CN104559894A - Active energy ray-curable adhesive composition - Google Patents
Active energy ray-curable adhesive composition Download PDFInfo
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- CN104559894A CN104559894A CN201410562754.6A CN201410562754A CN104559894A CN 104559894 A CN104559894 A CN 104559894A CN 201410562754 A CN201410562754 A CN 201410562754A CN 104559894 A CN104559894 A CN 104559894A
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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
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- 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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Liquid Crystal (AREA)
Abstract
The task of the invention provides an active energy ray-curable adhesive composition, a polarization plate, an optical film and an image display device. The adhesive composition helps to improve adhesiveness of a polarizer and a transparent protection layer and to form an adhering layer with improved heat resistance and water resistance. The method of realization is the active energy ray-curable adhesive composition comprising following components: a (A) composition which is a vinyl lactam represented by a general formula (1) and a (B) composition which is a compound with 1 molecule comprising more than two ethylenically unsaturated groups and less than 1000 in molecular weight. In a formula (1), R1 and R2 are univalent saturated hydrocarbon radicals with number of hydrogen atoms or carbon atoms being 1 to 6. R1 and R2 can be identical and different as well and can be connected together to form an annular structure.
Description
Technical field
The present invention relates to the active energy ray curable binder composition for the formation of the binder layer by more than 2 adhering components; especially for the active energy ray curable binder composition of the binder layer formed between polarizer and transparent protective film, and polarization plates.This polarization plates can form the image display devices such as liquid crystal indicator (LCD) in an individual manner or as by its stacked blooming.
Background technology
In table, portable phone, PDA, notebook computer, computer indicating meter, DVD player, TV etc., the market of liquid crystal indicator expands just rapidly.Liquid crystal indicator is the visual display unit of polarization state making to be formed by the on-off action of liquid crystal, due to its displaying principle, so use polarizer.Particularly in the purposes such as TV, more and more require high brightness, high-contrast, wide viewing angle, also high-transmission rate, high-polarization, high colorrendering quality etc. are more and more required to polarization plates.
As polarizer, from the viewpoint of having high-transmission rate, high-polarization, usually using the most widely such as to have and make polyvinyl alcohol (hereafter also referred to as " PVA ") adsorb iodine and the iodine system polarizer of the structure stretched.Usually, for polarization plates, use the so-called aqueous adhesive by having dissolved polyvinyl alcohol based material in water to have fitted on the two sides of polarizer the polarization plates of transparent protective film.As transparent protective film, use the cellulose triacetate (hereafter also referred to as " TAC ") etc. that Water Vapour Permeability is high.
When manufacturing polarization plates, when using the aqueous adhesive as polyethenol series tackiness agent (so-called wet method lamination), after polarizer and transparent protective film are fitted, need to carry out drying process.In order to improve the productivity of polarization plates, expecting to shorten drying process, or adopting other adhesive bonding method not needing drying process.
In addition, when using aqueous adhesive, if do not make the water ratio of polarizer also relatively improve to make to improve with the binding property of polarizer (water ratio of usual polarizer is about 30%), then the good polarization plates of binding property can not be obtained.But the polarization plates obtained by this way, has the problems such as dimensional change under high temperature, high-temperature high-humidity is large, optical characteristics.On the other hand, in order to suppress dimensional change, the water ratio of polarizer can be reduced, use the transparent protective film that Water Vapour Permeability is low.But if use aqueous adhesive this polarizer and transparent protective film to be fitted, then drying efficiency reduction, polarization characteristic reduce or produce bad order, thus can not obtain polarization plates useful in fact.
In addition, take particularly TV as representative, in recent years along with the propelling of the large screen of image display device, consider from productivity, cost aspect (yield rate, acquisition number rise), the maximization of polarization plates also becomes extremely important.But, state before use in the polarization plates of aqueous adhesive and there is such problem: caused polarization plates generation dimensional change by the heat of backlight, thus it becomes uneven, in the part in picture entirety, can see that the so-called light leak (uneven) that the position of display black is turned white such becomes remarkable.
In order to solve the problem points in above-mentioned wet method lamination, propose the scheme of the active energy ray curable tackiness agent not containing water, organic solvent.Such as, Patent Document 1 discloses the active energy ray curable tackiness agent containing following composition: the free-radical polymerised compound of (A) molecular weight less than 1000 containing polar group, the free-radical polymerised compound of (B) molecular weight less than 1000 not containing polar group and (D) Photoepolymerizationinitiater initiater.But, for the combination of free-radical polymerised compound (monomer) forming such tackiness agent, particularly because it designs the fusible order of norbornene resin film as raising, so there is the tendency with the poor adhesion of polarizing coating.
In patent documentation 2, as the radiation cure type resin composition of the sticking power excellence of Dichlorodiphenyl Acetate cellulose membrane, disclose the resin combination employing multifunctional (methyl) acrylate with isocyanuric acid ester skeleton.The affinity with multifunctional (methyl) acrylate Dichlorodiphenyl Acetate cellulose membrane class of isocyanuric acid ester skeleton is very high; although very useful in the radiation-curable adhesive of the tri cellulose acetate membrane for the protective membrane as polarizer; but due to poor to the affinity of the polyvinyl alcohol forming polarizer, so the resin combination being only the use of multifunctional (methyl) acrylate with isocyanuric acid ester skeleton is inadequate.
Patent Document 3 discloses the active energy ray curable binder composition containing N-hydroxyethyl acrylamide and N-acryloyl morpholine.But; when only having N-hydroxyethyl acrylamide and N-acryloyl morpholine; to forming the binding property of polyvinyl alcohol of polarizer and insufficient, in addition owing to being only made up of simple function (methyl) acrylic monomer, so insufficient in water tolerance, thermotolerance.
In patent documentation 4 and patent documentation 5, disclose the active energy ray curable binder composition containing N-hydroxyethyl acrylamide and multifunctional (methyl) acrylic compound.But, even N-hydroxyethyl acrylamide and multifunctional (methyl) acrylic compound, also insufficient to the binding property of the polyvinyl alcohol forming polarizer.In addition, for multifunctional (methyl) acrylic compound, as shown in patent documentation 4, when adding the addition of high heat-resisting multifunctional (methyl) acrylic compound, easily cause fusible reduction, as shown in patent documentation 5, as multifunctional (methyl) acrylic compound, when using polyester multifunctional (methyl) acrylic compound, easily cause the reduction of water tolerance.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2008-9329 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2004-2774 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2008-287207 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2010-78699 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2010-78700 publication
Summary of the invention
The problem that invention will solve
The present invention makes in view of the foregoing; problem of the present invention is to provide a kind of active energy ray curable binder composition, polarization plates, blooming and image display device; described binder composition can improve the binding property of polarizer and clear protective film layer, and can form the binder layer that thermotolerance and water tolerance improve.
Solve the means of problem
The present inventors are in order to solve above-mentioned problem; for the unsaturated compound monomer with the affinity excellence of free-radical polymerised unsaturated compound monomer and the TAC film used the transparent protective film as polarizer and PMMA film of the affinity excellence of the PVA to formation polarizer, be studied.In addition, for the object improving adhesion stability, water tolerance, the interpolation of reactive polymer and polymkeric substance is studied.Consequently, binding property and thermotolerance, the whole excellent active energy ray curable tackiness agent composition of water tolerance has been found.
That is, the present invention is as described below.
