CN102012535B - Polarizing plate and photocurable adhesive for forming polarizing plate - Google Patents
Polarizing plate and photocurable adhesive for forming polarizing plate Download PDFInfo
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- CN102012535B CN102012535B CN201010266175.9A CN201010266175A CN102012535B CN 102012535 B CN102012535 B CN 102012535B CN 201010266175 A CN201010266175 A CN 201010266175A CN 102012535 B CN102012535 B CN 102012535B
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- polarizer
- radical polymerised
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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
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Liquid Crystal (AREA)
- Adhesive Tapes (AREA)
Abstract
The present invention provides a polarizing plate, wherein two surfaces of a polyvinyl alcohol series polarizer are respectively protected by a protecting film while the two surfaces are separated from the protecting films by adhesion layers. The adhesion layers are obtained through solidifying a photo-curing adhesive which comprises the following components: (a) 60-99.8wt% of free radical polymeric compound, (c) 0.02-40wt% of cation polymeric compound which comprises cation polymeric functional groups and does not comprise (methyl)acryloyl group, (d) an optical free radical initiating agent, and (e) an optical cation polymerization initiating agent.
Description
Technical field
The present invention relates to Polarizer and this photocurable adhesive for forming polarizing plate for liquid crystal indicator etc.
Background technology
At wrist-watch, mobile phone, personal portable terminating machine (PDA), notebook, for computer in monitor, DVD player and TV etc., liquid crystal indicator is flooded with market just hastily.Liquid crystal indicator is that the polarized condition that the switch by liquid crystal is caused is carried out visible apparatus, from its displaying principle, can use polarizer.Special high brightness, high-contrast and the wide visual angle of more and more requiring in the purposes such as TV, and also more and more require high permeability, high degree of polarization and high colorrendering quality etc. for polarizer.
The polarizer using in liquid crystal display association area etc. normally has the material of iodine or dyestuff to carry out uniaxial tension to manufacture by adsorbing in polyvinyl alcohol (PVA) (PVA).This polyethenol series polarizer, because heat or moisture shrink, causes the reduction of polarizing properties.Here, the object that the surface that at PVA is polarizer is fitted with to diaphragm is used as Polarizer.
As for polarizer being sticked together to the bonding agent of diaphragm, use widely the aqueous solution (PVA is bonding agent) (with reference to patent documentation 1,2) of polyvinyl alcohol resin in the past.
In addition, in patent documentation 3, disclosing a kind of aqueous polyurethane that uses is the Polarizer that bonding agent forms.
Yet, along with particularly take in recent years the progress of large screen of the image display device that TV is representative, Polarizer has also been improved to the requirement of maximizing, become important problem.
But, use in the Polarizer of aforesaid water system bonding agent, size by thermal conductance deflection tabula rasa backlight changes, the distortion being caused by this change in size is just present in a part for picture partly, its result is, the integral body of original picture should be shown as when black, seepage part light, that is, there is light leak (spot) the significantly such problem that becomes.
From above-mentioned reason, motion has the technology (with reference to patent documentation 4) that replaces water system bonding agent with cationically polymerizable ultraviolet hardening bonding agent.
But cationically polymerizable ultraviolet hardening bonding agent is owing to producing dark reaction (rear polymerization) after ultraviolet ray is irradiated, therefore, when by the solidfied material coiling tubular of long size, has and when keeping, easily produce the such problem of curling custom.And the impact of humidity when cationically polymerizable ultraviolet hardening bonding agent is easily subject to solidify, has the easily such problem of inequality of solid state.Here, in order to manifest the solid state of homogeneous, be not ambient humidity, and need to strictly manage the water percentage that PVA is polarizer.
Free-radical polymerised ultraviolet hardening bonding agent such problem fewer aspect on be excellent.
But liquid crystal indicator, along with the expansion of its purposes, becomes and uses under various environment, for the Polarizer that forms liquid crystal indicator, require high environment resistant.
For example, for take the liquid crystal indicator of the mobile purposes that mobile phone is representative, require high wet-heat resisting durability.
As mentioned above, free-radical polymerised ultraviolet hardening bonding agent is compared with cationically polymerizable curing type bonding agent, is excellent on aspect all.
But, while using free-radical polymerised ultraviolet hardening bonding agent, if be exposed to for a long time under hygrothermal environment, easily reduce polarizing properties, have in the color of cutting off end and easily occur the polarizer crossed with iodine or dye coloring such problem that comes off.
In addition, for example, than hygrothermal environment more under exacting terms (, impregnated in the warm water of 60 ℃), the color that polarizer significantly occurs comes off.
That is, the today that becomes harsher in the environment for use of Polarizer, wish to have that further to have improved the Polarizer of the humidity resistance of Polarizer be in the past truth.
Further, for with the bonding Polarizer polyvinyl alcohol mesentery of easy and sufficient intensity and plastic foil, again motion and with the adhesive composition (patent documentation 5) of (methyl) acrylic acid series free-radical polymerised compound and cationically polymerizable compound.But this technology requires further to improve for punch process.
Patent documentation 1: Japanese kokai publication hei 09-258023 communique
Patent documentation 2: TOHKEMY 2005-208456 communique
Patent documentation 3: TOHKEMY 2004-37841 communique
Patent documentation 4: TOHKEMY 2008-233874 communique
Patent documentation 5: TOHKEMY 2008-260879 communique
Summary of the invention
The object of the present invention is to provide a kind of Polarizer, it take polyethenol series polarizer and diaphragm is constituting layer, excellent aspect the cementability of diaphragm and polarizer and punch process, and also excellent in water tolerance.
The inventor has carried out further investigation repeatedly in order to solve above-mentioned problem, it found that can reach described target by Polarizer shown below, thereby has completed the present invention.
