CN102344763B - Photocurable adhesive composition, polarizing plate and a process of producing the same, optical member, and liquid crystal display device - Google Patents

Photocurable adhesive composition, polarizing plate and a process of producing the same, optical member, and liquid crystal display device Download PDF

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Publication number
CN102344763B
CN102344763B CN201110168572.7A CN201110168572A CN102344763B CN 102344763 B CN102344763 B CN 102344763B CN 201110168572 A CN201110168572 A CN 201110168572A CN 102344763 B CN102344763 B CN 102344763B
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composition
protective membrane
polarization element
methyl
resin
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CN102344763A (en
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稻田和正
佐内康之
竹内智康
藤田政大
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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods

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

Abstract

To provide a photocurable adhesive with which a protective film is bonded to a polarizer with sufficient adhesive strength in a short-time process even when a resin film with low moisture vapor transmission is used as the protective film, and which has low viscosity, and with which no problem such as poor appearance is caused after an endurance test, and to provide a polarizing plate including a polarizer with the protective film bonded thereto by using the adhesive. The photocurable adhesive composition is an adhesive composition used for the purpose of bonding the protective film which is composed of a transparent resin film selected from predetermined four kinds of transparent resin films to the polarizer composed of a polyvinyl alcohol-based resin film, and includes: (A) an epoxy compound having two or more epoxy groups and one or more aromatic rings; (B) a di(meth)acrylate of a 5-10C diol (except an ether compound) optionally having an ester skeleton; and (C) a cationic photopolymerization initiator, and 20-60 wt.% of the component (A), 5-45 wt.% of the component (B), and 0.5-10 wt.% of the component (C) are included in the composition.

Description

Photocurable adhesive composition, polaroid and manufacture method thereof, optics and liquid crystal indicator
Technical field
The present invention relates to the Photocurable adhesive composition of the laminating for polarization element in polaroid and protective membrane, use this binder composition to be fitted with the polaroid of protective membrane and the manufacture method of this polaroid at polarization element.The invention still further relates to the optics and liquid crystal indicator that use this polaroid.
Background technology
Polaroid is used as a kind of optics forming liquid crystal indicator.Polaroid is usually assembled in liquid crystal indicator with the state being laminated with protective membrane on the two sides of polarization element and uses.Although it is known for only arranging protective membrane in the one side of polarization element, as a rule, not as simple protective membrane but the layer with other optical function doubles as protective membrane and is fitted in another side.In addition, as the manufacture method of polarization element, as we all know there are utilizing the uniaxial extension polyvinyl alcohol resin film of dichroism pigment dyeing to carry out boric acid process, the rear dry method of washing.
Usually, after above-mentioned washing and drying, immediately to polarization element laminating protective membrane.This is because the physical strength of dried polarization element is weak, once be reeled, then can produce problems of crack on machine direction.Thus, usually polarization element is after the drying coated with immediately the tackiness agent of water system, is then fitted on the two sides of polarization element protective membrane by this tackiness agent simultaneously.Usually, as protective membrane, use thickness is the tri acetyl cellulose film of 30 ~ 120 μm.
At polarization element and protective membrane, particularly with the bonding of the protective membrane be made up of tri acetyl cellulose film, mostly use the tackiness agent of polyethenol series, also have and attempt using the tackiness agent of polyurethane series to replace the tackiness agent of this polyethenol series.Such as, in Japanese Unexamined Patent Publication 7-120617 publication (patent documentation 1), describe and use polyurethane prepolymer as tackiness agent, polarization element high for water ratio and cellulose acetate prime system protective membrane such as tri acetyl cellulose film are bonded.
On the other hand, because the Water Vapour Permeability of tri acetyl cellulose is high, be therefore fitted with the polaroid of this resin molding as protective membrane, under the condition that such as temperature 70 C, relative humidity 90% are such under damp and hot, have problems such as causing deterioration.Therefore, also proposed by using Water Vapour Permeability lower than the resin molding of tri acetyl cellulose film as protective membrane, solve the method for this problem, such as, there will be a known noncrystalline polyolefin system resin as protective membrane.Specifically, describe in Japanese Unexamined Patent Publication 6-51117 publication (patent documentation 2) and close thermoplasticity saturated norbornene series resin sheet material as protective membrane at least one surface layer of polarization element.
In the situation of the low protective membrane of such Water Vapour Permeability of fitting with device in the past; use with water be primary solvent tackiness agent such as polyvinyl alcohol water solution, protective membrane is fitted to polyethenol series polarization element after make the so-called wet type lamination of solvent seasoning; have and can not get enough bond strengths, or the problem such as bad order.This is because, the low film of Water Vapour Permeability is compared with tri acetyl cellulose film, be generally hydrophobic, and due to Water Vapour Permeability low, thus can not the fully dry water as solvent.
Therefore, propose in Japanese Unexamined Patent Publication 2000-321432 publication (patent documentation 3) and the polarization element of polyethenol series and the protective membrane that comprises thermoplasticity saturated norbornene system resin are carried out by polyurethane series tackiness agent the scheme that bonds.But polyurethane series tackiness agent has solidification needs long problem, and its bounding force is also not necessarily abundant.
On the other hand, also there will be a known the scheme of different types of protective membrane of fitting on the two sides of polarization element, such as propose in Japanese Unexamined Patent Publication 2002-174729 publication (patent documentation 4), the protective membrane of noncrystalline polyolefin system resin is comprised in the one side laminating of the polarization element be made up of polyvinyl alcohol resin film, the protective membrane of the resin such as tri acetyl cellulose different with this noncrystalline polyolefin system resin is comprised in another side laminating, and propose in Japanese Unexamined Patent Publication 2005-208456 publication (patent documentation 5), by water system first tackiness agent containing particular polyurethane resin at the laminated cyclic olefine resin molding of the one side of the light polarizing film comprising polyvinyl alcohol resin, by the aqueous solution of the water system second tackiness agent such as polyvinyl alcohol resin different with the first tackiness agent at the laminated cellulose acetate resin film of another side.
In above-mentioned patent documentation 4, be called as noncrystalline polyolefin system resin or in above-mentioned patent documentation 5, be called as the resin of cyclic olefine resin, that there is the monomeric unit be made up of the polycycle cycloolefin that norbornylene or derivatives thereof, dimethano-octahydro naphthalene are such, and when remaining double bond as ring-opening polymerization polymer, the thermoplastic resin be hydrogenated in preferred double bond.
In addition; disclose with not containing the tackiness agent that the epoxy resin of aromatic nucleus is principal constituent in Japanese Unexamined Patent Publication 2004-245925 publication (patent documentation 6); and propose and make it carry out cationoid polymerisation to this tackiness agent irradiation active energy beam, thus the method for bonding polarization element and protective membrane.Although epoxy adhesive disclosed in it is for that the various transparent resin films being representative with noncrystalline polyolefin system resin and cellulose-based resin are fitted in polarization element is effective especially; but gradually find; special in taking acrylic resin as protective membrane, its bounding force is not necessarily abundant.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 7-120617 publication
Patent documentation 2: Japanese Unexamined Patent Publication 6-51117 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2000-321432 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2002-174729 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2005-208456 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2004-245925 publication
Summary of the invention
The problem that invention will solve
In order to solve the problem when polarization element of polyethenol series and the low protective membrane of Water Vapour Permeability being fitted by wet type lamination; consider the dry furnace superintendent after by laminating to lengthen to obtain more time of drying; but during the dry furnace superintendent of simple increase, produce the problem easily causing variable color because of the thermal degradation when of polarization element.Therefore, consider and reduce drying temperature to make to cause polarization element thermal degradation when, but in this case, in order to abundant drying, need to increase dry furnace superintendent further, have the problem that facility investment is excessive.In addition; fit on the two sides of polarization element different types of protective membrane time; the shrinking percentage of being heated due to these protective membranes is different; therefore be under the state that the shrinkage of two surface protective films is different and polarization element bonding; having when being back to normal temperature after the drying, easily there is curling problem in polaroid.
In order to improve this problem, can consider to adopt the applying method by dry lamination.But; because the viscosity of the tackiness agent with dry lamination suitability is high; from the problem that the physical strength of polarization element is weak, the adhesive bonding method of polarization element and protective membrane is limited at protective membrane coating adhesive, and then is conformed to the method for polarization element.In the method, when being attached with foreign matter at the coated face of tackiness agent before fitting, cannot hidden foreign matter, and be that starting point produces bubble between tack coat and polarization element with foreign matter after laminating, therefore become the reason of fleck defect.
The present inventor is in order to develop when using the low resin molding of the Water Vapour Permeability being selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin system resin as polarization element protective membrane; the light curable adhesive of good adhesion can be revealed with the activity list of short period of time; and carried out positive research; found that by using specific light curable adhesive, can to fit these protective membranes with the operation of short period of time.So find, even if this tackiness agent is when using acrylic resin film as protective membrane, also high bounding force can be played between itself and polarization element.
In addition, the adhesive thickness of polaroid, from the viewpoint such as slimming and weather resistance, is preferably less than 5 μm, but in order to be coated with solvent-free light curable adhesive, and obtain the level and smooth coated face that thickness is less than 5 μm, need the lowering viscousity carrying out tackiness agent., when making solvent-free system's tackiness agent lowering viscousity, bounding force usually can decline.But; the present inventor finds; by using specific light curable adhesive, the while that it being low viscous, at polarization element and vibrin, polycarbonate resin can being selected from, between acrylic resin and the protective membrane of noncrystalline polyolefin system resin, having given play to high adhesion.
Therefore; the object of the invention is to; light curable adhesive is provided and uses this tackiness agent to be fitted with the polaroid of protective membrane at polarization element; even if wherein this light curable adhesive is when using the low resin molding of the Water Vapour Permeability being selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin system resin as protective membrane; also protective membrane and polarization element can be bonded with sufficient bond strength with the operation of short period of time; and viscosity is low, and also the problems such as bad order can not be caused after long duration test.Another object of the present invention is to, the optics using this polaroid can form liquid crystal indicator excellent in reliability is provided, and is applied to liquid crystal indicator.
For the method for dealing with problems
Namely; according to the present invention; Photocurable adhesive composition is provided; it is the binder composition having the polarization element of the polyvinyl alcohol resin film of dichroism pigment for protective membrane being bonded in the gas absorption quantity comprising uniaxial extension; this protective membrane comprises the transparent resin film being selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin system resin, and said composition is characterised in that and contains
(A) have in molecule the epoxy compounds of at least 2 epoxy group(ing) and at least 1 aromatic nucleus,
(B) what can have ester skeleton has two (methyl) acrylate that carbon number is the glycol (wherein, except ether compound) of 5 ~ 10, and
(C) light cationic polymerization initiators,
Described (A) ~ (C) composition containing proportional be in the composition
(A) composition: 20 ~ 60 % by weight
(B) composition: 5 ~ 45 % by weight
(C) composition: 0.5 ~ 10 % by weight.