[1] an active energy ray curable binder composition, it contains following composition:
(A) composition, the ethenyl amide compound prodn represented by following general formula (1), and
(B) composition, in 1 molecule with more than 2 have free-radical polymerised ethylenically unsaturated group, the compound of molecular weight below 1000,
In formula (1), R
1and R
2for 1 valency alkyl of hydrogen atom or carbonatoms 1 ~ 6, R
1and R
2can be the same or different, R
1with R
2can link together and form ring texture.
[2] the active energy ray curable binder composition Gen Ju [1], described (B) composition (methyl) acryl compound (B1) represented by following general formula (2).
In formula (2), X
1, X
2and X
3for 1 valency alkyl of (methyl) acryl, hydrogen atom or carbonatoms 1 ~ 6, and X
1, X
2and X
3in at least 2 be (methyl) acryl, R
3, R
4and R
5represent carbonatoms 1 ~ 6 and Sauerstoffatom is bonded in X respectively
1, X
2, X
3the oxyalkylene of side.
[3] according to [1] or the active energy ray curable binder composition described in [2], aforementioned (A) composition is any one in N-vinyl formamide, N-vinyl acetamide, NVP, N-caprolactam.
[4] the active energy ray curable binder composition Gen Ju [2], (methyl) acryl compound (B1) represented by aforementioned formula (2) is three (acryl oxygen base ethyl) isocyanuric acid esters or two (acryl oxygen base ethyl) hydroxyethyl isocyanuric acid ester.
[5] according to the active energy ray curable binder composition according to any one of [1] ~ [4], in total composition, contain aforementioned (A) composition with 25 ~ 75 quality %, contain aforementioned (B) composition with the scope of 25 ~ 75 quality %.
[6] according to the active energy ray curable binder composition according to any one of [1] ~ [5], it is also containing (C) composition, described (C) composition be when measuring with GPC the weight-average molecular weight of polystyrene conversion be 1000 ~ 20000, epoxy acrylate and/or urethane acrylate.
[7] the active energy ray curable binder composition Gen Ju [6], in total composition, containing 1 ~ 20 quality % aforementioned (C) composition.
[8] according to the active energy ray curable binder composition according to any one of [1] ~ [7], it is also containing (D) composition, described (D) composition be when measuring with GPC the weight-average molecular weight of polystyrene conversion be 10000 ~ 300000, at least a kind of being selected from polybutyral resins, vibrin and polyvinylamide resin.
[9] the active energy ray curable binder composition Gen Ju [8], in total composition, containing 1 ~ 10 quality % aforementioned (D) composition.
[10] according to the active energy ray curable binder composition according to any one of [1] ~ [9], it contains the Photoepolymerizationinitiater initiater of effective absorbing wavelength with more than 380nm.
[11] the active energy ray curable binder composition Gen Ju [10], described in there is effective absorbing wavelength of more than 380nm Photoepolymerizationinitiater initiater be acylphosphine oxide compound.
[12] cured article, it is solidified by the active energy ray curable binder composition according to any one of [1] ~ [11], and its second-order transition temperature is more than 60 DEG C.
[13] a kind of polarization plates; it forms binder layer between at least 1 face and transparent protective film of polarizer, and described binder layer is obtained the active energy ray curable binder composition solidification according to any one of [1] ~ [11].
[14] polarization plates Gen Ju [13], the material of described transparent protective film is be selected from least a kind in celluosic resin, (methyl) acrylic resin, polycarbonate resin, vibrin and cyclic polyolefin resin.
[15] blooming, it is stacked multiple layer and forms, and wherein at least 1 layer is [13] or the polarization plates described in [14].
[16] image display device, it uses [13] or the polarization plates described in [14] to obtain.
[17] image display device, it uses the blooming described in [15] to obtain.
Invention effect
The binder layer be solidified to form by active energy ray curable binder composition involved in the present invention, has excellent binding property between polarizer and clear protective film layer, and can form the binder layer that thermotolerance and water tolerance improve.
Binder layer involved by the application of the invention, can change to dry process by polarizer/transparent protective film bonding process from wet processing, can reduce production cost by simplifying polarization plates manufacturing process.
Accompanying drawing explanation
Fig. 1 shows an example of the formation of polarization plates involved in the present invention.
Fig. 2 shows an example of the formation of blooming involved in the present invention.
Fig. 3 shows an example of the formation of image display device involved in the present invention.
Description of reference numerals
1 polarization plates
2 polarizers
3 binder layers
4 transparent protective films
5 bloomings
6 bonding coats
The functional layers such as 7 anti-reflecting layers
8 hard coats or anti-reflecting layer
9 polarizers, vision compensate film etc.
10 image display devices
11 backlights
12 glass substrates
13 liquid crystal
14 colour filters
Embodiment
(A) composition forming active energy ray curable tackiness agent is the ethenyl amide compound prodn of vinyl and nitrogen Direct Bonding, has the structure shown in following general formula (1),
In formula (1), R
1and R
2for 1 valency alkyl of hydrogen atom or carbonatoms 1 ~ 6, R
1and R
2can be the same or different, R
1with R
2can link together and form ring texture.At R
1and R
2when 1 valency alkyl for carbonatoms 1 ~ 6, the alkyl of preferred carbonatoms 1 ~ 6.In addition, at R
1with R
2when being joined together to form ring texture, by R
1and R
2the alkyl formed is preferably the alkylidene group of carbonatoms 1 ~ 12.
As the concrete example of (A) composition, can enumerate, such as N-vinyl formamide, N-vinyl acetamide, NVP, N-caprolactam etc.In addition, these monomers can be used alone a kind and also can be mixed with two or more.
(B) composition be in 1 molecule with more than 2 have free-radical polymerised ethylenically unsaturated group, the compound of weight-average molecular weight less than 1000, wherein from the viewpoint of making binding property, thermotolerance, water tolerance good, multifunctional (methyl) acrylic compound (B1) with triple polyisocyanate annulus represented by preferred following general formula (2).In addition, in this application, " (methyl) acrylate " is methacrylate and/or acrylate." (methyl) acryl " refers to methacryloyl and/or acryl similarly." (methyl) acrylic acid series " refers to metha crylic and/or acrylic acid series similarly.
In formula (2), X
1, X
2and X
3for 1 valency alkyl of (methyl) acryl, hydrogen atom or carbonatoms 1 ~ 6, and X
1, X
2and X
3in at least 2 be (methyl) acryl, R
3, R
4and R
5represent carbonatoms 1 ~ 6 and Sauerstoffatom is bonded in X respectively
1, X
2, X
3the oxyalkylene of side.At X
1, X
2and X
3when 1 valency alkyl for carbonatoms 1 ~ 6, the alkyl of preferred carbonatoms 1 ~ 6.
As the concrete example with multifunctional (methyl) acrylic compound (B1) of triple polyisocyanate annulus represented by general formula (2), three (acryl oxygen base ethyl) isocyanuric acid ester, two (acryl oxygen base ethyl) hydroxyethyl isocyanuric acid ester etc. can be enumerated.In addition, these monomers can be used alone a kind, also can be mixed with two or more.
As the concrete example of (B) composition beyond multifunctional (methyl) acrylic compound (B1) with triple polyisocyanate annulus represented by aforementioned formula (2), following various material can be enumerated.