; the present invention relates to Polarizer, it is characterized in that, it contains polyethenol series polarizer, Photocurable adhesive agent solidifies adhesive linkage and the diaphragm forming; its for across described adhesive linkage by the diaphragm Polarizer that the two sides of polarizer forms described in coating respectively
Described Photocurable adhesive agent contains host, optical free radical polymerization initiator and the light cationic polymerization initiators being comprised of free-radical polymerised compound and cationically polymerizable compound,
As described free-radical polymerised compound, the formed glass temperature that contains 60～99.8 quality % in described host is the free-radical polymerised compound (a) of the homopolymer of-80 ℃～0 ℃,
As described cationically polymerizable compound, in described host, contain the cationically polymerizable compound (c) that does not possess (methyl) acryloyl group of 0.02～40 quality %,
With respect to described host 100 mass parts, contain respectively described optical free radical polymerization initiator 1～10 mass parts, described smooth cationic polymerization initiators 0.5～5 mass parts.
Further, the present invention relates to photocurable adhesive for forming polarizing plate, it is characterized in that, contain the host, optical free radical polymerization initiator and the light cationic polymerization initiators that by free-radical polymerised compound and cationically polymerizable compound, are formed,
As described free-radical polymerised compound, the formed glass temperature that contains 60～99.8 quality % in described host is the free-radical polymerised compound (a) of the homopolymer of-80 ℃～0 ℃,
As described cationically polymerizable compound, in described host, contain the cationically polymerizable compound (c) that does not possess (methyl) acryloyl group of 0.02～40 quality %,
With respect to described host 100 mass parts, contain respectively described optical free radical polymerization initiator 1～10 mass parts, described smooth cationic polymerization initiators 0.5～5 mass parts.
Accompanying drawing explanation
Fig. 1 is for showing the sectional view (schematic diagram) of Polarizer one example of the present invention.
Fig. 2 is for showing the process flow diagram (schematic diagram) of polarizing plate making method one example of the present invention.
Symbol description
1,5 diaphragms
2 the 1st bond layers
3 polyethenol series polarizers
4 the 2nd bond layers
1 ' diaphragm 1 and layer 2 ' the duplexer being formed by solidification compound
5 ' diaphragm 5 and layer 4 ' the duplexer being formed by solidification compound
6 active energy beams
Embodiment
Below, for the preferred embodiment of the present invention, describe.By the present invention, can provide and take the Polarizer that polyethenol series polarizer and diaphragm be constituting layer, excellent Polarizer in cementability, punch process and water tolerance.
Adhesive linkage
Below, the relevant adhesive linkage (or bond layer) that forms Polarizer of the present invention is described.
Adhesive linkage (in Fig. 1 and 2, symbol is 2,4) is to solidify the layer that Photocurable adhesive agent forms.
Photocurable adhesive agent contains host and the polymerization initiator being comprised of photocurable compound.Host comprises free-radical polymerised composition (free-radical polymerised compound) and cationically polymerizable composition (cationically polymerizable compound).
Free-radical polymerised composition is to take can form the free-radical polymerised compound (a) that glass temperature is the homopolymer of-80 ℃～0 ℃ (below, also referred to as " free-radical polymerised compound (a) " or " low Tg free-radical polymerised compound (a) ") as neccessary composition, also can further contain and can form the free-radical polymerised compound (b) that glass temperature is the homopolymer of 60 ℃～250 ℃ (following, also referred to as " free-radical polymerised compound (b) " or " high Tg free-radical polymerised compound (b) ").; as free-radical polymerised composition; the glass temperature that contains homopolymer is the free-radical polymerised compound (a) of-80 ℃～0 ℃, and the glass temperature that at random contains homopolymer is the free-radical polymerised compound (b) of 60 ℃～250 ℃.
In low Tg free-radical polymerised compound (a), compound for simple function for example can be enumerated: with acrylic acid 2-hydroxy methacrylate (Tg:-9 ℃ of homopolymer, below identical), acrylic acid 2-hydroxy propyl ester (7 ℃), acrylic acid 4-hydroxyl butyl ester (55 ℃), be (methyl) acrylic acid terminal hydroxy group Arrcostab of representative;
Take (methyl) acrylic acid end alkyl-alkyl ester that acrylic acid 2-methoxyl ethyl ester (43 ℃), acrylic acid 3-methoxyl butyl ester (47 ℃), tridecyl acrylate (65 ℃) and methacrylic acid tridecyl ester (37 ℃) be representative;
Take end alkyl (gathering) aklylene glycol system (methyl) acrylate that diethylene glycol monoethyl ether acrylate (54 ℃), ethoxy diethylene glycol acrylate (51 ℃), methoxy poly (ethylene glycol) (n=9) acrylate (71 ℃) and methoxyl tripropylene glycol acrylate (75 ℃) be representative;
Acrylic acid phenoxy ethyl (15 ℃), acrylic acid trifluoro ethyl ester (10 ℃), ω-carboxyl-polycaprolactone acrylate (46 ℃) etc.
In addition, in low Tg free-radical polymerised compound (a), for polyfunctional compound, can enumerate: polyglycol (400) diacrylate (28 ℃), polyglycol (600) diacrylate (42 ℃), TEGDMA (5 ℃), ethoxylation (9) trimethylolpropane triacrylate (19 ℃) etc.
Photocurable adhesive agent in the present invention can combine aptly these materials and use.
Compound for the preferred simple function of low Tg free-radical polymerised compound (a).Even low Tg free-radical polymerised compound (a), if only use polyfunctional compound, has in the not preferred situation of cutting test aspect of performance described later.Here, in order to become also good compound of this cutting test performance, and with polyfunctional compound during as low Tg free-radical polymerised compound (a), in low Tg free-radical polymerised compound (a) (being 100 quality %), control as less than 40 quality % left and right, be preferably less than 10 quality % left and right.