In this Photocurable adhesive composition, as (A) composition, be preferably bisphenol A type epoxy resin.Or, as (B) composition, be preferably neopentyl glycol, hydroxy new pentane acid and acrylic acid esterification reaction product.
In addition, with regard to Photocurable adhesive composition, in order to make composition lowering viscousity, and obtain good solidified nature and binding property, the oxetane compound shown in following formula (1) being preferably (D) composition containing 5 ~ 45 % by weight in the composition.
[chemical formula 1]
In addition, with regard to Photocurable adhesive composition, in order to obtain the better binding property to dry polarization element, in the composition preferably containing 1 ~ 20 % by weight as (E) composition following formula (2) shown in oxetane compound.
[chemical formula 2]
The free-radical polymerised compositions such as (B) composition contained in these Photocurable adhesive compositions, can by (C) composition solidifying by the free radical that produce during photolysis, but in order to obtain sufficient reactivity with few irradiation dose, preferably contain optical free radical polymerization starter as (F) composition using the ratio of less than 10 % by weight.
With regard to these Photocurable adhesive compositions, in order to obtain the coated face of smoothness excellence, preferably in the composition also containing 0.01 ~ 0.5 % by weight as the flow agent of (G) composition.
In addition; according to the present invention; polaroid is provided; it by tackiness agent, the protective membrane comprising the transparent resin film being selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin system resin is fitted in the gas absorption quantity comprising uniaxial extension have the polarization element of the polyvinyl alcohol resin film of dichroism pigment and formed, and this tackiness agent is formed by any one Photocurable adhesive composition above-mentioned.
This polaroid can be manufactured by following method; the method comprises: at the adhesive coated operation of at least coated on one side any one Photocurable adhesive composition aforementioned, the binder layer by gained of the binding face of polarization element and protective membrane; the bonding process of fit polarization element and protective membrane and under the state of polarization element and protective membrane being fitted by this binder layer, makes the curing process that Photocurable adhesive composition solidifies.Particularly, can adopt: after uncured above-mentioned Photocurable adhesive composition is coated polarization element, protective membrane is fitted in this binder composition coated face, then make this binder composition solidify with the method forming binder layer; After uncured above-mentioned Photocurable adhesive composition is coated protective membrane, polarization element is fitted in this binder composition coated face, then make this binder composition solidify with the method forming binder layer; The above-mentioned Photocurable adhesive composition that curtain coating is uncured between polarization element and protective membrane; the laminating thing of polarization element and protective membrane is clamped with roller etc.; and binder composition is rolled equably wide; make its pressing simultaneously, then make this binder composition solidify with the method etc. forming binder layer.
Further, according to the present invention, provide the laminated optics of optical layers having above-mentioned polaroid and show other optical function.Other optical layers under this situation preferably comprises phase difference film.Also provide the one or both sides this optics being configured in liquid crystal cell and the liquid crystal indicator formed.
Invention effect
Photocurable adhesive composition of the present invention, is easily solidified by irradiation ultraviolet radiation isoreactivity energy-ray, bonds polarization element and protective membrane securely with the operation of short period of time.This binder composition is particularly useful when protective membrane is made up of acrylic resin.Because this binder composition solidifies with the operation of short period of time, therefore, productivity the polaroid obtained by this binder composition laminating polarization element and protective membrane can be manufactured well.Further, by the optics that this polaroid and other optical layers combine, liquid crystal indicator excellent in reliability can be formed.
Embodiment
Below, the present invention is described in detail.The present invention, when the protective membrane be made up of transparent resin film being bonded in the polarization element having the polyvinyl alcohol resin film of dichroism pigment to form by the gas absorption quantity of uniaxial extension, uses the Photocurable adhesive composition of specific composition.Like this, by using Photocurable adhesive composition polarization element and protective membrane to be fitted, polaroid is obtained thus.Can by this polaroid with to have the optical layers of other optical function laminated and form optics.In addition, this optics can be configured at least side of liquid crystal cell and form liquid crystal indicator.Below, be described according to the order of the manufacture method of Photocurable adhesive composition, polaroid, polaroid, optics, liquid crystal indicator.
[Photocurable adhesive composition]
The present invention, in order to polarization element and protective membrane be fitted, uses the Photocurable adhesive composition of specific composition.Below, sometimes by this Photocurable adhesive composition referred to as " light curable adhesive " or " composition ".Light curable adhesive of the present invention must containing following (A), (B) and (C) three kinds of compositions.
(A) have in molecule the epoxy compounds of at least 2 epoxy group(ing) and at least 1 aromatic nucleus,
(B) what can have ester skeleton has two (methyl) acrylate that carbon number is the glycol (wherein, except ether compound) of 5 ~ 10, and
(C) light cationic polymerization initiators.
Above-mentioned (A) epoxy compounds is also called " (A) composition " or " epoxy compounds (A) " by this specification sheets, also (B) two (methyl) acrylate is called " (B) composition " or " two (methyl) acrylate (B) ", also (C) light cationic polymerization initiators is called " (C) composition " or " light cationic polymerization initiators (C) ".
Make (A) ~ (C) composition ratio is in the composition that (A) composition is 20 ~ 60 % by weight, (B) composition is 5 ~ 45 % by weight, and (C) composition is 0.5 ~ 10 % by weight.
This light curable adhesive, can arbitrarily containing the oxetane compound shown in the following formula (1) as (D) composition, as (E) composition following formula (2) shown in oxetane compound, as the optical free radical polymerization starter of (F) composition, and as the flow agent of (G) composition.
[chemical formula 3]
[chemical formula 4]
Above-mentioned (E) oxetane compound is also called " (E) composition " or " oxetane compound (E) " by this specification sheets, also (F) optical free radical polymerization starter is called " (F) composition " or " optical free radical polymerization starter (F) ", also (G) flow agent is called " (G) composition " or " flow agent (G) ".
< epoxy compounds (A) >
In light curable adhesive of the present invention, form the epoxy compounds of (A) composition, be the compound in molecule with at least 2 epoxy group(ing) and at least 1 aromatic nucleus, it can use usually known various solidified nature epoxy compoundss.
As the object lesson of (A) composition, the bisphenol-type epoxy resin as the diglycidylether of the diglycidylether of dihydroxyphenyl propane, the diglycidylether of Bisphenol F and brominated bisphenol A can be enumerated; As the phenolic resin varnish type epoxy resin phenol novolak type epoxy resin and cresol novolak type epoxy resin; And biphenyl type epoxy resin, quinhydrones diglycidylether, resorcinol diglycidyl ether, terephthalic acid diglycidyl ester, o-phthalic acid diglycidyl ester, end are the polyhutadiene of carboxylic acid and the addition reaction etc. of bisphenol A type epoxy resin.
Herein, epoxy resin refers in molecule the epoxy group(ing) on average with more than 2, the compound solidified by reacting or polymkeric substance.According to the convention of this area, in this specification sheets, as long as there is the solidified nature compound of more than 2 epoxy group(ing), even monomer is also referred to as epoxy resin in molecule.
As (A) composition, according to the viewpoint that the solidified nature of composition and binding property etc. are excellent, the glycidyl ether of preferred fragrance compounds of group, more preferably the diglycidylether of dihydroxyphenyl propane, the diglycidylether of Bisphenol F and phenol novolak type epoxy resin, particularly preferably bisphenol A type epoxy resin.
As bisphenol A type epoxy resin, from aspects such as solidified nature, goods that cl content is few or the few goods of number of repeat unit can be selected.
(A) epoxy compounds of composition can be used alone a kind, also can be used in combination by two or more.
With whole compositions for benchmark, the mixing ratio of the epoxy compounds of (A) composition is the scope of 20 ~ 60 % by weight.By being this ratio, composition can being made to have the low viscosity that can obtain level and smooth coated face, good binding property and solidified nature can be obtained.
< bis-(methyl) acrylate (B) >
In light curable adhesive of the present invention, form (B) composition two (methyl) acrylate, be (B) can have an ester skeleton there is two (methyl) acrylate that carbon number is the glycol (wherein, except ether compound) of 5 ~ 10.
As (B) composition, when using intramolecular (methyl) acryloyl radix to be two (methyl) acrylate of more than 3, the binding property of polarization element is easily become bad.In addition, when intramolecular (methyl) acryloyl radix is 1, when ultraviolet irradiation amount is few, often have residual monomers residual or cause binding property and weather resistance bad.In addition, even if the glycol for having carbon number 5 ~ 10, the glycol as ether compound is also not enough to the binding property of polarization element.
By using (B) composition, not only reduce the viscosity of composition, even and if when the polarization element high to ridity bonds, binding property and weather resistance are also excellent.
In (B) composition, as the object lesson of two (methyl) acrylate of glycol with 5 ~ 10 carbon numbers, two (methyl) vinylformic acid DOPCP, two (methyl) vinylformic acid 1 can be enumerated, 6-hexylene glycol ester, two (methyl) vinylformic acid 3-methyl isophthalic acid, 5-pentadiol ester, two (methyl) vinylformic acid 2-butyl-2-ethyl-1, ammediol ester and two (methyl) vinylformic acid 1,9-nonanediol ester etc.
(B) composition can have ester skeleton, as object lesson, can enumerate neopentyl glycol, hydroxy new pentane acid and (methyl) acrylic acid esterification reaction product etc.
Wherein, according to the viewpoint of lowering viscousity, binding property, weather resistance, low odor, low skin irritability excellence, particularly preferably neopentyl glycol, hydroxy new pentane acid and (methyl) acrylic acid esterification reaction product.
With whole composition for benchmark, the mixing ratio of (B) composition is the scope of 5 ~ 45 % by weight.By being this ratio, excellent coating that viscosity brings and good binding property can be obtained.(B) the more preferably mixing ratio of composition is 10 ~ 40 % by weight, and more preferably 15 ~ 40 % by weight.
< light cationic polymerization initiators (C) >
Light curable adhesive of the present invention, containing epoxy compounds explained above (A) and oxetane compound described later as required as cure component, any one in them is all solidified by cationoid polymerisation, therefore coordinates light cationic polymerization initiators as (C) composition.This light cationic polymerization initiators, by irradiating visible ray, ultraviolet, X-ray, electron beam isoreactivity energy-ray, and produces positively charged ion kind or Lewis acid, thus causes the polyreaction of epoxy group(ing) or oxetanyl.