Two (methyl) acrylate etc. of tristane dihydroxymethyl two (methyl) acrylate, Isosorbide-5-Nitrae-cyclohexane dimethylol two (methyl) acrylate, norcamphane dihydroxymethyl two (methyl) acrylate and Hydrogenated Bisphenol A has two (methyl) esters of acrylic acid of ester ring type ring, two (methyl) acrylate etc. of two (methyl) acrylate and bisphenol A diglycidyl ether that comprise the bisphenol-A epoxy alkane affixture of two (methyl) acrylate of bisphenol A epoxy ethane additive product and two (methyl) acrylate of bisphenol A propylene oxide affixture has two (methyl) esters of acrylic acid of aromatic ring, two (methyl) esters of acrylic acid of the aklylene glycols such as ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, pentanediol two (methyl) acrylate and hexylene glycol two (methyl) acrylate, two (methyl) esters of acrylic acid of the multi alkylidene diols such as Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate and polypropylene glycol two (methyl) acrylate, two (methyl) acrylate of the glycerols such as two (methyl) acrylate of two (methyl) acrylate of glycerine or three (methyl) acrylate and Glycerol dimer or three (methyl) acrylate or three (methyl) esters of acrylic acid, two (methyl) acrylate of the oxirane affixture of glycerols or three (methyl) esters of acrylic acid, two (methyl) esters of acrylic acid of the bisphenol epoxies alkane affixtures such as two (methyl) acrylate of bisphenol-A epoxy alkane affixture and two (methyl) acrylate of Bisphenol F epoxy alkane affixture, trimethylolpropane tris (methyl) acrylate, ditrimethylolpropane three (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, with polyvalent alcohol many (methyl) esters of acrylic acids such as Dipentaerythritol six (methyl) acrylate, many (methyl) esters of acrylic acid of the oxirane affixture of these polyvalent alcohols.
They can be used alone a kind, also can be mixed with two or more, and in addition, also can use with multifunctional (methyl) acrylic compound (B1) with triple polyisocyanate annulus represented by aforementioned formula (2).
The use level of (A) composition in active energy ray curable binder composition and (B) composition, in total composition (namely when being 100 quality % with composition total mass), (A) composition is preferably 25 ~ 75 quality %, be more preferably 30 ~ 70 quality %, (B) composition is preferably 25 ~ 75 quality %, is more preferably 30 ~ 70 quality %.If (A) composition is less than 25 quality %, then to the poor adhesion of polarizer, if more than 75 quality %, then there is the situation causing water tolerance to reduce.If (B) composition is less than 25 quality %, then all poor to the binding property of transparent protective film, water tolerance, if more than 75 quality %, then there is the situation causing reducing the binding property of polarizer.
As the composition forming active energy ray curable binder composition, also can coordinate further into (C) composition.(C) composition is be selected from least a kind in epoxy acrylate and urethane acrylate, and the weight-average molecular weight of the polystyrene conversion measured by GPC is altogether 1000 ~ 20000.
When the weight-average molecular weight of (C) composition is less than 1000, can't see the raising of adhesion stability, water tolerance, if more than 20000, then the viscosity of obtained resin combination rises large, thus has problems in coating.When adding (C) composition, its use level is preferably 1 ~ 20 quality % in total composition, is more preferably 5 ~ 15 quality %.If more than 20 quality %, then there is the situation causing reducing the binding property of polarizer.
Epoxy acrylate refers to, the epoxy group(ing) of epoxy resin and (methyl) vinylformic acid are reacted and the compound that obtains, usual use has 2 officials can above epoxy resin, and it is undertaken reacting obtaining by the scope being 1/1 ~ 1/1.2 in epoxy group(ing)/(methyl) acrylic acid mol ratio.As the epoxy resin used in reaction, can use Racemic glycidol ethers and glycidyl ester class etc., particularly Racemic glycidol ethers is suitable, and wherein preferably 2 officials can Racemic glycidol ethers.
As the concrete example of diglycidyl ether type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A epoxy resin, biphenyl type epoxy resin, phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthalene aralkyl-type epoxy resin can be enumerated, as the concrete example of glycidyl ester type epoxy resin, dimer acid glycidyl ester etc. can be enumerated.
As the concrete example that can be used as the epoxy acrylate of (C) composition suitably, can enumerate, vinyl ester resin " RIPOXY (registered trademark) VR-60 ", " RIPOXY (registered trademark) VR-90 " etc. that such as Showa electrician society produces.
Urethane acrylate refers to, makes the compound that polyvalent alcohol, organic multiple isocyanate and (methyl) acrylate containing hydroxyl carry out urethane reaction and obtain under the existence of the catalyzer such as organo-tin compound, amine compound such as dibutyl tin laurate.
As polyvalent alcohol, can enumerate, low molecular weight polyols, polyether glycol, polycarbonate polyol and polyester polyol etc.
As low molecular weight polyols, can enumerate, the polyvalent alcohol with at least 2 hydroxyls of such as molecular weight about 50 ~ 300, as concrete example, ethylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, butyleneglycol, 1 can be enumerated, 6-hexylene glycol, 2-methyl isophthalic acid, 8-ethohexadiol, nonanediol, cyclohexanedimethanol, neopentyl glycol and 3-methyl isophthalic acid, 5-pentanediol etc.
As polyether glycol, can enumerate, such as, there is the polyalkylene glycol of more than 3 oxygen alkylidene units, as concrete example, polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol etc. can be enumerated.
As polycarbonate polyol, can enumerate, the resultant of reaction of such as carbonic ether and glycol.As carbonic ether, specifically can enumerate, the diaryl carbonates such as diphenyl carbonate and the dialkyl carbonate such as methylcarbonate and diethyl carbonate etc.As glycol, aforesaid low molecular weight polyols can be enumerated.
As polyester polyol, can enumerate, be such as selected from least a kind in these low molecular weight polyols, polyether glycol and polycarbonate polyol with the resultant of reaction of sour composition.As sour composition, can enumerate, diprotic acid or their acid anhydrides etc. such as such as hexanodioic acid, sebacic acid, succinic acid, toxilic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid.In addition, the ring-opening reaction resultant etc. of polycarbonate diol and caprolactone can also be enumerated.
As organic multiple isocyanate, can enumerate, such as vulcabond and triisocyanate etc.
As vulcabond, can enumerate, such as tolylene diisocyanate, 4, the aromatic diisocyanates such as 4 '-diphenylmethanediisocyanate, xylylene diisocyanate and naphthalene diisocyanate; The aliphatic diisocyanate such as hexamethylene diisocyanate and trimethyl hexamethylene diisocyanate; The ester ring type vulcabond etc. such as isophorone diisocyanate, HMDI, norbornylene vulcabond and hydrogenated xylylene vulcabond.
As triisocyanate, can enumerate, such as 1,6,11-undecane triisocyanate, 1,3,6-hexa-methylene triisocyanate and norbornane triisocyanate etc.
In the middle of them, from the viewpoint of the viscosity of reaction product, preferred vulcabond.
As (methyl) acrylate containing hydroxyl, can enumerate, (methyl) hydroxyalkyl acrylates etc. such as such as (methyl) vinylformic acid 2-hydroxy methacrylate and (methyl) vinylformic acid 2-hydroxy propyl ester.
In the middle of them, preferably (methyl) vinylformic acid 2-hydroxy methacrylate.
These (C) compositions can be used alone a kind, also can be mixed with two or more.
As the composition forming active energy ray curable binder composition, can coordinate further into (D) composition.(D) composition is be selected from least a kind in polybutyral resins, vibrin and polyvinylamide resin, and the weight-average molecular weight of the polystyrene conversion measured by GPC is respectively 10000 ~ 300000.When the weight-average molecular weight of (D) composition is less than 10000, easily cause the reduction of water tolerance, more than 300000, the remarkable thickening of resin combination can be caused, have problems in coating.When add (D) composition, as use level, when using composition total mass as 100 quality %, be preferably 1 ~ 10 quality %, be more preferably 1 ~ 5 quality %.When use level is more than 10 quality %, exists and to cause because of thickening coating to reduce, cause situation that the binding property of polarizer is reduced.
