with at least 1 olefinic unsaturated link(age) with the ratio of less than 35 % by weight in composition.
11. Photocurable adhesive agent compositions according to claim 10, wherein, contain unsaturated compound (D) with the ratio of 5 ~ 25 % by weight in composition.
12. Photocurable adhesive agent compositions according to claim 10, wherein,
Unsaturated compound (D) is for having (methyl) acrylic compounds of at least 1 (methyl) acryl and at least 1 alicyclic skeleton or aromatic nucleus skeleton in molecule.
13. Photocurable adhesive agent compositions according to claim 12, wherein, unsaturated compound (D) is for having two (methyl) acrylate of tricyclodecane skeleton.
14. Photocurable adhesive agent compositions according to claim 10, wherein, in the composition, also contain (E) optical free radical polymerization starter with the ratio of less than 10 % by weight.
15. Photocurable adhesive agent compositions according to claim 1, wherein, the amount of (F) methyl methacrylate based polymer is less than 10 % by weight.
16. 1 kinds of polarization plates, is characterized in that,
It is that protective membrane is bonded to the polarization plates of polaroid by caking agent; wherein; polaroid by through unilateral stretching, be adsorbed with dichroism pigment and the polyvinyl alcohol resin film of dichroism pigment through orientation is formed; described protective membrane is made up of the transparent resin film being selected from vibrin, polycarbonate resin and acrylic resin
Described caking agent is formed by Photocurable adhesive agent composition according to claim 1.
The manufacture method of 17. 1 kinds of polarization plates; it is, by caking agent, protective membrane is fitted in polaroid to manufacture the method for polarization plates; wherein; polaroid by through unilateral stretching, be adsorbed with dichroism pigment and the polyvinyl alcohol resin film of dichroism pigment through orientation is formed; described protective membrane is made up of the transparent resin film being selected from vibrin, polycarbonate resin and acrylic resin
The manufacture method of polarization plates comprises following operation:
Adhesive applicating operation, described polaroid and the described at least one party stated in the binding face of protective membrane, applies Photocurable adhesive agent composition according to claim 1;
Bonding process, by the bond layer of gained, fits described polaroid and described protective membrane;
Curing process, with the state of polaroid and protective membrane being fitted by described bond layer, makes described Photocurable adhesive agent composition solidify.
18. 1 kinds of opticses, is characterized in that, polarization plates according to claim 16 is laminated with other optical layers.
19. opticses according to claim 18, wherein, other optical layers comprise polarizer.
20. 1 kinds of liquid crystal indicators, is characterized in that, the optics described in claim 18 or 19 is configured in the one-sided of liquid crystal cells or bilateral forms.
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