By coordinating as the light cationic polymerization initiators of (C) composition, can solidify at normal temperatures, the thermotolerance of considering polarization element can be reduced and because to expand or contraction causes the necessity of distortion, and bond protective membrane well.In addition, because light cationic polymerization initiators plays catalyst action under the irradiation of active energy beam, therefore, even if mix with epoxy compounds (A) and oxetane compound (B), its storage stability, workability are also excellent.Producing positively charged ion kind or lewis acidic compound as by irradiating active energy beam, the salt as aromatic diazonium salt, aromatic iodonium salts and aromatic series sulfonium salt, iron-allene complex thing etc. can be enumerated.
As aromatic diazonium salt, such as, can enumerate following compound.
Benzene diazonium hexafluoro antimonate,
Benzene diazonium hexafluorophosphate,
Benzene diazonium hexafluoro borate etc.
As aromatic iodonium salts, such as, can enumerate following compound.
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, such as, can enumerate following compound.
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoro antimonate,
Triphenylsulfonium four (pentafluorophenyl group) borate,
The two hexafluorophosphate of 4,4 '-bis-(phenylbenzene sulfonium base) 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 (to toluyl) sulfonium base)-ITX hexafluoro antimonate,
7-[two (to toluyl) sulfonium base)-ITX four (pentafluorophenyl group) borate,
4-phenylcarbonyl group-4 '-phenylbenzene blunderbuss base-diphenyl sulfide hexafluorophosphate,
4-(to tert-butyl-phenyl carbonyl)-4 '-phenylbenzene blunderbuss base-diphenyl sulfide hexafluoro antimonate,
4-(to tert-butyl-phenyl carbonyl)-4 '-two (to toluyl) sulfonium base-diphenyl sulfide four (pentafluorophenyl group) borate etc.
As iron-allene complex thing, following compound can be enumerated.
Dimethylbenzene-cyclopentadienyl iron (II) hexafluoro antimonate,
Cumene-cyclopentadienyl iron (II) hexafluorophosphate,
Dimethylbenzene-cyclopentadienyl iron (II)-three (trifluoromethyl sulfonyl) methide etc.
These light cationic polymerization initiators, can be used alone a kind separately, also can be used in combination by two or more.Wherein, even if also there is Ultraviolet Light due to particularly aromatic series blunderbuss salt in the wavelength region may of more than 300nm, thus the cured article that solidified nature is excellent, have good mechanical strength and bond strength can be provided, therefore preferably use.
With regard to (C) composition, easily can obtain commercially available product, such as, can enumerate respectively with " カ ヤ ラ Star De PCI-220 " that trade(brand)name represents, " カ ヤ ラ Star De PCI-620 " (being Japanese chemical drug (strain) system above), " UVI-6992 " (De ウ ケ ミ カ Le society system), " ア デ カ オ プ ト マ mono-SP-150 ", " ア デ カ オ プ ト マ mono-SP-160 " (being (strain) ADEKA 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 " (being body ど り chemistry (strain) system above), " PI-2074 " (ロ mono-デ イ ア society system), " IRGACURE 250 ", " IRGACURE PAG103 ", IRGACURE PAG108 ", IRGACURE PAG121 ", IRGACURE PAG203 " (being Qi Si Inc. above), " CPI-100P ", " CPI-101A ", " CPI-210S " (being サ Application ア プ ロ (strain) system above) etc.Particularly, according to solidified nature and fusible viewpoint, the particularly preferably CPI-100P that manufactures of サ Application ア プ ロ (strain).
With whole composition for benchmark, the mixing ratio of (C) composition is the scope of 0.5 ~ 10 % by weight.When this ratio is less than 0.5 % by weight, the solidification of tackiness agent is insufficient, and physical strength and bond strength decline, on the other hand, when this ratio is more than 10 % by weight, the ionic substance in cured article increases, therefore the water absorbability of cured article increases, and endurance quality reduces, therefore not preferred.
< oxetane compound (D) >
In light curable adhesive of the present invention, in order to obtain the lowering viscousity of composition and good solidified nature and binding property, the compound of structure shown in the preferred previously described formula (1) coordinated as (D) composition, i.e. 3-ethyl-3-[(3-Ethyloxetane-3-base) methoxymethyl] trimethylene oxide.
As the mixing ratio of (D) composition, with whole composition for benchmark, it is the scope of 5 ~ 45 % by weight.By being this ratio, composition can being made to have the low viscosity that can obtain level and smooth coated face, good binding property and solidified nature can be obtained.
< oxetane compound (E) >
In light curable adhesive of the present invention, even if when when polarization element is more dry, composition also needs to play excellent adhesiveness, the compound of structure shown in the preferred previously described formula (2) coordinated as (E) composition, i.e. 3-ethyl-3-hydroxymethyl oxetane.
When good to the binding property of more dry polarization element, the mixing ratio of the oxetane compound of formation (E) composition for benchmark, preferably contains 1 ~ 20 % by weight with whole composition.If it is less than 1 % by weight, then often additive effect is little, when its more than 20 % by weight time, often solidified nature be deteriorated, binding property decline.
< optical free radical polymerization starter (F) >
The radically curing compositions such as (B) composition contained in light curable adhesive of the present invention can by (C) composition solidifying by the free radical that produce during photolysis, but in order to obtain sufficient reactivity with few irradiation dose, preferably coordinate the optical free radical polymerization starter as (F) composition.With whole composition for benchmark, the mixing ratio of (F) composition is preferably less than 10 % by weight, is more preferably 0.1 ~ 3 % by weight.When use level is more than 10 % by weight, often cause the decline of weather resistance, therefore not preferred.
As the object lesson of (F) composition, such as, following compound can be enumerated.
As 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-methylthio group phenyl)-2-morpholinyl third-1-ketone, 1-hydroxycyclohexylphenylketone, α, α-diethoxy phenyl methyl ketone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl third-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl third-1-ketone and the such acetyl benzene series Photoepolymerizationinitiater initiater of 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) fourth-1-ketone,
Benzoin ether system Photoepolymerizationinitiater initiater as bitter almond oil camphor, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
As benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide and the such benzophenone series Photoepolymerizationinitiater initiater of 2,4,6-tri-methyl benzophenone;
Thioxanthone system Photoepolymerizationinitiater initiater as such in ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones and 1-chloro-4-propoxythioxanthone;
As 2,4,6-trimethylbenzoyldiphenyl oxide compound, two (2,6-Dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide and two (2,4,6-trimethylbenzoyl) the such acylphosphine oxide system Photoepolymerizationinitiater initiater of phenylphosphine oxide;
1,2-acetyl caproyl, 1-[4-(Phenylsulfanylphenyl)]-, the oxime ester system Photoepolymerizationinitiater initiater that 2-(O-benzoyl oxime) is such;
Camphorquinone etc.
With regard to (F) 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 (F) composition, its mixing ratio for benchmark with whole composition, is preferably less than 10 % by weight, is more preferably 0.1 ~ 3 % by weight.When the amount of optical free radical polymerization starter (F) is too much, often cannot obtain enough intensity, in addition, during its quantity not sufficient, often tackiness agent cannot fully solidify.
< flow agent (G) >
In light curable adhesive of the present invention, in order to obtain the coated face of smoothness excellence, preferably containing (G) composition flow agent.
As (G) composition, silicon-type flow agent and fluorine system flow agent etc. can be enumerated, commercially available various flow agents can be used.
(G) the optimizing mixing proporiton example of composition, with whole composition for benchmark, is 0.01 ~ 0.5 % by weight.When adding number and being less than 0.01 part, the additive effect of flow agent is little, and on the contrary, when it is more than 0.5 part, binding property declines.
Other solidified nature composition of < >
Light curable adhesive of the present invention, except above-mentioned (A) ~ (G) composition, can also containing other cation-curable composition or radically curing composition.
As the cation-curable composition beyond (A) composition, (D) composition and (E) composition, various epoxy compounds or oxetane compound and vinyl ether compound can be enumerated.
As the object lesson of the epoxy compounds beyond (A) composition, dicyclopentadiene can be enumerated, limonene dioxide, 4 vinyl cyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, two (3,4-epoxycyclohexylmethyl) adipic acid ester, 1,6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, tetramethylolmethane four glycidyl ether, poly-BDDE, Hydrogenated Bisphenol A diglycidylether, epoxidized vegetable oil, 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-expoxycyclohexyl) ethyl triethoxysilane, 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl dimethoxysilane, two ends are the polyhutadiene diglycidylether of hydroxyl, the inner loop oxide compound of polyhutadiene, the double bond of styrene-butadiene copolymer is by the compound of PART EPOXY (such as, ダ イ セ Le chemical industry (strain) manufacture " エ Port Off レ Application De "), and the isoprene unit of the segmented copolymer of ethylene-butene copolymer and polyisoprene is by the compound of PART EPOXY (such as, KRATON company manufacture " L-207 ") etc.
As the object lesson of the oxetane compound beyond (D) composition and (E) composition, the simple function trimethylene oxide containing alkoxyalkyl that 3-ethyl-3-(2-Ethylhexoxymethyl) trimethylene oxide is such can be enumerated, the simple function trimethylene oxide containing aromatic series base that 3-ethyl-3-phenoxymethyloxetane is such, 1, two [(3-Ethyloxetane-3-base) methoxymethyl] benzene of 4-, 1, two [(3-Ethyloxetane-3-base) methoxyl group] benzene of 4-, 1, two [(3-Ethyloxetane-3-base) methoxyl group] benzene of 3-, 1, two [(3-Ethyloxetane-3-base) methoxyl group] benzene of 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, 2, two [(3-Ethyloxetane-3-base) methoxyl group] naphthalene of 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 utilizing 3-chloromethyl-3-Ethyloxetane of novolak phenolics, 3 (4), 8 (9)-bis-[(3-Ethyloxetane-3-base) methoxymethyl]-three ring [5.2.1.0 2.6] decane, 2, two [(3-Ethyloxetane-3-base) methoxymethyl] norbornane of 3-, 1, 1, 1-tri-[(3-Ethyloxetane-3-base) methoxymethyl] propane, 1-butoxy-2, two [(3-Ethyloxetane-3-base) methoxymethyl] butane of 2-, 1, two [{ 2-(3-Ethyloxetane-3-base) methoxyl group } ethylsulfanyl] ethane of 2-, two [{ 4-(3-Ethyloxetane-3-base) methylsulfany } phenyl] sulfide, 1, two [(3-Ethyloxetane-3-base) methoxyl group]-2 of 6-, 2, 3, 3, 4, 4, 5, 5-octafluoro hexane, 3-[(3-Ethyloxetane-3-base) methoxyl group] propyl trimethoxy silicane, 3-[(3-Ethyloxetane-3-base) methoxyl group] propyl-triethoxysilicane, the hydrolytic condensate of 3-[(3-Ethyloxetane-3-base) methoxyl group] propyl trialkoxy silane, the condenses etc. of four [(3-Ethyloxetane-3-base) methyl] silicon ester.