As the concrete example of (D) composition, if polybutyral resins, then can enumerate, エ ス レ ッ Network " BL-1 ", " BL-2 ", " BL-2H ", " BL-5 ", " BL-10 ", " BM-1 ", " BM-2 ", " BM-S ", " BH-3 ", " BH-S " etc. that such as ponding chemical industry society produces.
Polybutyral resins refers to, with butyraldehyde, polyvinyl alcohol is carried out the resin of acetalation, and the butyralization degree of aforementioned polyvinyl butyral acetal is preferably 50 ~ 95mol%, is more preferably 60 ~ 90mol%, more preferably 65 ~ 85mol%.In addition, when polyvinyl acetal resin is polyvinyl butyral resin, above-mentioned butyralization degree can be calculated by the result by measuring according to the method for JIS K6728 " polyvinyl butyral acetal test method ".
Vibrin refers to, the polymkeric substance of polycarboxylic acid and polyvalent alcohol, can be independent, or also multiple kind can be combined for the polycarboxylic acid that is polymerized and polyvalent alcohol.
As polycarboxylic acid, can enumerate, the aromatic dicarboxylic acids such as terephthalic acid, m-phthalic acid, naphthalic acid, the alicyclic dicarboxylic acid such as cyclohexane cyclohexanedimethanodibasic, Tetra Hydro Phthalic Anhydride, the aliphatic dicarboxylic acids such as succinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, dimeracid, hydrogenated dimer acids.
As polyvalent alcohol, can enumerate, low molecular weight polyols, polyether glycol, polycarbonate polyol and polyester polyol etc.
As low molecular weight polyols, can enumerate, the polyvalent alcohol with at least 2 hydroxyls of such as molecular weight about 50 ~ 300, as concrete example, can enumerate, ethylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, butyleneglycol, 1,6-hexylene glycol, 2-methyl isophthalic acid, 8-ethohexadiol, nonanediol, cyclohexanedimethanol, neopentyl glycol and 3-methyl isophthalic acid, 5-pentanediol etc.
As polyether glycol, can enumerate, such as, there is the polyalkylene glycol of more than 3 oxygen base alkylidene units, as concrete example, polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol etc. can be enumerated.
As polycarbonate polyol, can enumerate, the resultant of reaction of such as carbonic ether and glycol.As carbonic ether, specifically can enumerate, the diaryl carbonates such as diphenyl carbonate and the dialkyl carbonate such as methylcarbonate and diethyl carbonate etc.As glycol, aforesaid low molecular weight polyols can be enumerated.
As polyester polyol, can enumerate, be such as selected from least a kind in these low molecular weight polyols, polyether glycol and polycarbonate polyol with the reaction product of sour composition.As sour composition, can enumerate, diprotic acid or their acid anhydrides etc. such as such as hexanodioic acid, sebacic acid, succinic acid, toxilic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid.In addition, the ring-opening reaction product etc. of polycarbonate diol and caprolactone can also be enumerated.
As the concrete example of vibrin, polyethylene terephthalate, polybutylene terephthalate etc. can be enumerated.
Polyvinylamide resin refers to, (A) polymkeric substance of the vinyl with free-radical polymerised base represented by composition and the N-ethenyl amide compound prodn of nitrogen Direct Bonding, it can be independent for being polymerized the N-vinylamide monomers used, or also can be the multipolymer using multiple kind.In addition, also can be with N-ethenyl amide compound prodn beyond the multipolymer with free-radical polymerised monomer.
As there is free-radical polymerised monomer beyond N-ethenyl amide compound prodn, can be used alone monomer shown below, or using multiple monomer shown below.
(1) (methyl) esters of acrylic acid such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) Hydroxyethyl Acrylate.(2) (methyl) acrylamide derivative class such as (methyl) acrylamide, N-monomethyl (methyl) acrylamide, the mono-ethyl of N-(methyl) acrylamide, N, N-dimethyl (methyl) acrylamide.(3) the alkaline unsaturated monomer such as (methyl) acrylate, dimethyl aminoethyl (methyl) acrylamide, vinyl pyridine, vinyl imidazole.(4) vinyl
azoles quinoline, pseudoallyl
the imino-ethers such as azoles quinoline.(5) unsaturated monomer containing carboxyl such as (methyl) vinylformic acid, methylene-succinic acid, toxilic acid, fumaric acid.(6) (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxybutyl, (methyl) vinylformic acid 3-hydroxybutyl, (methyl) vinylformic acid 4-hydroxybutyl, 2-(hydroxymethyl) methyl acrylate, 2-(hydroxymethyl) ethyl propenoate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate etc. has the unsaturated monomer of hydroxyl.(7) unsaturated acid anhydride such as maleic anhydride, itaconic anhydride class.(8) vinyl ester such as vinyl acetate, propionate.
(9) vinylethylene carbonate (Vinyl Ethylene Carbonate) and its derivative.(10) vinylbenzene and its derivative.(13) vinyl ethers such as methylvinylether, ethyl vinyl ether, butyl vinyl ether.(14) olefines such as ethene, propylene, octene, divinyl.(15) glycidyl (methyl) acrylate etc. has the unsaturated monomer of glycidyl.
As the concrete example of polyvinylamide resin, can enumerate, polyvinylformamide, poly N-ethylene yl acetamide, poly N-vinyl pyrrolidone etc.
Active energy ray curable binder composition involved in the present invention can be cured by the active energy beam irradiated as electron rays, ultraviolet.
When using electron rays in the solidification of active energy ray curable binder composition involved in the present invention, it is not necessary especially for making to contain Photoepolymerizationinitiater initiater in composition, but when using ultraviolet to be cured, preferred use Photoepolymerizationinitiater initiater, particularly preferably uses the Photoepolymerizationinitiater initiater with the effective absorbing wavelength of more than 380nm.
As the Photoepolymerizationinitiater initiater with the effective absorbing wavelength of more than 380nm, can enumerate, acylphosphine oxide compound.As the concrete example of such compound; can enumerate, 2,4; 6-trimethylbenzoyl phenyl oxyethyl group phosphine oxide, 2; 4,6-trimethyl benzoyl diphenyl base phosphine oxide, two (2,6-Dimethoxybenzoyl)-2; 4; 4-trimethylpentylphosphine oxide, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide etc.On the other hand, as the initiator 1-hydroxycyclohexylphenylketone, owing to not having effective absorbing wavelength of more than 380nm, so the path irradiated according to active energy beam, there is solidification and become insufficient situation.
As for the use level of Photoepolymerizationinitiater initiater, relative to total amount 100 mass parts of aforementioned (A) composition and aforementioned (B) composition, be preferably 1 ~ 5 mass parts.
Generally speaking, the transparent protective film for the protection of polarizer has ultraviolet absorption ability for the object of protection polarizer.The sensitivity of acylphosphine oxide based compound in the wavelength region may side of more than 380nm is excellent, and the solidified nature when transmission transparent protective film is excellent especially.
In addition, can be used together known Photoepolymerizationinitiater initiater as required.Because the transparent protective film with ultraviolet absorption ability is difficult to the light through below 380nm, so as Photoepolymerizationinitiater initiater, preferably use the highly sensitive Photoepolymerizationinitiater initiater to more than 380nm.Specifically, can enumerate, " IRGACURE907 (2-methyl isophthalic acid-(4-methyl thio phenyl)-2-morpholinopropane-1-ketone) ", " IRGACURE369 (2-phenmethyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone) ", " IRGACURE379 (2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone) " etc. that such as BASF society produces.