Further, while using high Tg free-radical polymerised compound described later (b), this high Tg free-radical polymerised compound (b) is preferably not multifunctional yet, and preferred simple function.In other words, while using multifunctional free-radical polymerised compound as free-radical polymerised compound ((a) or (a)+(b)), preferably its ratio is less than 40 quality % left and right in host (being 100 quality %), more preferably less than 10 quality % left and right.
Or, more than the ratio of simple function free-radical polymerised compound in free-radical polymerised compound (free-radical polymerised compound (a) and the total (b) of the free-radical polymerised compound of simple function (a) or simple function) is preferably 60 quality %, more preferably more than 70 quality %, more preferably more than 90 quality %.
This free-radical polymerised compound (a) the more preferably glass temperature of homopolymer is the compound of-60 ℃～-20 ℃, and further preferably the glass temperature of homopolymer is the compound of-60 ℃～-40 ℃.
In these low Tg free-radical polymerised compounds (a), from the angle improving with the PVA cementability that is polarizer, preferably the compound with hydroxyl of (methyl) acrylic acid hydroxyalkyl acrylate etc., wherein, is preferably acrylic acid 4-hydroxyl butyl ester.Be difficult to reduce solidfied material Tg aspect on, even if there is hydroxyl, preferably do not use acrylic acid 2-hydroxy methacrylate and acrylic acid 2-hydroxy propyl ester yet.That is, the carbon number of the alkyl of (methyl) acrylic acid hydroxyalkyl acrylate is preferably 4～40 left and right.
In addition, at the cohesion that improves the bond layer after solidifying, strengthen in the aspect of bonding force, preferably further use ω-carboxyl-polycaprolactone list (methyl) acrylate as low Tg free-radical polymerised compound (a).Just; because the curability of ω-carboxyl-polycaprolactone list (methyl) acrylate is not fine; therefore can, by selecting aptly the kind of radical polymerization initiator or lamp that amount the is selected ultraviolet lamp aptly condition of cure such as Selective irradiation intensity or exposure or select aptly the kind of diaphragm or thickness etc. aptly, carry out Curing.There is no particular limitation for the degree of polymerization (n) of the caprolactone of ω-carboxyl-polycaprolactone list (methyl) acrylate, still, is preferably left and right, n=2～20.
For example, with the 100 quality % that add up to of host, the free-radical polymerised compound of 60～99.8 quality % (a) is preferably that 10～99.8 quality %, ω-carboxyl-polycaprolactone list (methyl) acrylate are that each scope of 0～50 quality % combines according to (methyl) acrylic acid hydroxyalkyl acrylates such as acrylic acid 4-hydroxyl butyl esters.
In addition, while mixing ω-carboxyl-polycaprolactone list (methyl) acrylate, according to (methyl) acrylic acid hydroxyalkyl acrylate, be preferably further that 10～99.7 quality %, ω-carboxyl-polycaprolactone list (methyl) acrylate are the scope use of 0.01～50 quality %.
High Tg free-radical polymerised compound (b) for any mixing, for example can enumerate: methacrylic acid dicyclopentenyloxyethyl methacrylate (Tg:180 ℃ of homopolymer, below identical), trifluoroethyl methacrylate (81 ℃), Tert-butyl Methacrylate (113 ℃), β-dimethyl-aminoethylmethacrylate (65 ℃), tetrahydrofurfuryl methacrylate (68 ℃), isobornyl acrylate (85 ℃) and acryloyl morpholine (106 ℃) etc.Wherein, from stable on heating viewpoint, preferably use isobornyl acrylate and acryloyl morpholine.
This free-radical polymerised compound (b) the more preferably glass temperature of homopolymer is the compound of 60 ℃～200 ℃, and further preferably the glass temperature of homopolymer is the compound of 80 ℃～150 ℃.
Photocurable adhesive agent of the present invention can combine aptly these materials and use.
In addition, the Tg by described low Tg free-radical polymerised compound (a), formed each homopolymer of high Tg free-radical polymerised compound (b) is the value of being obtained by following operation.
Each compound of appropriate amount and initiating agent are packed in plastic container, irradiation ultraviolet radiation, material after solidifying is got 10mg as mensurations sample, and use differential scanning calorimeter (DSC) is measured with the programming rate of 10 ℃/min or 20 ℃/min.
The cationically polymerizable compound (c) (below also referred to as " cationically polymerizable compound (c) ") without (methyl) acryloyl group is the compound that has the functional group of cationically polymerizable and do not have (methyl) acryloyl group, for example can enumerate: 3, 4-epoxycyclohexyl methyl-3, 4-epoxycyclohexane carboxylate, 2-(3, 4-epoxycyclohexyl-5, 5-spiral shell-3, 4-epoxy radicals) cyclohexane--diox, two (3, 4-epoxycyclohexyl methyl) adipate, two (3, 4-epoxy radicals-6-methyl cyclohexane ylmethyl) adipate, vinyl cyclohexene monoxide, 1, 2-epoxy radicals-4-vinyl cyclohexane etc. contains the compound of more than 1 ester ring type epoxy radicals or has the compound of oxa-cyclobutyl in 1 molecule.Cationically polymerizable compound (c) is being undertaken the task of the water tolerance that improves the adhesive linkage after solidifying.
In thering is the compound of ester ring type epoxy radicals, from reactive angle, preferably use 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexane carboxylate.
In the present invention, from the viewpoint of guaranteeing that bonding force and punch process are good, cationically polymerizable compound (c) selects not have the compound of (methyl) acryloyl group.Although can will there is cationically polymerizable compound and above-mentioned (c) the use of (methyl) acryloyl group; but; the combined amount of the cationically polymerizable compound with (methyl) acryloyl group in this case; in host 100 quality %; must be controlled at less than 20 quality % left and right, preferably be controlled at less than 10 quality % left and right.
Or, in whole cationically polymerizable compound, more than the shared ratio of cationically polymerizable compound (c) without (methyl) acryloyl group is preferably 50 quality %, more preferably more than 75 quality %.