As the object lesson of vinyl ether compound, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl base ether, triethyleneglycol divinylether, cyclohexanedimethanol divinyl base ether etc. can be enumerated.
(A) mixing ratio of the cation-curable composition beyond composition, (D) composition and (E) composition, with whole composition for benchmark, be preferably less than 20 % by weight, be more preferably less than 10 % by weight, particularly preferably less than 5 % by weight.
As the radically curing composition beyond (B) composition; various compound can be enumerated; such as, (methyl) esters of acrylic acid, (methyl) acrylic amide, maleimide, (methyl) vinylformic acid, toxilic acid, methylene-succinic acid, (methyl) propenal, (methyl) acryloyl morpholine, NVP, cyanacrylate, vinyl hexanediacetate, vinyltrimethoxy silane etc. can be enumerated.
As the object lesson of (methyl) esters of acrylic acid in molecule with 1 (methyl) acryl, (methyl) methyl acrylate can be enumerated, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxybutyl, (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, (methyl) benzyl acrylate, (methyl) acrylate of oxidation of phenol alkene affixture, (methyl) acrylate of p-cumylphenol alkylen oxide adducts, (methyl) acrylate of orthoxenol alkylen oxide adducts, (methyl) acrylate of nonylphenol alkylen oxide adducts, 2-methoxy ethyl (methyl) acrylate, ethoxyethoxyethyl (methyl) acrylate, (methyl) acrylate of the alkylen oxide adducts of 2-ethylhexyl alcohol, ethylene glycol list (methyl) acrylate, propylene glycol list (methyl) acrylate, pentanediol list (methyl) acrylate, hexylene glycol list (methyl) acrylate, list (methyl) acrylate of Diethylene Glycol, list (methyl) acrylate of triethylene glycol, list (methyl) acrylate of TEG, list (methyl) acrylate of polyoxyethylene glycol, list (methyl) acrylate of dipropylene glycol, list (methyl) acrylate of tripropylene glycol, list (methyl) acrylate of polypropylene glycol, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, 2-hydroxyl-3-butoxypropyl (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification (methyl) tetrahydrofurfuryl acrylate, (2-Ethyl-2-Methyl-1,3-dioxolane-4-base) methyl (methyl) acrylate, (2-isobutyl--2-methyl isophthalic acid, 3-dioxolane-4-base) methyl (methyl) acrylate, (Isosorbide-5-Nitrae-dioxy spiral shell [4,5] decane-2-base) methyl (methyl) acrylate, (methyl) glycidyl acrylate, 3,4-epoxycyclohexylmethyl (methyl) acrylate, (3-Ethyloxetane-3-base) methyl (methyl) acrylate, 2-(methyl) acryloyloxyethyl isocyanate, (methyl) allyl acrylate, N-(methyl) acryloyl-oxyethyl hexahydrophthalic phthalimide, N-(methyl) acryloyl-oxyethyl tetrahydric phthalimide, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, ω-carboxyl-polycaprolactone list (methyl) acrylate, 2-(methyl) acryloyl-oxyethyl acid phosphoric acid ester, 3-(methyl) acryloxypropyl Trimethoxy silane, 3-(methyl) acryloxypropyl dimethoxymethylsilane, 3-(methyl) acryloxypropyl triethoxyl silane etc.
In addition, as the object lesson of (methyl) esters of acrylic acid beyond (B) composition in molecule with more than 2 (methyl) acryls, tristane dihydroxymethyl two (methyl) acrylate can be enumerated, two (methyl) acrylate of dihydroxyphenyl propane alkylen oxide adducts, two (methyl) acrylate of Hydrogenated Bisphenol A, two (methyl) acrylate of bisphenol A diglycidyl ether, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, three (methyl) acrylate of the alkylen oxide adducts of TriMethylolPropane(TMP), two-TriMethylolPropane(TMP) four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, two of isocyanuric acid alkylen oxide adducts or three (methyl) acrylate, urethane (methyl) acrylate, polyester (methyl) acrylate and epoxy group(ing) (methyl) acrylate etc.
As the object lesson of (methyl) acrylic amide, (methyl) acrylamide, N can be enumerated, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-(3-N, N-dimethylaminopropyl) (methyl) acrylamide, methylene-bis (methyl) acrylamide, ethylenebis (methyl) acrylamide, N, N-diallyl (methyl) acrylamide etc.
As the object lesson of maleimide, the urethane acrylate etc. of N-methylmaleimido, N-hydroxyethyl maleimide, N-hydroxyethyl citraconimide, N-hydroxyethyl citraconimide and isophorone diisocyanate can be enumerated.
With whole composition for benchmark, the mixing ratio of the radically curing composition beyond (B) composition is preferably less than 20 % by weight, is more preferably and is less than 10 % by weight, and is particularly preferably less than 5 % by weight.
< does not have other composition > of solidified nature
Photocurable pressure-sensitive adhesive of the present invention also further cooperation arbitrarily can not have other composition of solidified nature in the scope not damaging effect of the present invention, particularly, can enumerate photosensitizers, hot cationic polymerization initiators, polyol compound, water etc.
As the object lesson of photosensitizers, benzophenone, o-benzoyl yl benzoic acid methyl esters, ITX, 9,10-dibutoxy anthracenes etc. can be enumerated.Wherein, although also there is the compound being equivalent to aforementioned (F) composition optical free radical polymerization starter, so-called photosensitizers becomes light splitting cationic polymerization initiators to be used as the material of sensitizer relative to (C) herein.They can be used independently, can also be 2 or more kinds in combination.
With whole composition for benchmark, the mixing ratio of photosensitizers is preferably less than 3 % by weight.
As the object lesson of hot cationic polymerization initiators, benzylsulfonium, thiophene salt, tetrahydro-thiophene salt (チ ォ ラ ニ ゥ system salt), benzyl ammonium salt, pyridinium salt, hydrazonium salt, carboxylicesters, sulphonate, amine imide etc. can be enumerated.These initiators can obtain commercially available product easily, such as, can enumerate represent with trade(brand)name respectively " ァ デ カ ォ プ ト Application CP77 " and " ァ デ カ ォ プ ト Application CP66 " (above is (strain) ADEKA system), " CI-2639 " and " CI-2624 " (above is Japanese Cao Da (strain) system), " サ Application ェ ィ De SI-60L ", " サ Application ェ ィ De SI-80L " and " サ Application ェ ィ De SI-100L " (being that three new chemical industry (strain) are made above) etc.
With whole composition for benchmark, the mixing ratio of hot cationic polymerization initiators is preferably less than 3 % by weight.
As the object lesson of polyol compound, polyether polyols, polyester polyol compound, polycaprolactone polyol compound, polycarbonate polyol compound etc. can be enumerated.
With whole composition for benchmark, the mixing ratio of polyol compound is preferably less than 5 % by weight.
With regard to the viscosity of Photocurable pressure-sensitive adhesive of the present invention, in order to obtain the coating that can use in the manufacturing process of polaroid, even if namely for film also obtains the coated face of smoothness excellence, the viscosity preferably at 25 DEG C is below 200mPas, is more preferably below 150mPas.
With regard to Photocurable pressure-sensitive adhesive of the present invention, in order to obtain the good adhesion to the high polarization element of ridity, also can add a small amount of water.Under this situation, with whole composition for benchmark, the addition of water is preferably less than 3 % by weight, be more preferably and be less than 1 % by weight.
In addition, only otherwise damage effect of the present invention, ion capturing agent, oxidation inhibitor, photostabilizer, chain-transfer agent, tackifier, thermoplastic resin, metal oxide microparticle, defoamer, pigment, organic solvent etc. can also be coordinated.
[polaroid]
Light curable adhesive described above, for protective membrane being bonded in the polarization element having the polyvinyl alcohol resin film of dichroism pigment to form by the gas absorption quantity of uniaxial extension, fits in polarization element thus to form polaroid by protective membrane.That is, the polaroid that the present invention relates to is the polaroid being fitted with protective membrane at the polarization element having the polyvinyl alcohol resin film of dichroism pigment to form by the gas absorption quantity of uniaxial extension.Protective membrane only can be fitted in the one side of polarisation optical element, also can be fitted in the two sides of polarization element.When the two sides of polarization element laminating protective membrane, each protective membrane can by the resin formation of identical type, also can by different types of resin formation.
< polarization element >
Form the polyvinyl alcohol resin of polarization element by the resin saponification of polyvinyl acetate system being obtained.As polyvinyl acetate system resin, except as except the polyvinyl acetate of leifa, can also illustrate vinyl-acetic ester and can with the multipolymer etc. of other monomer of its copolymerization.As can with other monomer of vinyl acetate copolymerization, such as, unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class etc. can be enumerated.The saponification deg of polyvinyl alcohol resin is generally 85 ~ 100 % by mole, the preferred scope of 98 ~ 100 % by mole.This polyvinyl alcohol resin, can modification further, such as, can use by the polyvinyl formal of aldehydes modification or polyvinylacetal etc.The polymerization degree of polyvinyl alcohol resin is generally 1000 ~ 10000, is preferably the scope of 1500 ~ 10000.
Polaroid is manufactured by following operation, such polyvinyl alcohol resin film is carried out the operation of uniaxial extension, with dichroism pigment to polyvinyl alcohol resin film dye the operation making it adsorb this dichroism pigment, the polyvinyl alcohol resin film having adsorbed dichroism pigment with boric acid aqueous solution process operation, use boric acid aqueous solution process after the operation of washing and protective membrane is fitted in implement these operations and the operation of the uniaxial extension polyvinyl alcohol resin film of gas absorption quantity dichroism pigment.