In addition, can be used together known sensitizing agent as required.Owing to having the light of transparent protective film not transmission below the 380nm of ultraviolet absorption ability, so as sensitizing agent, preferably use the highly sensitive sensitizing agent to more than 380nm.Specifically, can enumerate, " KAYACURE DETX-S (2,4-diethyl thioxanthone) ", " KAYACURE CTX (2-chlorothiaxanthenone) " that such as Japanese chemical drug society produces etc.
In addition, in active energy ray curable binder composition involved in the present invention, in the scope not damaging object of the present invention, effect, can coordinate into various additive as other any composition.As this additive, can enumerate, the stopper such as thiodiphenylamine, 2,6 di tert butyl 4 methyl phenol, polymerization cause auxiliary agent, flow agent, wettability improving agent, tensio-active agent, softening agent, UV light absorber, silane coupling agent, inorganic filler etc.
In above-mentioned additive, silane coupling agent acts on polarizer surface, can give further water tolerance.When use silane coupling agent, for its addition, using composition total mass as 100 quality % time, be generally 0.1 ~ 10 quality %, be preferably 0.5 ~ 5 quality %, most preferably be 0.5 ~ 3 quality %.
For silane coupling agent, preferably use and irradiate can carry out the compound of radical polymerization with (A), (B) composition by active energy beam.
As carrying out the concrete example of the silane coupling agent of radical polymerization with (A), (B) composition, can enumerate, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl diethoxy silane, 3-methacryloxypropyl, 3-acryloxypropyl Trimethoxy silane etc.
Active energy ray curable binder composition involved in the present invention can use with the embodiment of ultraviolet hardening or electron(beam)curing type.
In electron(beam)curing type, for the illuminate condition of electron rays, as long as the condition that above-mentioned active energy ray curable binder composition can be made to solidify, just condition suitable arbitrarily can be adopted.Such as, for electronbeam irradiation, acceleration voltage is preferably 5kV ~ 300kV, more preferably 10kV ~ 250kV.When acceleration voltage is less than 5kV, there is electron rays and can not arrive tackiness agent and become the not enough misgivings of solidification, if acceleration voltage is more than 300kV, then excessively strong by the penetration power of test portion, thus there are the misgivings making transparent protective film, polarizer deterioration.As useful to irradiation of rays amount, be preferably 5 ~ 100kGy, more preferably 10 ~ 75kGy.When useful to irradiation of rays amount is less than 5kGy, it is not enough that tackiness agent becomes solidification, if more than 100kGy, then exists and make the deterioration of transparent protective film, polarizer, physical strength occurs and reduces, turn yellow, can not obtain the situation of the optical characteristics of regulation.
For electronbeam irradiation, usually irradiate in rare gas element, but if needed, also can carry out in an atmosphere or under the condition introducing a small amount of oxygen.Although have difference according to the material of transparent protective film; but by suitably introducing oxygen; make the transparency protected face being subject to electronbeam irradiation at first produce resistance oxygen effect on the contrary, the damage to transparent protective film can be prevented, only effectively can irradiate electron rays to tackiness agent.
On the other hand; for ultraviolet hardening; when use imparts the transparent protective film of ultraviolet absorption ability; because the light than about 380nm short wavelength can not to be arrived the position of active energy ray curable binder composition, so there is the situation of not making contributions to this polyreaction by absorbing.In addition, the light that the wavelength ratio 380nm absorbed by transparent protective film is short is converted to heat, there is transparent protective film self-heating, thus becomes the situation of the bad reason such as curling fold of polarization plates.Therefore, in the present invention, when adopting ultraviolet hardening, as ultraviolet ray generating apparatus, the device of the light preferably using not emission wavelength shorter than 380nm.
As the light source meeting such luminescent spectrum and require, preferably enclose the metal halide lamp of gallium, the LED light source in the luminescence of 380 ~ 440nm wavelength region.Or, low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, incandescent light, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, luminescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight can be used as light source, use the light that passband filter blocks wavelength ratio 380nm is short.
For ultraviolet hardening, for improving the fusible object with base material, preferably before irradiation ultraviolet radiation, active energy ray curable binder composition is heated (pre-irradiation heating), in this case, preferably be heated to more than 40 DEG C, be more preferably heated to more than 60 DEG C.
Form one example of the polarization plates of binder layer having polarizer, transparent protective film and formed by active energy ray curable binder composition involved in the present invention has been shown in Fig. 1.
Active energy ray curable binder composition involved in the present invention; particularly when using the Photoepolymerizationinitiater initiater with the effective absorbing wavelength of more than 380nm, can compatibly for the formation of the situation of the binder layer of the transparent protective film bonding by having ultraviolet absorption ability.The transparent protective film with ultraviolet absorption ability refers to, the transparent protective film that the transmissivity for the light of the wavelength of below 380nm is less than 10%.Here; active energy ray curable binder composition involved in the present invention; particularly by containing above-mentioned acylphosphine oxide compound as Photoepolymerizationinitiater initiater, can the ultraviolet of more than 380nm wavelength be had via the transparent protective film irradiation with ultraviolet absorption ability and solidify to form binder layer.Therefore, have in the polarization plates of the transparent protective film of ultraviolet absorption ability even if all stacked on the two sides of polarizer, binder layer also can be made to solidify.
As the method for transparent protective film being given to ultraviolet absorption ability, can enumerate, make the method containing UV light absorber in transparent protective film, in the transparent protective film stacked method containing the surface-treated layer of UV light absorber on the surface.
As the concrete example of UV light absorber, can enumerate, such as existing known oxygen base benzophenone based compound, benzotriazole based compound, salicylate based compound, benzophenone based compound, cyanoacrylate based compound, nickel complex salt based compound, triazine based compound etc.
The binder layer formed by active energy ray curable binder composition of the present invention, compared with aqueous adhesive layer, thermotolerance is high.In the present invention, as binder layer, preferably use second-order transition temperature: Tg is the binder layer of more than 60 DEG C, more preferably Tg is more than 120 DEG C and less than 300 DEG C.
In addition, Tg is that the EXSTARDSC/SS7020 using Hitachi Ha イ テ Network サ イ エ Application ス society to produce measures under the Elevated Temperature Conditions of 10 DEG C/min.
The manufacture of polarization plates involved in the present invention has following operation: coat activated energy ray-curable binder composition on the face that will form binder layer of polarizer or transparent protective film; then polarizer and transparent protective film are fitted; then, form by irradiating active energy beam the binder layer that active energy ray curable binder composition have cured.
For polarizer, transparent protective film, before the above-mentioned active energy ray curable binder composition of coating, also surface modification treatment can be carried out.As concrete process, corona treatment, Cement Composite Treated by Plasma, saponification process etc. can be enumerated.
For the coating method of active energy ray curable binder composition, appropriate selection can be carried out according to the viscosity of composition, target thickness.As the example of coating method, can enumerate, such as reverse coating machine, gravure coater (directly, oppositely, hectograph), trans coiling rod coating machine (barreverse coater), roll coater, die coater, coiling rod coating machine (bar coater), rod coater etc.
Via the tackiness agent be coated with in the above described manner, polarizer and transparent protective film are fitted.The laminating of polarizer and transparent protective film can be undertaken by roll squeezer etc.
Making after polarizer and transparent protective film fit, to irradiate electron rays, ultraviolet isoreactivity energy-ray, make active energy ray curable binder composition solidify, thus formation binder layer.For the direction of illumination of active energy beam, can irradiate from direction suitable arbitrarily.Preferably irradiate from transparent protective film side.If irradiated from polarizer side, then there are the misgivings that deterioration occurs because of active energy beam polarizer.