It is that 60～99.8 quality %, cationically polymerizable compound (c) are 0.02～40 quality % that the host of Photocurable adhesive agent contains free-radical polymerised compound (a), preferably free-radical polymerised compound (a) is that 60～99 quality %, cationically polymerizable compound (c) are 1～40 quality %, and more preferably free-radical polymerised compound (a) is that 90～99 quality %, cationically polymerizable compound (c) are 1～10 quality %.
Low Tg free-radical polymerised compound (a) is if be less than 60 quality %, and formed adhesive linkage becomes really up to the mark, not only can not guarantee bonding force, and has worsened punch process.
And on the other hand, low Tg free-radical polymerised compound (a) is if more than 99.8 quality %,, the situation that contains hardly cationically polymerizable compound (c), the water tolerance variation of formed adhesive linkage, if Polarizer is immersed in warm water, the color relation of PVA polarizer can come off.
While using the cellulose acetate resin films such as Triafol T as diaphragm, high Tg free-radical polymerised compound (b) contributes to the raising of bonding force.
While using high Tg free-radical polymerised compound (b), preferred low Tg free-radical polymerised compound (a) is that 60～75 quality %, high Tg free-radical polymerised compound (b) are that 0.01～39.98 quality %, cationically polymerizable compound (c) are 0.02～24.99 quality %, and more preferably low Tg free-radical polymerised compound (a) is that 60～70 quality %, high Tg free-radical polymerised compound (b) are that 10～35 quality %, cationically polymerizable compound (c) are 5～20 quality %.
Or the Photocurable adhesive agent in a preferred embodiment is the bonding agent of following feature:
As host, contain and can form the simple function free-radical polymerised compound (a) that glass temperature is the homopolymer of-80 ℃～0 ℃: 60～99.8 quality %, can form the simple function free-radical polymerised compound (b) that glass temperature is the homopolymer of 60 ℃～250 ℃: 0～39.98 quality % and there is cationically polymerizable functional group and do not there is the cationically polymerizable compound (c) of (methyl) acryloyl group: 0.02～40 quality % (wherein, above-mentioned (a)～(c) add up to 100 quality %);
And contain optical free radical polymerization initiator (d) as polymerization initiator: 1～10 mass parts (adding up to 100 mass parts with respect to above-mentioned (a)～(c)) and light cationic polymerization initiators (e): 0.5～5 mass parts (adding up to 100 mass parts with respect to above-mentioned (a)～(c)).
Further preferably contain low Tg free-radical polymerised compound (a) 60～99 quality %, high Tg free-radical polymerised compound (b) 0～39 quality %, and cationically polymerizable compound (c) 1～40 quality %.
In Photocurable adhesive agent of the present invention, except low Tg free-radical polymerised compound (a) and high Tg free-radical polymerised compound (b), can also further add other free-radical polymerised compound.Free-radical polymerised compound as other can be enumerated urethane acrylate, epoxy acrylate, polyester acrylate and polyether acrylate.But as mentioned above, free-radical polymerised compound is preferably used in limited blend range.
In addition, in Photocurable adhesive agent of the present invention, if needed, can also add suitable adjuvant.At the bonding force that can increase with diaphragm, and can suppress the contraction aspect of Polarizer, preferred silane coupling agent is as adjuvant.As silane coupling agent, preferably there is acryloyl group.
Photocurable adhesive agent of the present invention contains optical free radical polymerization initiator (d).
For optical free radical polymerization initiator (d), have no particular limits, for example can enumerate gorgeous good solid (IRGACURE)-184,907,651,1700,1800,819,369,261, moral firmly-TPO (DAROCUR-TPO) (Ciba company system), moral is-1173 (DAROCUR-1173) (Merck & Co., Inc.'s system (Merck), Esacure-KIP 150, TZT (Japanese Waja company's system (Japanese SiberHegner)), Kayacure BMS, Kayacure DMBI (Japanese chemical drug company system) etc. firmly.
Wherein, aspect the bond layer after improving photocuring transparent, preferably use the DAROCUR-TPO that carried out photobleaching.
Total 100 mass parts with respect to described free-radical polymerised compound (a), (b) and cationically polymerizable compound (c), the blending ratio of optical free radical polymerization initiator (d) is 1～10 mass parts, is preferably 1～5 mass parts.
Photocurable adhesive agent of the present invention contains light cationic polymerization initiators (e).
As light cationic polymerization initiators (e) such as enumerating the sulfonium salts such as UVACURE 1590 (Daicel-Cytec system), CPI-110P (San-Apro system), or the salt compounded of iodine such as IRGACURE 250 (Ciba company system), WPI-113 (He Guangchun medicine company system), Rp-2074 (Luo Diya Japanese firm system) etc.
Total 100 mass parts with respect to described free-radical polymerised compound (a), (b) and cationically polymerizable compound (c), the blending ratio of light cationic polymerization initiators (e) is 0.5～10 mass parts, is preferably 0.5～5 mass parts.
With regard to Photocurable adhesive agent, except above-mentioned host and polymerization initiator, in not damaging the scope of effect of the present invention, can also contain as required the various known adjuvants such as polymerization inhibitor, polymerization initiation auxiliary agent, ultraviolet light absorber, plastifier, colorant, antioxidant, defoamer and plastifier.
Polarizer
The polyethenol series polarizer using in Polarizer of the present invention (in Fig. 1,2, symbol is 3) is described.
As forming polarizer, become the polyvinyl alcohol resin of polarizer base material, can enumerate polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer etc., but from water tolerance aspect, optimal ethylene-ethenol copolymer.As polyvinyl alcohol (PVA), can enumerate and remainingly have the partly-hydrolysed polyvinyl alcohol (PVA) of tens of % acetates or the not fully saponified polyvinyl alcohol (PVA) of remaining acetate or the modified polyvinylalcohol that hydroxyl is modified etc., but without particular limitation of in these alcohol.Polyvinyl alcohol resin can be used a kind individually, and also two or more kinds may be used.