Uniaxial extension, can carry out before utilizing dichroism pigment dyeing, also can carry out while utilizing dichroism pigment dyeing, can also carry out after utilizing dichroism pigment dyeing.When carrying out uniaxial extension after utilizing dichroism pigment dyeing, this uniaxial extension can carry out before boric acid process, also can carry out in boric acid process.In addition, uniaxial extension can certainly be carried out in these stages.Uniaxial extension, can, along uniaxial extension between the roller that circumferential speed is different, also can use hot-rolling along uniaxial extension.In addition, can be the dry type stretching stretched in an atmosphere, also can be that the wet type of carrying out stretching under the state utilizing solvent-swollen stretches.Stretching ratio is generally about 4 ~ 8 times.
When using dichroism pigment to dye to polyvinyl alcohol resin film, such as, as long as by polyvinyl alcohol resin film immersion in the aqueous solution containing dichroism pigment.As dichroism pigment, specifically, iodine or dichroic dye can be used.
When using iodine as dichroism pigment, be typically employed in the aqueous solution containing iodine and potassiumiodide the method for flooding polyvinyl alcohol resin film and carrying out dyeing.Normally every 100 weight parts waters of content of the iodine in this aqueous solution are about 0.01 ~ 0.5 weight part, and normally every 100 weight parts waters of content of potassiumiodide are about 0.5 ~ 10 weight part.The temperature of this aqueous solution is generally about 20 ~ 40 DEG C, and in addition, the dipping time in this aqueous solution is generally about 30 ~ 300 seconds.
On the other hand, when using dichroic dye as dichroism pigment, the method for flooding polyvinyl alcohol resin film to dye is typically employed in the aqueous solution comprising water-soluble dichroic dye.The content of the dichroic dye in this aqueous solution, normally every 100 weight parts waters are 1 × 10 -3~ 1 × 10 -2about weight part.This aqueous solution also can containing inorganic salt such as sodium sulfate.The temperature of this aqueous solution is generally about 20 ~ 80 DEG C, and in addition, the dipping time in this aqueous solution is generally about 30 ~ 300 seconds.
Boric acid process after utilizing dichroism pigment to dye, can by carrying out the polyvinyl alcohol resin film immersion of dyeing in boric acid aqueous solution.About normally every 100 weight parts waters of content of the boric acid in boric acid aqueous solution are 2 ~ 15 weight parts, be preferably 5 ~ 12 weight parts about.When using iodine as dichroism pigment, this boric acid aqueous solution is preferably containing potassiumiodide.The content of the potassiumiodide in boric acid aqueous solution, about normally every 100 weight parts waters are 2 ~ 20 weight parts, is preferably 5 ~ 15 weight parts.Dipping time in boric acid aqueous solution is generally about 100 ~ 1200 seconds, is preferably about 150 ~ 600 seconds, more preferably about 200 ~ 400 seconds.The temperature of boric acid aqueous solution is generally more than 50 DEG C, is preferably 50 ~ 85 DEG C.
Washing process is carried out usually to the polyvinyl alcohol resin film after boric acid process.Washing processing example is as by carrying out borated polyvinyl alcohol resin film immersion in water.Implement drying treatment after washing, obtain polarization element.The temperature of the water in washing process is generally about 5 ~ 40 DEG C, and 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.Drying temperature is generally 40 ~ 100 DEG C.Treatment time in drying treatment is generally about 120 ~ 600 seconds.
Like this, the polarization element formed as the iodine of dichroism pigment or the polyvinyl alcohol resin film of dichroic dye can have been obtained by gas absorption quantity.
< protective membrane >
Then, this polarization element, light curable adhesive illustrated before use, at its one or both sides laminating protective membrane.All the time, as the protective membrane of polarization element and the tri acetyl cellulose film extensively adopted, have and be roughly 400g/m 2the Water Vapour Permeability of about/24hr; and in the present invention; as at least one side protective membrane of fitting at polarization element, adopt as the vibrin of the resin demonstrating lower Water Vapour Permeability than described tri acetyl cellulose, polycarbonate resin, acrylic resin or noncrystalline polyolefin system resin.
There is no particular limitation to may be used for the kind of the vibrin of 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, and can containing the Component units from other copolymer composition.As other copolymer composition, can enumerate as m-phthalic acid, p-beta-hydroxy ethoxybenzoic acid, 4,4 '-dicarboxylate biphenyl, 4, the dicarboxylic acid component that 4 '-benzophenonedicarboxylic acid, two (4-carboxyl phenyl) ethane, hexanodioic acid, sebacic acid, 5-sodiosulfoisophthalic acid and Isosorbide-5-Nitrae-dicarboxylic acid butylcyclohexane are such; As the diol component etc. the ethylene oxide adduct of propylene glycol, butyleneglycol, neopentyl glycol, Diethylene Glycol, cyclohexanediol, dihydroxyphenyl propane, polyoxyethylene glycol, polypropylene glycol and poly-BDO.For these dicarboxylic acid component or diol component, can by it, two or more combinationally uses respectively as required.In addition, the hydroxycarboxylic acid as P-hydroxybenzoic acid and above-mentioned dicarboxylic acid component or glycol component can also be used.As other copolymer composition, the dicarboxylic acid component and/or glycol component with amido linkage, amino-formate 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 (and, other dicarboxylic acid as required and/or other dibasic alcohol) the so-called direct polymerization method of direct reaction, the dimethyl ester making terephthalic acid and ethylene glycol (and, the dimethyl esters of other dicarboxylic acid as required and/or other dibasic alcohol) carries out any means 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, such as, lubricant, anti blocking agent, thermo-stabilizer, antioxidant, static inhibitor, photostabilizer, shock resistance improving agent etc. can be enumerated.But because the protective membrane being laminated in light polarizing film needs the transparency, therefore the preferred amount by these additives is limited in inferior limit.
By being membranaceous by above-mentioned raw materials ester moulding, implementing uniaxial extension or biaxial stretch-formed process, the protective membrane be made up of the vibrin stretched 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 stretched is arbitrary, is not particularly limited, can enumerates following method, by above-mentioned raw materials resin melting, with at the temperature of tenter machine more than second-order transition temperature, be after the non-oriented film cross directional stretch of sheet by extrusion moulding, implement heat setting type process.
When using vibrin as protective membrane, in order to obtain good binding property, preferably before coating adhesive, implement corona treatment, or use the polyester resin film with the easy adhesion process layer in surface.
Polycarbonate resin for the protection of film is the polyester formed by carbonic acid and dibasic alcohol or bis-phenol.Wherein, there is in molecular chain the aromatic copolycarbonate of hydrocarbon with two phenyls alkane, because thermotolerance, weathering resistance and acid resistance are excellent, therefore preferably use.As such polycarbonate, can enumerate as 2, two (4-hydroxy phenyl) propane (having another name called dihydroxyphenyl propane), 2 of 2-, two (4-hydroxy phenyl) butane, 1 of 2-, 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (4-hydroxy phenyl) Trimethylmethane of 1-or two (4-hydroxy phenyl) ethane of 1,1-such by bisphenols the polycarbonate that derives.
As the manufacture method of polycarbonate resin adipose membrane, any one methods such as casting film method, extrusion by melting can be used.As the example of concrete manufacture method, can enumerate and polycarbonate resin is dissolved in suitable organic solvent, form polycarbonate resin solution, by its curtain coating on metal support, form reticulation, and this reticulation is peeled off from aforementioned metal support, then the reticulation after stripping carried out warm air drying and obtain the method for film.
For the protection of the acrylic resin of film, not limitting it especially, is normally the polymkeric substance of principal monomer with methacrylic ester, and preferably makes the multipolymer of other comonomer components a small amount of and its copolymerization.As the methacrylic ester of acrylic resin principal constituent, be generally alkyl methacrylate, and particularly preferably use methyl methacrylate.In addition, as comonomer components, methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA etc. are usually used.Also can further using the aromatic ethenyl compound as vinylbenzene or the thiazolinyl nitrile compound as vinyl cyanide etc. as comonomer components.
As the manufacture method of acrylic resin, any means such as common mass polymerization, suspension polymerization, letex polymerization can be adopted.Wherein, the mass polymerization that there is not water soluble component in polymerization system is particularly preferably adopted.In addition, in order to obtain suitable second-order transition temperature, or in order to obtain the suitable viscosity demonstrating film forming plasticity, the preferably usage chain transfer agent when being polymerized.The amount of chain-transfer agent, the kind according to monomer suitably determines with composition.In addition, for acrylic resin, known additive can be contained as required.As known additive, such as, can enumerate lubricant, anti blocking agent, thermo-stabilizer, antioxidant, static inhibitor, photostabilizer, shock resistance improving agent, tensio-active agent etc.But because the protective membrane being laminated in light polarizing film needs the transparency, therefore the amount of these additives is preferably limited to inferior limit.
As the manufacture method of acrylic resin film, any one method such as extrusion by melting, rolling process as melting casting method, T modulus method or blow moulding so also can be used.Wherein, according to the viewpoint that can obtain the good film of surface texture, preferably material resin is such as melt extruded by T mould, make gained membranoid substance at least-face and roller or be with contact and the method for masking.
From viewpoints such as the shock resistances of the masking of film forming and film, acrylic resin can containing the acrylic rubber particle as impact improving agent.So-called acrylic rubber particle herein, be the particle of the elastomeric polymer based on acrylate as neccessary composition, its particle can enumerating the single layer structure in fact only formed by this elastomeric polymer is maybe using the particle of this elastomeric polymer as the multilayered structure of 1 layer.As the example of described elastomeric polymer, can enumerate and be principal constituent with alkyl acrylate and allow to the cross-linking elasticity multipolymer that obtains with other vinyl monomer of its copolymerization and cross-linkable monomer copolymerization.As the alkyl acrylate forming elastomeric polymer principal constituent, such as, the carbon number can enumerating the alkyl such as methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA is the alkyl acrylate of about 1 ~ 8, and particularly preferably use has the acrylate that carbon number is the alkyl of more than 4.As can with other vinyl monomer of this alkyl acrylate copolymer, the compound in molecule with 1 polymerizability carbon-carbon double bond can be enumerated, more particularly, the methacrylic ester as methyl methacrylate, the aromatic ethenyl compound as vinylbenzene, thiazolinyl nitrile compound etc. as vinyl cyanide can be enumerated.In addition, as cross-linkable monomer, the cross-linked compound in molecule with at least 2 polymerizability carbon-carbon double bonds can be enumerated, more particularly, (methyl) esters of acrylic acid of the polyvalent alcohol as ethylene glycol bisthioglycolate (methyl) acrylate and butyleneglycol two (methyl) acrylate, (methyl) the acrylic acid alkenyl esters, Vinylstyrene etc. as (methyl) allyl acrylate can be enumerated.