When using tinuous production to manufacture polarization plates involved in the present invention, although linear velocity having difference according to the set time of tackiness agent, being preferably 1 ~ 500m/min, being more preferably 5 ~ 300m/min, more preferably 10 ~ 100m/min.When on-line velocity is excessively slow, produce rate variance, or excessive to the damage of transparent protective film, the polarization plates that can tolerate endurance test etc. can not be produced.When on-line velocity is too fast, the solidification of tackiness agent becomes insufficient, there is the situation that can not obtain target binding property, thermotolerance, water tolerance.
The binder layer that polarization plates of the present invention is formed across the solidification nitride layer by above-mentioned active energy ray curable binder composition at least one side of polarizer is fitted with transparent protective film.
Polarizer is not particularly limited, and can use various polarizer.As polarizer, can enumerate, in the hydrophilic macromolecule films such as polyvinyl alcohol mesentery, the formalized polyvinyl alcohol mesentery of part, the partly-hydrolysed film of ethylene vinyl acetate copolymer system, such as adsorb the dichroic material such as iodine, dichroic dye and the polarizer of uniaxial extension, the polyene system alignment films such as the processed thing of polyvinyl alcohol, the desalination acid treatment thing of polyvinyl chloride, etc.In the middle of them, the polarizer be preferably made up of the dichroic substance such as polyvinyl alcohol mesentery and iodine.The thickness of these polarizers is not particularly limited, but is generally less than about 80 μm.
For with iodine by polyvinyl alcohol mesentery dyeing and the polarizer of uniaxial extension, such as can dye by polyvinyl alcohol is flooded in the aqueous solution of iodine, made by 3 ~ 7 times of being stretched to former length.Also can flood in the aqueous solution of boric acid, potassiumiodide etc. as required.In addition, also can before dyeing polyvinyl alcohol mesentery be flooded in water and wash as required.By washing polyvinyl alcohol mesentery, except the spot on polyvinyl alcohol mesentery surface, antiblocking agent can being cleaned, also have by making the swelling effect preventing uneven dyeing etc. uneven of polyvinyl alcohol mesentery.Stretching can be carried out after with iodine staining, also can stretch by an Edge Coloring, or also can dye with iodine after the stretch.Also can in the aqueous solution of boric acid, potassiumiodide etc., stretch in water-bath.
In addition, as polarizer, the slim polarizer of thickness less than 10 μm can be used.Slim polarizer like this, because thickness is irregular less, visibility excellent and dimensional change is little, so excellent in te pins of durability, in addition, also preferred from the viewpoint of the thickness requirement slimming as polarization plates.
The material of the transparent protective film of the one or both sides of above-mentioned polarizer is arranged on, preferably the material of excellence in the transparency, physical strength, thermostability, moisture block, isotropy etc. as being formed.Can enumerate, the such as Polyester such as polyethylene terephthalate, PEN polymkeric substance, the cellulose-based polymkeric substance such as secondary cellulose acetate, cellulose triacetate, the acrylic acid polymer such as polymethylmethacrylate, the styrenics such as polystyrene, acrylonitrile styrene copolymer (AS resin), polycarbonate based polymer etc.In addition, as the example of the polymkeric substance of the above-mentioned transparent protective film of formation, polyethylene can also be enumerated, polypropylene, ring system or there is the cyclic polyolefin of norbornylene structure, the polyolefin polymkeric substance such as ethylene propylene copolymer, vinyl chloride-based polymer, polymeric amide, the acid amides based polymers such as aromatic polyamide, imide series polymkeric substance, sulfone based polymer, polyethersulfone based polymer, polyether-ether-ketone based polymer, polyphenylene sulfide based polymer, vinyl alcohol system polymer, vinylidene chloride based polymer, vinyl butyral based polymer, arylide based polymer, polyoxymethylene based polymer, epoxy polymkeric substance, or the blend etc. of above-mentioned polymkeric substance.Also the additive of more than a kind any appropriate can be contained in transparent protective film.As additive, can enumerate, such as UV light absorber, antioxidant, lubricant, softening agent, releasing agent, painted preventing agent, fire retardant, nucleator, static inhibitor, pigment, tinting material etc.
The thickness of transparent protective film can suitably be determined, but usually from the viewpoint of the workability such as intensity, operability, thin layer etc., is about 1 ~ 500 μm.Be particularly preferably 5 ~ 200 μm.
In addition, when the two sides of polarizer arranges transparent protective film, its surface can use with the back side transparent protective film formed by identical polymer materials, also can use the transparent protective film formed by different polymer materialss etc.
Above-mentioned transparent protective film do not carry out with the face of the bonding of polarizer on the functional layers such as hard coat, anti-reflecting layer, adherent layer, diffusion layer or antiglare layer can be set.In addition, the functional layers such as above-mentioned hard coat, anti-reflecting layer, adherent layer, diffusion layer, antiglare layer to arrange with the mode of transparent protective film one, also can be arranged as the formation of the split with transparent protective film in addition.
Polarization plates of the present invention can use as the blooming stacked with other optical layers when reality uses.Fig. 2 shows an example of the formation of blooming.Its optical layers is not particularly limited, but more than 1 layer or 2 layers such as reflector, semi-transparent plate, polarizer, compensation film for angular field of view etc. can be used for the formation of certain optical layers of liquid crystal indicator etc.
The stacked blooming of above-mentioned optical layers in polarization plates, although can be formed in mode stacked respectively successively in the manufacturing processed of liquid crystal indicator etc., but it is stacked in advance and when forming blooming, excellent in quality stability, assembling operation etc., there is the advantage of the workability of the manufacturing process can improving liquid crystal indicator etc.The adhesive means that bonding coat etc. is suitable can be used when carrying out stacked.When bonding above-mentioned polarization plates, other blooming, their optic axis can form suitable arrangement angles according to target phase difference characteristic etc.
Aforementioned polarization plates, at least stacked blooming of 1 layer of polarization plates also can be arranged for the bonding coat with other adhering components such as liquid crystal cells.Form the tackiness agent of bonding coat to be not particularly limited, but can suitably choice for use such as using polymkeric substance such as acrylic acid polymer, siloxane-based polymers, polyester, urethane, polymeric amide, polyethers, fluorine based polymer, rubber series as the tackiness agent of matrix polymer.Particularly preferably use the tackiness agent that optical transparence excellence, the wettability showing appropriateness and tackiness and fusible adhesion characteristic, weathering resistance, thermotolerance etc. are excellent as acrylic adhesive.
Bonding coat can be arranged on the one or both sides of polarization plates, blooming as the overlapping layer of the layers such as difference composition or kind.In addition, when being arranged at two sides, the bonding coat of different composition, kind, thickness etc. can be formed on the surface of polarization plates, blooming and the back side.The thickness of bonding coat suitably can be determined according to application target, bounding force etc., is generally 1 ~ 500 μm, is more preferably 1 ~ 100 μm.
For the exposed surface of bonding coat, during till for practicality, the object to pollute for preventing it etc., covers with dividing plate temporarily.Thus, can prevent from contacting with bonding coat under common operational stage.As dividing plate, except above-mentioned thickness condition, can use and such as with the suitable stripper such as siloxane-based, chain alkyl system, fluorine system, moly-sulfide, the suitable dividing plate according to prior art of the dividing plate of coating process etc. carried out to plastic film, sheet rubber, paper, cloth, their the suitable sheet such as duplexer as required.