As the object lesson of above-mentioned polyvinyl alcohol (PVA), can enumerate RS polymkeric substance RS-110 (saponification degree=99%, the degree of polymerization=1 of (strain) Kuraray system, 000), with Kuraray POVAL LM-20SO (saponification degree=40%, the degree of polymerization=2 of company's system, 000) the Gohsenol NM-14 (saponification degree=99%, the degree of polymerization=Isosorbide-5-Nitrae 00) that, Japanese synthetic chemical industry (strain) is made etc.Polyvinyl alcohol (PVA) is such as using base catalyst etc. that the polymkeric substance of the fatty acid vinyl esters such as vinyl acetate, propionate, pivalic acid vinyl acetate is carried out saponification and obtained.
Above-mentioned ethylene-vinyl alcohol copolymer is the saponified of ethene and vinyl acetate copolymer,, ethane-acetic acid ethyenyl ester random copolymers is carried out saponification and obtained, from the remaining partly-hydrolysed thing that has tens of % by mole of acetates, to only remaining have the saponified of several % by mole of acetates or not the fully saponified thing of remaining acetate all comprise, there is no particular limitation.
Polarizer can, according to known method,, be orientated iodine or dichromatic dye (bitintability pigment) absorption and obtain above-mentioned polyvinyl alcohol resin filming by methods such as cast-forming methods.Described polarizer can be also to carry out polarizer crosslinked or that stretch by boric acid etc.While stretching, can be before dyeing, these any one stages carry out in dyeing or after dyeing, as the shape of polarizer, there is no particular limitation, such as enumerating film etc.In addition, in this instructions, the term of " film ", except the little object of thickness (thickness is less than 1mm), also comprises thick sheet (for example, thickness is 1～5mm).There is no particular limitation for the thickness of polarizer, for example, preferably about 10～40 μ m.
Diaphragm
The diaphragm using in Polarizer of the present invention (in Fig. 1,2, symbol is 1,5) is described.
There is no particular limitation for diaphragm, concrete, can be used as present Polarizer diaphragm and by cellulose acetate resin films such as the most widely used Triafol Ts (TAC), or the transparent resin film lower than the moisture permeability of Triafol T.
As the material of the low diaphragm of the moisture permeability of constituent ratio Triafol T such as using the thermoplastic resin that the transparency, physical strength, thermal stability, dash minute property and isotropy etc. are excellent.Object lesson as such thermoplastic resin can be enumerated cyclic olefine resin and acrylic resin.
Cyclic olefine resin is using cyclic olefin as polymerized unit and the general name of the resin of polymerization.As concrete example, can enumerate open loop (being total to) polymkeric substance of cyclic olefin, the multipolymer of the alpha-olefins such as addition polymer, cyclic olefin and ethene, propylene of cyclic olefin (representative be random copolymers), with with these graft polymer of unsaturated carboxylic acid or derivatives thereof modification, and these hydride etc., preferred norbornene resin.Norbornene resin film can obtain by the known method of the records such as JP 2005-164632 communique, JP 2006-201736 communique, JP 2008-233279 communique.
As cyclic olefine resin, on market, there are various products.As concrete example, can enumerate the trade name " ZEONOR " of Japanese auspicious father-in-law (ZEON) Co., Ltd. system, the trade name " TOPAS " of the trade name " ARTON " of JSR Corp.'s system, TICONA company system and the trade name " Apel " of Mitsui Chemicals, Inc's system.
Acrylic resin is with headed by polymethylmethacrylate, the resin (=multipolymer) that alkyl esters (methyl) acrylate such as methyl methacrylate or butyl methacrylate of take are major component.According to circumstances, ooze and close and filming with other resin.Acrylic acid mesentery can obtain by the known method of the records such as JP 2002-361712 communique.
As acrylic acid mesentery, on market, there are various products.As concrete example, can enumerate the trade name " Acryplen " of Mitsubishi Rayon Co., Ltd's system, or the trade name " Sunduren " of KANEKA company system.
The diaphragm using in Polarizer of the present invention, 1,5 two sides can be same composition, can be also different compositions.For example, use cyclic olefine resin molding in 1, and in 5, use acrylic resin film, also without any problem.
Can determine aptly the thickness of diaphragm, still, from the workability such as intensity or treatability, thin layer equal angles, be generally 1～500 μ m left and right.Be particularly preferably 1～300 μ m, more preferably 5～200 μ m.Diaphragm 1 and 5 thickness can be identical, also can be different.
In addition, while diaphragm being set in the both sides of polarizer, its inside and outside side can use the diaphragm being formed by identical polymeric material, also can use the diaphragm being formed by different polymeric material etc.For example, even if use the situation of acrylic acid mesentery on the two sides of polarizer, the kind of acrylic acid series polymeric compounds can be mutually different, and the adjuvant of mixing also can be mutually different, without any restriction.
Polarizer of the present invention can carry out following operation and obtain.
That is, preferably by following method, manufacture: on the face of the 1st diaphragm 1 one sides, apply the 1st Photocurable adhesive agent, form the 1st curability bond layer 2 ',
On the face of the 2nd diaphragm 5 one sides, apply the 2nd Photocurable adhesive agent, form the 2nd curability bond layer 4 ',
Then, on each face of polyethenol series polarizer 3, simultaneously/or overlap in order the 1st curability bond layer 2 ' and the 2nd curability bond layer 4 ',
From the 2nd diaphragm 5 sides, irradiate active energy beam, solidify the 1st curability bond layer 2 ' and the 2nd curability bond layer 4 '.
Above-mentioned curability bond layer 2 ' and 4 ', diaphragm 1 and 5 can be identical mutually separately, also can be mutually different separately.That is, curability bond layer 2 ' and curability bond layer 4 ' (in other words, the 1st Photocurable adhesive agent and the 2nd Photocurable adhesive agent) can be same compositions, can be also different compositions.The bond layer 2 forming and 4 thickness can be identical mutually, also can be different, and there is no particular limitation, but be generally preferably 0.1 μ m～50 μ m, more preferably 0.5 μ m～20 μ m.