In addition, also can using by the laminates of the film do not formed containing the acrylic resin of rubber particles and the film be made up of the acrylic resin comprising rubber particles as protective membrane.
When using acrylic resin as protective membrane; when using composition of the present invention, even if do not carry out corona treatment can obtain good binding property, but in order to obtain good fusible coating yet; or make binding property better, also can implement corona treatment before coating adhesive.
For the protection of the noncrystalline polyolefin system resin of film; normally have by the such polycycle cycloolefin of norbornylene or derivatives thereof, dimethano-octahydro naphthalene the polymerized unit that derives; and when remaining double bond as ring-opening polymerization polymer, the thermoplastic resin that preferred double bond is hydrogenated.Noncrystalline polyolefin system resin also can be the multipolymer of cyclic olefin and chain olefin, also can import polar group in addition.Wherein, thermoplasticity saturated norbornene system resin is representational.Enumerate the example of commercially available noncrystalline polyolefin system resin, have " the ア mono-ト Application ", " ZEONEX " and " ZEONOR " of Japanese ゼ オ Application (strain) of JSR (strain), " APO " of Mitsui Chemicals (strain) and " ア ペ Le " etc.When noncrystalline polyolefin system resin masking is formed film, masking can suitably use the known method such as solvent cast method, extrusion by melting.
When using noncrystalline polyolefin system resin as protective membrane, in order to obtain good binding property, preferably before coating adhesive, implement corona treatment.
For liquid crystal indicator depending on recognizing in the polaroid of side, can be configured in this depending on recognize side namely and the protective membrane of liquid crystal cell opposition side give anti-glare properties.Under this situation, formed protective membrane depending on recognize side surface, namely with the face of opposition side, face being fitted in polarization element, the antiglare layer with concave-convex surface is set usually.Antiglare layer is generally formed by following method, namely, use embossing to give concavo-convex on active energy ray-curable resin, or cooperation has the particulate with its different refractivity in active energy ray-curable resin, and make it solidification and give concavo-convex method.In addition; when forming protective membrane by acrylic resin, being used in the acrylic resin as binding agent and coordinating that to have with the particulate of its different refractivity and the optical diffusion layer that obtains with being made up of protective membrane the laminate film of the transparent layer not coordinating the acrylic resin of described particulate to form also be effective.Under this situation, the form of will be fitted with its optical diffusion layer side and polarization element by above-mentioned optical diffusion layer and these 2 layers of laminate films formed of above-mentioned transparent layer can be adopted, maybe by form etc. that the laminate film clamping the 3-tier architecture on above-mentioned optical diffusion layer two sides with above-mentioned transparent layer is fitted with its transparent layer and polarization element.And using the acrylic resin laminate film by giving anti-glare properties containing such optical diffusion layer as protective membrane time; formed this depending on recognize side surface namely with the face of opposition side, face being fitted in polarization element; arranging anti-dazzle photosphere as above, is also effective for improving anti-dazzle performance further.
As previously mentioned; particularly when using acrylic resin film as protective membrane; the binding property not containing the epoxy monomer of aromatic nucleus shown in patent documentation 6 (Japanese Unexamined Patent Publication 2004-245925 publication) is in the past not necessarily abundant; and composition of the present invention; even if when using described acrylic resin film as protective membrane, also give good bounding force.Therefore, the present invention is particularly useful when using acrylic resin film as protective membrane.
The light curable adhesive of the present invention by illustrating above, at the protective membrane be made up of the transparent resin film being selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin system resin explained above of at least simultaneously fitting of polarization element.Only when the one side laminating protective membrane of polarization element, such as, also can take on the another side of polarization element, the form for the binder layer of fitting with other parts such as liquid crystal cell is directly set.
On the other hand, when the two sides of polarization element laminating protective membrane, each protective membrane can be identical type, also can be different sorts.Specifically, such as can adopt following form: in the form of laminating polyester resin film in the two sides of polarization element as protective membrane, in the form of laminating polycarbonate resin in the two sides of polarization element as protective membrane, in the form of laminating acrylic resin in the two sides of polarization element as protective membrane, in the form of the two sides of polarization element laminating noncrystalline polyolefin system resin as protective membrane, vibrin is selected from the one side laminating of polarization element, polycarbonate resin, any one transparent resin film of acrylic resin and noncrystalline polyolefin system resin is as protective membrane, and be selected from vibrin in the another side laminating of polarization element, polycarbonate resin, the acrylic resin transparent resin film different with the protective membrane of any one above-mentioned of amorphism polyolefin-based resins is as the form etc. of protective membrane.Further; also following form can be adopted: the transparent resin film of any one that laminating is selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin system resin in the one side of polarization element is as protective membrane, and any one different transparent resin film of laminating and vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin system resin is as the form of protective membrane on the another side of polarization element.When the two sides of polarization element laminating protective membrane, can divide and relate to 2 protective membranes of simultaneously simultaneously fitting, also can with a step laminating two sides.
When the two sides of polarization element laminating protective membrane; when making its one side for other resin molding different with noncrystalline polyolefin system resin from vibrin, polycarbonate resin, acrylic resin; as the preferred example of this other resin, cellulose-based resin can be enumerated.In addition; be fitted in the protective membrane be made up of vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin system resin of polarization element one side; according to the present invention; although bonded by the light curable adhesive illustrated above, the protective membrane being fitted in polarization element another side also can be bonded by other tackiness agent.Such as; when the one side of polarization element arranges the protective membrane be made up of the resin molding that the Water Vapour Permeability that cellulose-based resin molding is such is higher; at the binding face of the high resin molding of described Water Vapour Permeability, the tackiness agent beyond the epoxies such as polyethenol series tackiness agent also can be used.Even if but also can give high adhesion for the cellulose-based resin molding of illustrating herein due to light curable adhesive of the present invention, therefore, using the method operation of same binder simpler on the two sides of polarization element, is therefore favourable.
As the cellulose-based resin of the protective membrane of another side, be cellulosic partially or completely carboxylate, such as, cellulosic acetic ester, propionic ester, butyric ester, their mixed ester etc. can be enumerated.Specifically can enumerate tri acetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate etc.When enumerating the example of the commercially available product of the film be made up of such cellulose ester system resin, " Off ジ タ Star Network TD80 ", " Off ジ タ Star Network TD80UF " that Fuji Off イ Le system (strain) manufactures and " KC8UX2M " and " KC8UY " that " Off ジ タ Star Network TD80UZ ", コ ニ カ ミ ノ Le タ オ プ ト (strain) manufacture etc. can be enumerated.In addition, the cellulose-based resin molding giving optical compensation function can also be used.As described optical compensation films, such as, can enumerate make in cellulose-based resin containing have adjusting offset function compound film, there is in the surface coated of cellulose-based resin molding the film of the compound of adjusting offset function, cellulose-based resin molding is carried out to the film etc. of single shaft or biaxial stretch-formed gained.When enumerating the example of commercially available cellulose-based optical compensation films, can enumerate " ワ イ De PVC ユ mono-Off イ Le system WV BZ 438 " and " ワ イ De PVC ユ mono-Off イ Le system WV EA " that Fuji Off イ Le system (strain) manufactures, " KC4FR-1 " and " KC4HR-1 " that コ ニ カ ミ ノ Le タ オ プ ト (strain) company manufactures etc.
Can be used as the example of the low transparent resin of the Water Vapour Permeability of the protective membrane of another side as other resin different with noncrystalline polyolefin system resin from vibrin, polycarbonate resin, acrylic resin, polysulfone resin, ester ring type polyimide resin etc. can be enumerated.
Protective membrane, before fitting with polarization element, can implement the easily adhesion process such as saponification process, corona treatment, Cement Composite Treated by Plasma, bottoming coating process to binding face.In addition, protective membrane with the surface of the opposition side of polarization element binding face, also can have the various processing layers such as hard coat, anti-reflection layer, anti-dazzle photosphere.The thickness of protective membrane is generally the scope of about 5 ~ 200 μm, is preferably 10 ~ 120 μm, and more preferably 10 ~ 85 μm.
[manufacture method of polaroid]
Polaroid of the present invention can be manufactured by following method, the method comprises: the polarization element illustrated above and at least one side of the binding face of the protective membrane be made up of the transparent resin film being selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin system resin, be coated with the adhesive coated operation of the light curable adhesive illustrated above; By the bonding process that polarization element and protective membrane are fitted by the binder layer of gained; And under the state of polarization element and protective membrane being fitted by this binder layer, make the curing process that Photocurable adhesive composition solidifies.
< adhesive coated operation >
In adhesive coated operation, the light curable adhesive that at least coated on one side in the binding face of polarization element and protective membrane illustrates above.When the surface of polarization element or protective membrane is directly coated with light curable adhesive, there is no particular limitation for its coating process.Such as, scraper, coiling rod, mould can be adopted to be coated with the various coating methods such as machine, comma formula coating machine, gravure coater.In addition, after also can adopting the light curable adhesive that curtain coating illustrates between polarization element and protective membrane above, roller etc. is used to carry out pressurizeing thus the method it evenly spread out.
< bonding process >
After being so coated with light curable adhesive, be provided to bonding process.In this bonding process, such as, in painting process before when the surface coated light curable adhesive of polarization element, protective membrane is superimposed with it; In painting process before when the surface coated light curable adhesive of protective membrane, polarization element is superimposed with it.In addition, between polarization element and protective membrane during curtain coating light curable adhesive, with this state by polarization element and protective membrane superimposed.When the two sides of polarization element laminating protective membrane and when all using light curable adhesive of the present invention on two sides, by light curable adhesive respectively at the superimposed protective membrane in the two sides of polarization element.Then, roller etc. is usually used (when the superimposed protective membrane of the one side of polarization element, to be polarization element side and protective membrane side from two sides in this condition; In addition, when the superimposed protective membrane in the two sides of polarization element, the protective membrane side for this two sides) clamping, pressurize thus.Herein, the material of roller can use metal or rubber etc.The roller being configured in two sides can, for identical material, also can be different materials.
< curing process >
As mentioned above, the material under the state of polarization element and protective membrane being fitted by uncured light curable adhesive is provided to ensuing curing process.In this curing process, active energy beam is irradiated to light curable adhesive, the binder layer containing epoxy compounds or oxetane compound etc. is solidified, make polarization element and protective membrane bonding.When the one side laminating protective membrane of polarization element, active energy beam can from polarization element side, any side of protective membrane side irradiates.In addition; when the two sides of polarization element laminating protective membrane; under state protective membrane being fitted in polarization element two sides respectively by light curable adhesive, irradiate active energy beam from the protective membrane side of any surface, it is favourable that the light curable adhesive on two sides is solidified simultaneously.But; UV light absorber is combined with (such as in the protective membrane of any surface; the cellulose-based resin molding that will be combined with UV light absorber is as the situation of the protective membrane of one side) time and active energy beam when being ultraviolet, usually there is no the protective membrane side irradiation ultraviolet radiation of combined with ultraviolet radiation absorption agent from another side.