Polarization plates of the present invention or blooming can be preferred for the formation etc. of the various image display devices such as liquid crystal indicator.One example of the formation of image display device has been shown in Fig. 3.Such as, the formation of liquid crystal indicator can be carried out according to existing method.Namely, liquid crystal indicator generally by liquid crystal cells and polarization plates or the component parts such as blooming and lighting system as required are suitably assembled, driving circuit etc. be installed formed, but in image display device of the present invention, except using according to except polarization plates of the present invention or blooming this point, be not particularly limited, can be formed according to existing method.For liquid crystal cells, the liquid crystal cells of any types such as such as TN type, STN type, π type can be used.
The liquid crystal indicator that the one or both sides that can be formed in liquid crystal cells are configured with the liquid crystal indicator of polarization plates or blooming, use the liquid crystal indicator of backlight or reflector etc. suitable in the illumination system.In this case, the one or both sides of liquid crystal cells can be arranged on according to polarization plates of the present invention or blooming.When both sides arrange polarization plates or blooming, they can be the same or different.In addition, when forming liquid crystal indicator, more than 1 layer or the 2 layers parts that such as diffuser plate, antiglare layer, anti-reflective film, protecting sheet, prism array, lens array plate, light diffusing sheet, backlight etc. are suitable can be configured in place.
Embodiment
Although describe embodiments of the invention below, embodiments of the present invention are not by the restriction of these embodiments.
<Tg: second-order transition temperature >
For Tg, in the mould that the tetrafluoroethylene of 10mm × 10mm × 0.5mm is made, add the liquid of binder composition, with 2000mJ/cm
2the ultraviolet of integrating light quantity illumination wavelength 405nm, thus obtain cured article.Obtained cured article is cut into 2mm square, as mensuration sample.Measure the EXSTAR DSC/SS7020 using Hitachi Ha イ テ Network サ イ エ Application ス society to produce.
Specimen size: 2mm × 2mm × 0.5mm × 4 piece
Sample weight: 9.6mg
Mode determination: heat-up rate: 10 DEG C/min
Carry out DSC mensuration, adopt peak temperature as the DDSC figure of its differential as Tg.
< weight-average molecular weight >
Gel permeation chromatograph is used to measure.In addition, when measuring, use Shodex (registered trademark) the GPC System-21 (post KF-802, KF-803, KF-805) that Showa electrician society produces, condition determination is column temperature 40 DEG C, elutriant tetrahydrofuran (THF), elution speed 1ml/ minute.Represent with the polystyrene standard molecular weight (Mw) that converts.
< polarizer >
By the polyvinyl alcohol of the thickness 75 μm of mean polymerisation degree 2400, saponification deg 99.9 % by mole (hereafter also referred to as PVA.) film floods 60 seconds in the warm water of 30 DEG C, makes it swelling.Then, flood in the aqueous solution of the concentration 0.3% of iodine/potassiumiodide (weight ratio=0.5/8), be stretched to 3.5 times, while dye to film.Then, the mode being 6 times with total stretching ratio in the boric acid ester aqueous solution of 65 DEG C stretches.After the stretch, in the baking oven of 40 DEG C, drying 3 minutes, obtains PVA system polarizer.
< transparent protective film 1>
As transparent protective film, do not carry out saponification corona treatment etc. and use the tri cellulose acetate membrane of thickness 80 μm (hereafter also referred to as TAC film.)。
< transparent protective film 2>
As transparent protective film, do not carry out corona treatment etc. and use the polymethyl methacrylate film (PMMA film) of thickness 80 μm.
< active energy beam >
As active energy beam, use ultraviolet (enclosing the metal halide lamp of gallium) irradiating unit: ML-251A/B: illumination optics unit PM25C-90 illumination: the 23mW/cm that ウ シ オ motor society produces
2, integrating irradiation dose 300/mJ/cm
2(wavelength 365nm).In addition, ultraviolet illumination is that the UIT-250 using ウ シ オ motor society to produce measures.
(modulation of active energy ray curable binder composition)
Embodiment 1 ~ 9, comparative example 1 ~ 5
According to the cooperation table described in table 1 and table 2, each composition is mixed, stir 0.5 hour at 40 DEG C, thus obtain embodiment 1 ~ 9, active energy ray curable binder composition involved by comparative example 1 ~ 5.The each composition used is as described below.
(A) composition
The N-vinyl formamide " PVC ー system セ ッ ト 770 " that NVF: Huang Chuan chemical industry society produces
NVA: the N-vinyl acetamide " NVA モ ノ マ ー (registered trademark) " that Showa electrician society produces
V-CAP: Tokyo changes into the N-caprolactam that society produces
(B) composition
TAEIC: Tokyo changes into three (methacryloyl oxygen base ethyl) isocyanuric acid ester that society produces
BAEHEIC: Tokyo changes into two (methacryloyl oxygen base ethyl) hydroxyethyl isocyanuric acid ester that society produces
SP-1507: the low-molecular-weight ethylenic base ester resin that Showa electrician society produces, weight-average molecular weight (Mw): 480
(C) composition
VR-60: the high molecular weight ethylene base ester resin that Showa electrician society produces, weight-average molecular weight (Mw): 7500
(D) composition
The butyral resin " BL-10 " that BL-10: ponding chemical industry Zhu Shi society produces, weight-average molecular weight (Mw): 58000
(initiator)
2,4, the 6-trimethylbenzoyl diphenyl phosphine oxides " Le シ リ Application TPO " that TPO:BASF society produces
(other composition)
4HBA: the vinylformic acid 4-hydroxybutyl " 4HBA " that Osaka Organic Chemical Industry society produces
HEAA: the Xing Renshe hydroxyethyl acrylamide produced
IBXA: the isobornyl acrylate " IBXA " that Osaka Organic Chemical Industry society produces
DPCA60: the Dipentaerythritol 6-caprolactone affixture that Japanese chemical drug society produces and acrylic acid carboxylate " DPCA60 ", weight-average molecular weight (Mw): 1260
(making of polarization plates)
Use coiling rod coating (bar coat) on above-mentioned transparent protective film 1 and 2 to form the active energy ray curable binder composition involved by the mode coating Examples 1 ~ 9 of 4 μm of thickness, comparative example 1 ~ 5, be fitted in the two sides of above-mentioned polarizer with roll squeezer.Then, from side illumination wavelength 405nm, the integrating light quantity 1000mJ/cm of the transparent protective film of laminating
2ultraviolet, make embodiment 1 ~ 9, active energy ray curable binder composition solidification involved by comparative example 1 ~ 5, then warm air drying 3 minutes at 70 DEG C, obtains the polarization plates in the both sides of polarizer with transparent protective film.According to following condition, the bounding force (to TAC, to PMMA) of obtained each polarization plates, water tolerance (warm water immersion test) are evaluated.
< bounding force >
Polarization plates is cut into the size of 150mm × 20mm, forms otch with cutting knife at transparent protective film 1 or between transparent protective film 2 and polarizer, polarization plates is fitted on SUS plate.Along 90 degree of directions, transparent protective film and polarizer are peeled off with the peeling rate of 300mm/min by tensile testing machine, according to following benchmark, stripping interface is evaluated.
A: the cohesion failure of transparent protective film or polarizer
B: although find the interface peel between binder layer/polarizer in a part, there is the cohesion failure of transparent protective film or polarizer in major part
C: although find the cohesion failure of transparent protective film or polarizer in one, there is the interface peel between binder layer/polarizer in major part
D: the interface peel between binder layer/polarizer
According in the evaluation of said reference, evaluation result A is best, is then followed successively by B, C, D.Below evaluation result C is judged as Poor cohesion.