Below, take Fig. 2 as basis, each operation is described.
Operation (a)
Operation (a) is following operation: as shown in Fig. 2 (a); in the one side separately of diaphragm 1 and 5; coating adhesive layer formation Photocurable adhesive agent, is dried etc. as required, obtains having curability bond layer 2 ', 4 ' duplexer 1 ', 5 '.
As the coating process of Photocurable adhesive agent, there is no particular limitation, such as enumerating squash type (die) rubbing method, rolling method, intaglio plate rubbing method, spin-coating method etc.
Operation (b)
Operation (b) is following operation: as shown in Fig. 2 (b); respectively; the duplexer 1 ' will with diaphragm 1 and curability bond layer 2 ' overlaps at a face of polyethenol series polarizer 3 (in figure for above), will have the duplexer 5 ' coincidence of diaphragm 5 and curability bond layer 4 ' at another face of polyethenol series polarizer 3 (in figure for below).
Operation (c)
Operation (c) is following operation: as shown in Fig. 2 (c), by irradiating active energy beam 6, the curability bond layer 2 ', 4 ' that makes to be clipped between diaphragm 1,5 and polyethenol series polarizer 3 solidifies, and forms bond layer 2,4.
In figure, although shown the situation of irradiating active energy beams 6 from diaphragm 5 sides,, also can irradiate active energy beam 6 from diaphragm 1 side, also can be from both sides simultaneously, or from both sides, irradiate in turn active energy beam 6.
The exposure of active energy beam is not the amount being specially limited, and still, preferably illumination wavelength is that 200～450nm, illumination are 1～500mW/cm
2light to make exposure be 10～5000mJ/cm
2and expose.Exposure is less than 10mJ/cm
2time, can not promote solidifying of ultra-violet solidified composition, likely can not bring into play desirable performance, exposure is greater than 5000mJ/cm
2time, it is very long that irradiation time becomes, and has problem in throughput rate.As the kind of the active energy beam irradiating, can enumerate visible ray, ultraviolet ray, infrared ray, X ray, alpha ray, β ray, gamma-rays etc., particularly preferably ultraviolet ray.Such as preferred use high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, metal halide lamp and Excimer lamp etc. of irradiation unit as light.
Irradiate after active energy beam 6, also can at room temperature carry out about 1 week aging.
Via operation (c), curability bond layer 2 ', 4 ' solidifies and becomes bond layer 2,4, completes polarizer 3 and diaphragm 1 and 5 across the bonding Polarizer forming of bond layer 2,4 (with reference to (d) in Fig. 1, Fig. 2).
In addition, Polarizer of the present invention can also be manufactured by following method: on a face of polyethenol series polarizer 3, apply Photocurable adhesive agent, form the 1st curability bond layer 2 ', with the 1st diaphragm 1, cover the surface of formed the 1st curability bond layer 2 ', then, on another face of polyethenol series polarizer 3, apply Photocurable adhesive agent, form the 2nd curability bond layer 4 ', with the 2nd diaphragm 5, cover the surface of formed the 2nd curability bond layer 4 ', next, from the 2nd diaphragm 5 sides, irradiate active energy beam, solidify the 1st curability bond layer 2 ' and the 2nd curability bond layer 4 '.
Polarizer is to contain as mentioned above to take the plate that polarizer, adhesive linkage and diaphragm be necessary formation, but also can contain other any formation.For example, in position arbitrarily, can contain as required reflection horizon, anti-reflection layer, hard conating, stain-proofing layer, anti-fog layer, adherent layer etc.
Embodiment
The Production Example of (polyethenol series polarizer)
Boric acid 20 mass parts, iodine 0.2 mass parts and potassium iodide 0.5 mass parts are dissolved in the water of 480 mass parts, are modulated into dyeing liquor.In this dyeing liquor, flood PVA film (vinylon (Vinylon) film #40, Aicello company system) after 30 seconds, in one direction with 2 times of stretched film, dry, obtaining thickness is the PVA polarizer of 30 μ m.
Embodiment 1
Use the acrylic film that contains ultraviolet light absorber of the beautiful sun of Mitsubishi (strain) system: HBD-002 (50 μ m) is as diaphragm 1; use the cycloolefin film ZEONOR film " ZF-14 " (100 μ m) that does not contain ultraviolet light absorber of Nippon Zeon Co., Ltd.'s system as diaphragm 5; on its surface separately, with 300Wmin/m
2discharge capacity, carry out corona treatment.After surface treatment in 1 hour; use ring rod coater #3 on diaphragm 1 and 5, to be coated with respectively the photopolymerizable composition shown in table 1; form curability bond layer 2 ', 4 '; between this curability bond layer 2 ', 4 ', clamp above-mentioned PVA polarizer, obtaining by diaphragm 1/ curability bond layer 2 '/PVA is the duplexer that polarizer 3/ curability bond layer 4 '/diaphragm 5 forms.
With cellophane tape, fix this duplexer surrounding, diaphragm 1 and tinplate dermatotome are joined, thereby be fixed on tinplate dermatotome.
With UV irradiation unit (Toshiba's system, high-pressure mercury-vapor lamp), from diaphragm 5 sides, irradiating maximal illumination is 500mW/cm
2, integration light quantity is 800mJ/cm
2ultraviolet ray, make Polarizer.The thickness of formed each bond layer is 3～4 μ m.
Embodiment 2～8, comparative example 1～7
Except changing as shown in Table 1 and Table 2 photo-curable polymeric compositions, make similarly to Example 1 Polarizer, according to method described later, evaluate its performance.