As active energy beam, visible ray, ultraviolet, X-ray, electron beam etc. can be used, but from the viewpoint of easy process and curing speed is also enough, usually preferably use ultraviolet.There is no particular limitation for the light source of active energy beam, 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. that below wavelength 400nm has luminescence distribution.
The photo-irradiation intensity of light curable adhesive is determined according to each objective composition, it is not particularly limited equally, but preferably to make as UV-B (the medium wavelength region ultraviolet of 280 ~ 320nm) to the exposure intensity of the effective wavelength region may of the activation of polymerization starter be 1 ~ 3000mW/cm 2.Exposure intensity is less than 1mW/cm 2time, the reaction times is long, and on the other hand, this exposure intensity is more than 3000mW/cm 2time, due to the heating when heat of lamp institute radiation and light curable adhesive polymerization, likely produce the xanthochromia of light curable adhesive or the deterioration of polarization element.
Regulate according to the composition that respectively will solidify the rayed time of light curable adhesive, it is not particularly limited equally, but preferably set with exposure intensity and irradiation time long-pending represented by accumulated light for 10 ~ 5000mJ/cm 2.Accumulated light is less than 10mJ/cm 2time, the generation coming from the spike of polymerization starter is insufficient, and the solidification of binder layer may be not enough, and on the other hand, this accumulated light is more than 5000mJ/cm 2time, irradiation time is very long, unfavorable for boosting productivity.
When irradiating active energy beam and making light curable adhesive solidify, under the condition preferably do not declined in each function of polaroid such as the transparency of the degree of polarization of polarization element, transmissivity and color and luster and protective membrane, it is made to solidify.
In the polaroid of gained like this, the thickness of binder layer is generally less than 50 μm, is preferably less than 20 μm, more preferably less than 10 μm.
[optics]
When using polaroid, the laminated optics showing the optical layers of the optical function beyond polarisation function in its side also can be formed in.Being laminated in the optical layers of polaroid to form optics, such as, is various optical layers that reflecting layer, Semitransmissive reflecting layer, optical diffusion layer, phase difference film, light-collecting piece, brightness improving film etc. use in the formation of liquid crystal indicator etc.Aforementioned reflecting layer, Semitransmissive reflecting layer and optical diffusion layer are the materials that use when forming the optics that the dual-purpose type polaroid that comprises reflection-type or Semitransmissive or diffusion type is formed.
The polaroid of reflection-type is for making to consider oneself as the reflected incident light recognizing side and the liquid crystal indicator carrying out display type, owing to can omit the light sources such as backlight, therefore easy by liquid crystal indicator slimming.In addition, the polaroid of Semitransmissive is used for the liquid crystal indicator carrying out display type at bright place as light sources such as reflection-type displays, in the dark use backlight.As the optics of reflective polaroid, such as, can set up the paper tinsel or vapor-deposited film that are made up of metals such as aluminium and form reflecting layer by the protective membrane on polarization element.As the optics of the polaroid of Semitransmissive, by using aforesaid reflecting layer as semi-permeable mirror, maybe the reflector plate and polaroid that demonstrate transmitance containing pearly pigment etc. are bonded and are formed.On the other hand; as the optics of diffusion type polaroid; such as use and the method for delustring process is implemented to the protective membrane on polaroid, coating containing the various method such as method of fine-grained film, forms minute concave-convex structure on surface containing the method for fine-grained resin, bonding.
Further, as the formation of the optics of the dual-purpose polaroid of reflected diffusion, such as, can be undertaken by arranging the methods such as the reflecting layer of this concaveconvex structure of reflection in the minute concave-convex structure face of diffusion type polaroid.The reflecting layer of minute concave-convex structure, have utilize diffuse-reflectance to make incident light diffusion, prevent directional property or dazzle, the advantage etc. of suppression light and shade inequality.In addition, containing fine-grained resin layer or film, also have when incident light and reflected light thereof are through the advantage suppressing light and shade unequal further containing being diffused during fine-grained layer.Reflect the reflecting layer of surperficial minute concave-convex structure, such as, by by methods such as evaporation or plating such as vacuum evaporation, ion plating, sputterings, directly can set up metal on the surface of minute concave-convex structure and formed.As the particulate coordinated for the formation of surperficial minute concave-convex structure, such as, the inorganic system particulate formed by silicon-dioxide, aluminum oxide, titanium oxide, zirconium white, stannic oxide, Indium sesquioxide etc. that median size is 0.1 ~ 30 μm can be used, or the organic system particulate etc. formed by be cross-linked or uncrosslinked polymkeric substance etc.
On the other hand, as the phase difference film of above-mentioned optical layers, be phase differential in order to compensate because liquid crystal cell causes and use.As its example, the film of birefringence film, dish-type liquid crystal or the nematic liquid crystal orientation setting formed by the stretched film etc. of various plastics can be enumerated, on film base material, form the material etc. of above-mentioned liquid crystal layer.Under this situation, as the film base material supporting aligned liquid-crystal layer, preferably use the Mierocrystalline cellulose mesenterys such as tri acetyl cellulose.
As the plastics of form dielectric grid film, such as, can enumerate polycarbonate, polyvinyl alcohol, polystyrene, polymethylmethacrylate, polyolefine, polyarylester, polymeric amide, noncrystalline polyolefin system resin etc. as polypropylene.Stretched film can be carry out processing the film of gained by single shaft or the suitable mode such as biaxial stretch-formed.In addition, also can be by applying convergent force and/or drawing force thus the birefringence film of the specific refractory power of the thickness direction of controlling diaphragm under the state bonded with heat-shrinkable film.In addition, in order to control the optical characteristics such as broadband, also can combine more than 2 to use phase difference film.
Light-collecting piece, in order to control light path etc. and use, it can be set up sheet etc. as prism array sheet, lens array sheet or point and be formed.
Brightness improving film uses in order to the brightness improving liquid crystal indicator etc., as its example, the mutually different film of anisotropy of laminated multi-disc specific refractory power can be enumerated and be designed on reflectivity, produce anisotropic reflection-type rectilinearly polarized light separate sheet, on film base material, support the alignment films of cholesteric liquid crystal polymers or the circularly polarizing separation sheet etc. of its aligned liquid-crystal layer.
Optics can be by polaroid and the laminate being undertaken more than 2 layers or 3 layers that combine according to application target by the optical layers of more than 1 layer or 2 layers selected in aforesaid reflecting layer or Semitransmissive reflecting layer, optical diffusion layer, phase difference film, light-collecting piece or brightness improving film etc.Under this situation, the optical layers such as optical diffusion layer or phase difference film, light-collecting piece or brightness improving film, also can configure more than 2 layers respectively.In addition, the configuration of each optical layers is not particularly limited.
, be just not particularly limited integrated with polaroid for the various optical layers forming optics as long as tackiness agent for this reason used can form bonding coat well by using tackiness agent.From the simplicity of bonding operation with prevent the viewpoints such as optical skew, preferably use pressure sensitive adhesive (being also referred to as pressure-sensitive tackiness agent).Pressure sensitive adhesive can use the pressure sensitive adhesive of polymkeric substance based on acrylic acid polymer, silicon-type polymkeric substance, polyester, urethane or polyethers etc.Wherein, the such optical transparence of preferred choice for use acrylic pressure-sensitive adhesive is excellent, maintain suitable wettability and cohesive force, also excellent and further there is weathering resistance and thermotolerance etc. with the binding property of base material, and the pressure sensitive adhesive of stripping problems such as tilting or strip off can not be there is under the condition of heating or humidification.In acrylic pressure-sensitive adhesive, coordinate by have (methyl) acrylic acid alkyl ester of the alkyl that the carbon number as methyl, ethyl or butyl is less than 20 and (methyl) vinylformic acid, (methyl) Hydroxyethyl Acrylate etc. the acrylic monomer containing functional group that formed, second-order transition temperature is made to be preferably less than 25 DEG C, and more preferably less than 0 DEG C, and make it be polymerized and obtain the acrylic copolymer that weight-average molecular weight is more than 100,000, based on this acrylic copolymer, polymkeric substance is useful.
Pressure sensitive adhesive layer is in the formation of polaroid, can by contact adhesive composition being dissolved or dispersed in the organic solvent as toluene or ethyl acetate, be modulated into the liquid that solid component concentration is 10 ~ 40 % by weight, and it is directly coated on mode polaroid being formed pressure sensitive adhesive layer, or, by forming pressure sensitive adhesive layer in advance on barrier film, being shifted and be bonded in mode polaroid being formed pressure sensitive adhesive layer etc. and carry out again.The thickness of pressure sensitive adhesive layer is determined according to its bounding force etc., and the scope of about 1 ~ 50 μm is suitable.
In addition, pressure-sensitive adhesive layer can be combined with weighting agent, pigment or the tinting material, antioxidant, UV light absorber etc. that are formed by glass fibre, granulated glass sphere, resin bead, metal powder or other inorganic powder etc. as required.As UV light absorber, can be salicylate based compound, benzophenone based compound, benzotriazole based compound, cyanoacrylate based compound or nickel complexing salt based compound etc.
[liquid crystal indicator]
Can optics as above be configured on the one or both sides of liquid crystal cell, form liquid crystal indicator.The liquid crystal cell used is arbitrary, such as, can use with film transistor type the liquid crystal cell of the active matrix drive-type being representative, be that the various liquid crystal cells such as the driving liquid crystal cell of the simple matrix of representative are to form liquid crystal indicator with super-twist nematic.The optics being arranged on liquid crystal cell both sides can be identical, also can be different.
[embodiment]
Below, enumerate embodiment and comparative example, further illustrate the present invention, but the present invention is not limited to these examples.In the example shown, represent the % of usage quantity or content, be weight basis unless otherwise specified.
In embodiment and comparative example, the various compositions for light modulated curing adhesive composition are as described below, below with compound name or separately symbol (trade(brand)name itself or its a part of) represent.
(A) composition: epoxy compounds
JER-828: bisphenol A type epoxy resin, " jER-828 " that japan epoxy resin (strain) manufactures.