< water tolerance (warm water immersion test) >
Polarization plates is cut into the rectangle of the draw direction 50mm along polarizer, vertical direction 25mm.Involved polarization plates flooded 6 hours in the warm water of 60 DEG C, then visual observations polarizer/transparency protected intermembranous stripping, evaluates according to following benchmark.
A: the stripping of end is below 2mm from end to inside
B: the stripping of end is 2mm ~ 5mm from end to inside
C: the stripping of end is 5mm ~ 10mm from end to inside
D: the stripping of end is more than 10mm from end to inside
According in the evaluation of above-mentioned standard, evaluation result A is best, is then B, C, D successively.Below evaluation result C is judged as that water tolerance is bad.
Table 1
Table 2
In embodiment 1 ~ 9, Tg>120 DEG C in any embodiment, and binding property, water tolerance are the evaluation of more than B.
In comparative example 1,4, very poor to the binding property of base material.In addition, in comparative example 2,3, binding property is slightly poor, in addition, according to the kind (polarizer/TAC, polarizer/PMMA) of base material, binding property occurs bad.
Utilizability in industry
Active energy ray curable binder composition of the present invention can form the binder layer of the binding property of polarizer and transparent protective film, thermotolerance, excellent water resistance, can obtain polarization plates excellent in reliability, blooming and image display device by using this binder composition.
In addition, in the manufacturing process of polarization plates using active energy ray curable tackiness agent of the present invention, compared with existing aqueous adhesive, significantly can simplify, cost degradation, energy-saving can be expected.
Claims (17)
1. an active energy ray curable binder composition, it contains following composition:
(A) composition, its ethenyl amide compound prodn represented by following general formula (1), and
(B) composition, it is in 1 molecule, have more than 2 have free-radical polymerised ethylenically unsaturated group and molecular weight is the compound of less than 1000,
In formula (1), R
1and R
2for 1 valency alkyl of hydrogen atom or carbonatoms 1 ~ 6, R
1and R
2can be the same or different, R
1and R
2can connect and form ring texture.
2. active energy ray curable binder composition according to claim 1, described (B) composition (methyl) acryl compound (B1) represented by following general formula (2),
In formula (2), X
1, X
2and X
3for 1 valency alkyl of (methyl) acryl, hydrogen atom or carbonatoms 1 ~ 6, and X
1, X
2and X
3in at least 2 be (methyl) acryl, R
3, R
4and R
5represent carbonatoms 1 ~ 6, Sauerstoffatom respectively with X
1, X
2, X
3the oxyalkylene that side switch closes.
3. active energy ray curable binder composition according to claim 1, described (A) composition is any one in N-vinyl formamide, N-vinyl acetamide, NVP, N-caprolactam.
4. active energy ray curable binder composition according to claim 2, (methyl) acryl compound (B1) represented by aforementioned formula (2) is three (acryl oxygen base ethyl) isocyanuric acid esters or two (acryl oxygen base ethyl) hydroxyethyl isocyanuric acid ester.
5. active energy ray curable binder composition according to claim 1, in total composition, contains described (A) composition with the scope of 25 ~ 75 quality %, contains described (B) composition with the scope of 25 ~ 75 quality %.
6. active energy ray curable binder composition according to claim 1, it is also containing (C) composition, and described (C) composition is that the weight-average molecular weight of polystyrene conversion is epoxy acrylate and/or the urethane acrylate of 1000 ~ 20000 when measuring with GPC.
7. active energy ray curable binder composition according to claim 6, in total composition, containing (C) composition described in 1 ~ 20 quality %.
8. active energy ray curable binder composition according to claim 1, it is also containing (D) composition, described (D) composition be when measuring with GPC the weight-average molecular weight of polystyrene conversion be 10000 ~ 300000, at least a kind of being selected from polybutyral resins, vibrin and polyvinylamide resin.
9. active energy ray curable binder composition according to claim 8, in total composition, containing (D) composition described in 1 ~ 10 quality %.
10. active energy ray curable binder composition according to claim 1, it contains the Photoepolymerizationinitiater initiater with the effective absorbing wavelength of more than 380nm.
11. active energy ray curable binder compositions according to claim 10, described in there is the effective absorbing wavelength of more than 380nm Photoepolymerizationinitiater initiater be acylphosphine oxide compound.
12. 1 kinds of cured articles, its second-order transition temperature is more than 60 DEG C, and it is solidified by the active energy ray curable binder composition according to any one of claim 1 ~ 11.
13. 1 kinds of polarization plates, it forms binder layer between at least 1 face and transparent protective film of polarizer, and described binder layer is obtained the active energy ray curable binder composition solidification according to any one of claim 1 ~ 11.
14. polarization plates according to claim 13, the material of described transparent protective film is be selected from least a kind in celluosic resin, (methyl) acrylic resin, polycarbonate resin, vibrin and cyclic polyolefin resin.
15. 1 kinds of bloomings, it is stacked multiple layer and forms, and wherein at least 1 layer is polarization plates according to claim 13.
16. 1 kinds of image display devices, it uses the polarization plates described in claim 13 to obtain.
17. 1 kinds of image display devices, it uses the blooming described in claim 15 to obtain.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013220933 | 2013-10-24 | ||
| JP2013-220933 | 2013-10-24 |
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| Publication Number | Publication Date |
|---|---|
| CN104559894A true CN104559894A (en) | 2015-04-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410562754.6A Pending CN104559894A (en) | 2013-10-24 | 2014-10-21 | Active energy ray-curable adhesive composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6412747B2 (en) |
| KR (1) | KR20150047430A (en) |
| CN (1) | CN104559894A (en) |
| TW (1) | TW201516114A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108290970A (en) * | 2015-11-13 | 2018-07-17 | 株式会社德山 | Photocurable resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2019523813A (en) * | 2016-06-13 | 2019-08-29 | アカテコール・インコーポレイテッドＡＣａｔｅｃｈｏｌ， Ｉｎｃ． | Ionic polymers and their use as wet adhesives and paints |
| JP2019188898A (en) * | 2018-04-20 | 2019-10-31 | 矢崎総業株式会社 | Cover for vehicle display unit and vehicle display device |
| KR20210104056A (en) * | 2018-12-21 | 2021-08-24 | 세키스이가가쿠 고교가부시키가이샤 | Adhesive composition, adhesive for electronic component, and adhesive for display device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08311418A (en) * | 1995-05-23 | 1996-11-26 | Sekisui Chem Co Ltd | Production of self-adhesive sheet for liquid crystal display |
| JPH11100419A (en) * | 1997-09-26 | 1999-04-13 | Jsr Corp | Radiation-curable resin composition |
| WO2011151890A1 (en) * | 2010-06-01 | 2011-12-08 | リケンテクノス株式会社 | Adhesive composition, bonding method, and laminate |
-
2014
- 2014-09-11 JP JP2014185096A patent/JP6412747B2/en active Active
- 2014-10-21 KR KR1020140142597A patent/KR20150047430A/en not_active Application Discontinuation
- 2014-10-21 CN CN201410562754.6A patent/CN104559894A/en active Pending
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108290970A (en) * | 2015-11-13 | 2018-07-17 | 株式会社德山 | Photocurable resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201516114A (en) | 2015-05-01 |
| JP2015108115A (en) | 2015-06-11 |
| KR20150047430A (en) | 2015-05-04 |
| JP6412747B2 (en) | 2018-10-24 |
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Application publication date: 20150429 |