Embodiment 9 and 10
Except respectively the diaphragm in embodiment 91 being changed to the Triafol T mesentery containing ultraviolet light absorber of Fujiphoto (strain) system: trade name " FujiTac " (80 μ m); by the diaphragm in embodiment 10 1 be changed to Nippon Zeon Co., Ltd.'s system containing the cycloolefin film ZEONOR film " ZF-14 " (100 μ m) of ultraviolet light absorber not in addition; obtain similarly to Example 3 Polarizer, carry out same evaluation.
Embodiment 11
Except diaphragm 1 being changed to the Triafol T mesentery containing ultraviolet light absorber of Fujiphoto (strain) system: trade name " FujiTac " (80 μ m); diaphragm 5 is changed to the Triafol T mesentery that does not contain ultraviolet light absorber: trade name " TACPHAN N882GL " (80 μ m) in addition; obtain similarly to Example 3 Polarizer, carry out same evaluation.
Embodiment 12
By diaphragm 1,5 similarly to Example 11, the Photocurable adhesive agent that contains high Tg free-radical polymerised compound (b) shown in use table 1, obtains Polarizer similarly to Example 3, carries out same evaluation.
Embodiment 13
Except diaphragm 1,5 is become Nippon Zeon Co., Ltd.'s system not containing the cycloolefin film ZEONOR film " ZF-14 " (100 μ m) of ultraviolet light absorber, use Photocurable adhesive agent similarly to Example 12, obtain Polarizer, carry out same evaluation.
Embodiment 14 and 15
By diaphragm 1,5 similarly to Example 13; comprising polyfunctional acrylic ester (b) or thering is the Photocurable adhesive agent of the cationically polymerizable compound (x) of acryloyl group shown in use table 1; obtain similarly to Example 13 Polarizer, carry out same evaluation.
Comparative example 8～11
Diaphragm 1,5 be Nippon Zeon Co., Ltd.'s system not containing cycloolefin film ZEONOR film " ZF-14 " (100 μ of ultraviolet light absorber.M), the Photocurable adhesive agent that uses table 2 to record, obtains Polarizer, carries out same evaluation.
Bonding force (peel strength)
Use cutting machine the Polarizer obtaining to be cut into the size of 25mm * 150mm, as sample.By two sides adhesion adhesive tape (DF8712S processed of Toyo Ink Manufacturing Co., Ltd.), sample is sticked on sheet metal.Between the diaphragm of sample (Polarizer) and polarizer, set in advance the beginning of peeling off, under 23 ℃, 50%RH environment, with peeling rate: 300mm/min, measure bonding force.Bonding force in table is evaluated by following benchmark.
2.5 (N/25mm) above ◎
More than 1.5 (N/25mm)～less than 2.5 (N/25mm) zero
More than 1.0 (N/25mm)～less than 1.5 (N/25mm) △
Less than 1.0 (N/25mm) *
Cutting test (closing force test)
Between the diaphragm of the Polarizer obtaining and polarizer, put into the cutter of cutting machine, the cutter mode of entrance while advancing cutter with following benchmark evaluation.
The cutter of cutting machine is not easy to enter intermembranous ◎
While advancing the cutter of cutting machine, cutter stops zero in the place that enters intermembranous 4～5mm
That the cutter of cutting machine successfully enters is intermembranous *
Punch process
For the Polarizer of making, use the cutter of the 100mm * 100mm of Dumbbell company system, from diaphragm 1 side blow, press.
With the state of peeling off around the Polarizer of visualization institute punching press.
Area (100cm with respect to Polarizer
2), the ratio of the area of peeling off (%) be less than 1% for ◎, more than 1% and be less than 2% be more than zero, 2% and be less than 3% be △, peel off area and be more than 3% be *.
Warm water immersion test (water tolerance)
Use cutting machine the Polarizer obtaining to be cut into the size of 25mm * 50mm, as sample, it is flooded respectively after 24 hours and 72 hours in thermostatted water (60 ℃), by the color of visualization sample (Polarizer) degree that comes off.
With respect to the area of Polarizer, color come off the ratio (%) of area be less than 10% be ◎, more than 10% and be less than 30% be more than zero, 30% be *.
In table 1 and table 2, show evaluation result.About the details of the compound that uses and diaphragm on the books below table 1.
As shown in table 1, any one embodiment can be formed on polarizer excellent in cementability, punch process and water tolerance.
Embodiment 3 and embodiment 6 are that to use the content that does not contain high Tg free-radical polymerised compound (b) and low Tg free-radical polymerised compound (a) be the situation of the Photocurable adhesive agent of 90 quality %, as low Tg free-radical polymerised compound (a) except acrylic acid 4-hydroxyl butyl ester, and higher than the cohesion of embodiment 6 with the embodiment 3 of ω-carboxyl-polycaprolactone acrylate, excellent aspect bonding force.
In addition; embodiment 12 is situations of using the Photocurable adhesive agent that contains high Tg free-radical polymerised compound (b); compare with the embodiment 11 that does not contain high Tg free-radical polymerised compound (b); due at diaphragm for excellent aspect the cementability of three cellulose acetate membrane; therefore, excellent aspect bonding force and water tolerance.
Further, embodiment 13 compares with embodiment 12, is the situation that diaphragm is used the cycloolefin film that moisture-penetrability is low, more excellent aspect water tolerance.
And on the other hand, use the comparative example 1 of the Photocurable adhesive agent that does not contain cationically polymerizable compound (c), even the water tolerance of 24 hours is also bad.
In addition, any one in the poor comparative example 2～5 and 10 of low Tg free-radical polymerised compound (a) is all possible because of the adhesive linkage after solidifying, become really up to the mark, and bonding force is diminished, and punch process is also bad.
Further; comparative example 6,7 is that the content of low Tg free-radical polymerised compound (a) is few; and replace the high Tg free-radical polymerised compound of simple function (b) with the free-radical polymerised compound of 3 officials' energy; and use the compound with cationically polymerizable functional group and (methyl) acryloyl group to replace the situation of cationically polymerizable compound (c), bonding force is minimum.