(B) composition: two (methyl) acrylic compound
FM-400: neopentyl glycol, hydroxy new pentane acid and acrylic acid esterification reaction product, " カ ヤ ラ Star De FM-400 " that Japanese chemical drug (strain) manufactures.
HDDA:1,6-hexanediyl ester, " ラ イ ト ア Network リ レ mono-ト 1,6HX-A " that common prosperity society chemistry (strain) manufactures.
(B) ' composition: (methyl) acrylic compound beyond (B) composition
M-309: Viscoat 295, " ア ロ ニ Star Network ス M-309 " that East Asia synthesis (strain) manufactures.
M-203: tristane dihydroxymethyl diacrylate, " ア ロ ニ Star Network ス M-203 " that East Asia synthesis (strain) manufactures.Carbon number is the diacrylate of the dibasic alcohol of 12.
M-220: polypropylene glycol (average repeat unit number is about 3) diacrylate, " ア ロ ニ Star Network ス M-220 " that East Asia synthesis (strain) manufactures.The average carbon number with ether structure is the diacrylate of the dibasic alcohol of 9.
M-240: polyoxyethylene glycol (average repeat unit number is about 4) diacrylate, " ア ロ ニ Star Network ス M-240 " that East Asia synthesis (strain) manufactures.The average carbon number with ether structure is the diacrylate of the dibasic alcohol of 8.
(C) composition: light cationic polymerization initiators
CPI-100P: the effective constituent being main component with triaryl matte hexafluorophosphate is the carbonic allyl ester solution of 50%, " CPI-100P " that サ Application ア プ ロ (strain) manufactures.The number of effective constituent is described in table.
(D) composition: the oxetane compound represented in previously described formula (1)
OXT-221:3-ethyl-3-[(3-Ethyloxetane-3-base) methoxymethyl] trimethylene oxide, " ア ロ Application オ キ セ タ Application OXT-221 " that East Asia synthesis (strain) manufactures.
(E) composition: the oxetane compound represented in previously described formula (2)
OXT-101:3-ethyl-3-hydroxymethyl oxetane, " ア ロ Application オ キ セ タ Application OXT-101 " that East Asia synthesis (strain) manufactures.
(F) composition: optical free radical polymerization starter
Irg184:1-hydroxycyclohexylphenylketone, " IRGACURE 184 " that Qi Si company manufactures.
(G) composition: flow agent
8019 Additive: the polysiloxane series flow agent " 8019Additive " that eastern beautiful DOW CORNING (strain) manufactures.
Other composition
Propylene carbonate
[modulation of Photocurable pressure-sensitive adhesive composition]
Each composition shown in table 1 and table 2 is coordinated with respective ratio, and is uniformly mixed according to usual method, light modulated curing adhesive composition.In addition, as previously mentioned, because " CPI-100P " that use as (C) composition is the carbonic allyl ester solution containing 50% effective constituent, therefore, in table, (C) composition and propylene carbonate are separately represented.That is, the use level of " CPI-100P " in table, represents the ratio of effective constituent, and the use level that " CPI-100P " is own is that (C) becomes the amount sum shown in the amount shown in subfield and propylene carbonate hurdle.
The viscosity of resulting composition at 25 DEG C is 100 ± 20mPas, and coating is all good.
[making of polaroid]
Herein, use 2 kinds of following films as protective membrane.
Stretching norbornene resin film: thickness is 70 μm, commodity are called " ZEONOR film ", Japanese ゼ オ Application (strain) system.Corona discharge Treatment is implemented to this film, then uses it for the laminating with polarization element.
Acrylic resin film: thickness is 80 μm, trade(brand)name " テ Network ノ ロ イ S001 ", Sumitomo Chemical (strain) is made.Also Corona discharge Treatment is implemented to this film, then uses it for the laminating with polarization element.
Use bar coater, be coated with the composition of above-mentioned modulation in the Corona discharge Treatment face of above-mentioned stretching norbornene resin film and the Corona discharge Treatment face of acrylic resin film with the thickness of 3 μm.Then, to be clamped in the mode that gas absorption quantity in polyvinyl alcohol has the polarization element of iodine between these 2 films, use roller to fit 3 films simultaneously.By being accompanied with the UV irradiation equipment (" Fusion H bulb " that lamp uses Fusion company to manufacture) of belt conveyer, since the two sides of gained like this being fitted with to the polarization element of protective membrane, the accumulated light on self stretch norbornene resin film surface is 300mJ/cm 2(UV-B) irradiation ultraviolet radiation is carried out; then 23 DEG C, place 1 day under the environment of 50%R.H., be produced on one side the fitted protective membrane and the polaroid of stretching norbornene resin film of having fitted on another side that are made up of acrylic resin film.
23 DEG C, the standard conditions of 50 ~ 60%R.H., and 23 DEG C, under the drying conditions both of these case of 20 ~ 30%R.H., implement this test.
[evaluation test]
To the polaroid of gained, evaluate binding property and weather resistance by the following method, will table 1 and table 2 be the results are summarized in.
< binding property >
Zero shear knife inserts test
When the blade of shear knife is inserted from the inclined upward of acrylic resin film; the blade average evaluation that cannot be inserted between polarization element is zero; blade is inserted a little but there is some strength and the average evaluation that protective membrane breaks during the course is △, and by the average evaluation that easily inserts for ×.
This evaluation is implemented to the polaroid made at the standard conditions and the polaroid that makes in dry conditions, and as described belowly carries out fusible comprehensive evaluation.
◎: be all zero under two conditions
Zero: be zero under a kind of condition, be △ under another kind of condition
△: be all △ under two conditions
×: under a kind of condition be ×
××: be all under two conditions ×
< weather resistance >
For in table 1 and table 2, be the sample of more than △ for binding property, implement to place 60 minutes at-35 DEG C, then place 60 minutes at+70 DEG C, and the circulation thermal shock round-robin test of 300 times repeatedly, result bad order unconfirmed, its weather resistance known is good.
[table 1]
[table 2]
As shown in table 1, the composition comprising the embodiment 1 of the whole composition of appropriate amount (A) ~ (E) of the present invention, all demonstrates excellent binding property under two conditions.
Do not comprise the composition of the embodiment 2 ~ embodiment 4 of (E) composition, demonstrate excellent binding property at the standard conditions, poorer than embodiment 1 in dry conditions, but demonstrate the binding property of the degree that do not have problems in practical.
Do not comprise the embodiment 5 of (D) composition and the composition of embodiment 6, at the standard conditions with drying conditions under all poor than embodiment 1, but demonstrate the binding property of the degree that do not have problems in practical.
On the other hand, do not comprise the composition of the comparative example 1 of (B) composition, although demonstrate excellent binding property at the standard conditions, Poor cohesion in dry conditions.In addition, the mixing ratio of (B) composition exceedes the composition of the comparative example 2 of the present invention (B) the components matching ratio upper limit 45%, at the standard conditions with equal Poor cohesion under drying conditions.Further, the M-309 of 3 functional acrylates, the carbon number containing 37% be the diacrylate of the dibasic alcohol of 12 M-203, there is ether structure M-220 and M-240 of diacrylate as acrylate beyond (B) composition time, as shown in comparative example 3 ~ comparative example 6, at the standard conditions with equal Poor cohesion under drying conditions.
Industrial utilizability
Photocurable pressure-sensitive adhesive composition of the present invention, is easily solidified by irradiation ultraviolet radiation isoreactivity energy-ray, for being effective with the short period of time by polarization element and protective membrane good bond.

Claims (11)

1. Photocurable adhesive composition; it is the binder composition having the polarization element of the polyvinyl alcohol resin film of dichroism pigment for protective membrane being bonded in the gas absorption quantity comprising uniaxial extension; this protective membrane is made up of the transparent resin film being selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin system resin; the feature of described composition is, contains
(A) there is the epoxy compounds of at least 2 epoxy group(ing) and at least 1 aromatic nucleus in molecule,
(B) neopentyl glycol, hydroxy new pentane acid and (methyl) acrylic acid class resultant of reaction, and
(C) light cationic polymerization initiators,
Described (A) ~ (C) composition containing proportional be in the composition
(A) composition: 20 ~ 60 % by weight
(B) composition: 5 ~ 45 % by weight
(C) composition: 0.5 ~ 10 % by weight.
2. Photocurable adhesive composition as claimed in claim 1, is characterized in that (A) composition is bisphenol A type epoxy resin.
3. Photocurable adhesive composition as claimed in claim 1, is characterized in that in the composition also containing the oxetane compound shown in 5 ~ 45 % by weight (D) following formula (1),
4. Photocurable adhesive composition as claimed in claim 1, is characterized in that in the composition also containing the oxetane compound shown in 1 ~ 20 % by weight (E) following formula (2),
5. Photocurable adhesive composition as claimed in claim 1, is characterized in that (F) optical free radical polymerization starter in the composition also containing less than 10 % by weight ratios.
6. Photocurable adhesive composition as claimed in claim 1, is characterized in that in the composition also containing 0.01 ~ 0.5 % by weight (G) flow agent.
7. polaroid; it by tackiness agent, the protective membrane comprising the transparent resin film being selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin system resin is fitted in polarization element to form; the gas absorption quantity that this polarization element comprises uniaxial extension has the polyvinyl alcohol resin film of dichroism pigment, and it is characterized in that the Photocurable adhesive composition of described tackiness agent according to any one of claim 1 ~ 6 is formed.
8. the manufacture method of polaroid, it will be comprised by tackiness agent to be selected from vibrin, polycarbonate resin, the protective membrane of the transparent resin film of acrylic resin and noncrystalline polyolefin system resin fits in polarization element, thus manufacture the method for polaroid, the gas absorption quantity that this polarization element comprises uniaxial extension has the polyvinyl alcohol resin film of dichroism pigment, the method is characterized in that and comprise: at least one side of the binding face of described polarization element and described protective membrane, the adhesive coated operation of the Photocurable adhesive composition of coating according to any one of claim 1 ~ 6,
By the binder layer of gained, by the bonding process that described polarization element and described protective membrane are fitted;
And under the state of polarization element and protective membrane being fitted by described binder layer, make the curing process that described Photocurable adhesive composition solidifies.
9. optics, is characterized in that in polaroid according to claim 7 other optical layers laminated.
10. optics as claimed in claim 9, other optical layers described comprises phase difference film.
11. liquid crystal indicators, is characterized in that the one or both sides optics described in claim 9 or 10 being configured in liquid crystal cell.
CN201110168572.7A 2010-04-06 2011-04-02 Photocurable adhesive composition, polarizing plate and a process of producing the same, optical member, and liquid crystal display device Active CN102344763B (en)

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