Comparative example 8 and 9 low Tg free-radical polymerised compound (a) although content be sufficient; but it is to use the compound with cationically polymerizable functional group and (methyl) acryloyl group to replace the situation of cationically polymerizable compound (c), and bonding force is minimum.
In addition, although comparative example 4～9 bonding forces are minimum, water tolerance is good, and it is good that one of its reason is considered to test shown adaptation by cutting machine.
Claims (11)
1. a Polarizer, is characterized in that, it is to contain polyethenol series polarizer, Photocurable adhesive agent to solidify adhesive linkage and the diaphragm forming, and the Polarizer that formed by diaphragm coating respectively across described adhesive linkage of the two sides of described polarizer,
Described Photocurable adhesive agent contains host, optical free radical polymerization initiator and the light cationic polymerization initiators being comprised of free-radical polymerised compound and cationically polymerizable compound,
As described free-radical polymerised compound, the free acrylic acid 2-of the choosing hydroxy methacrylate that contains 60～99.8 quality % in described host, acrylic acid 4-hydroxyl butyl ester, acrylic acid 2-methoxyl ethyl ester, acrylic acid 3-methoxyl butyl ester, methacrylic acid tridecyl ester, diethylene glycol monoethyl ether acrylate, ethoxy diethylene glycol acrylate, acrylic acid phenoxy ethyl, acrylic acid trifluoro ethyl ester, ω-carboxyl-polycaprolactone acrylate, polyglycol (400) diacrylate, polyglycol (600) diacrylate, the group that ethoxylation (9) trimethylolpropane triacrylate forms, can form glass temperature is the free-radical polymerised compound (a) of the homopolymer of-80 ℃～0 ℃,
The ratio of the simple function free-radical polymerised compound in described free-radical polymerised compound (a) is more than 90 quality %,
As described cationically polymerizable compound; in described host, contain the choosing free 3 of 0.02～40 quality %; 4-epoxycyclohexyl methyl-3; 4-epoxycyclohexane carboxylate, 2-(3; 4-epoxycyclohexyl-5; 5-spiral shell-3; 4-epoxy radicals) cyclohexane--diox, two (3; 4-epoxycyclohexyl methyl) adipate, two (3; 4-epoxy radicals-6-methyl cyclohexane ylmethyl) adipate, 1; the cationically polymerizable compound (c) group, that do not possess (methyl) acryloyl group that 2-epoxy radicals-4-vinyl cyclohexane forms
With respect to described host 100 mass parts, contain respectively described optical free radical polymerization initiator 1～10 mass parts, described smooth cationic polymerization initiators 0.5～5 mass parts.
2. Polarizer according to claim 1, wherein, the group that described free-radical polymerised compound (a) selects free acrylic acid 4-hydroxyl butyl ester, ω-carboxyl-polycaprolactone single-acrylate, Hydroxyethyl Acrylate, polyglycol (400) diacrylate to form
Described cationically polymerizable compound (c) is 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexane carboxylate.
3. Polarizer according to claim 1, wherein, in described host, contains acrylic acid 4-hydroxyl butyl ester 10～99.8 quality %, ω-carboxyl-polycaprolactone single-acrylate 0～50 quality % as described free-radical polymerised compound (a).
4. Polarizer according to claim 1, wherein, described Photocurable adhesive agent further contains can form the free-radical polymerised compound (b) that glass temperature is the homopolymer of 60 ℃～250 ℃.
5. Polarizer according to claim 1, wherein, described cationically polymerizable compound (c) shared ratio in described cationically polymerizable compound is more than 75 quality %.
6. a photocurable adhesive for forming polarizing plate, is characterized in that, contains the host, optical free radical polymerization initiator and the light cationic polymerization initiators that free-radical polymerised compound and cationically polymerizable compound, consist of,
As described free-radical polymerised compound, the free acrylic acid 2-of the choosing hydroxy methacrylate that contains 60～99.8 quality % in described host, acrylic acid 4-hydroxyl butyl ester, acrylic acid 2-methoxyl ethyl ester, acrylic acid 3-methoxyl butyl ester, methacrylic acid tridecyl ester, diethylene glycol monoethyl ether acrylate, ethoxy diethylene glycol acrylate, acrylic acid phenoxy ethyl, acrylic acid trifluoro ethyl ester, ω-carboxyl-polycaprolactone acrylate, polyglycol (400) diacrylate, polyglycol (600) diacrylate, the group that ethoxylation (9) trimethylolpropane triacrylate forms, can form glass temperature is the free-radical polymerised compound (a) of the homopolymer of-80 ℃～0 ℃,
The ratio of the simple function free-radical polymerised compound in described free-radical polymerised compound (a) is more than 90 quality %,
As described cationically polymerizable compound; in described host, contain the choosing free 3 of 0.02～40 quality %; 4-epoxycyclohexyl methyl-3; 4-epoxycyclohexane carboxylate, 2-(3; 4-epoxycyclohexyl-5; 5-spiral shell-3; 4-epoxy radicals) cyclohexane--diox, two (3; 4-epoxycyclohexyl methyl) adipate, two (3; 4-epoxy radicals-6-methyl cyclohexane ylmethyl) adipate, 1; the cationically polymerizable compound (c) group, that do not possess (methyl) acryloyl group that 2-epoxy radicals-4-vinyl cyclohexane forms
With respect to described host 100 mass parts, contain respectively described optical free radical polymerization initiator 1～10 mass parts, described smooth cationic polymerization initiators 0.5～5 mass parts.
7. photocurable adhesive for forming polarizing plate according to claim 6, wherein, the group that described free-radical polymerised compound (a) selects free acrylic acid 4-hydroxyl butyl ester, ω-carboxyl-polycaprolactone single-acrylate, Hydroxyethyl Acrylate, polyglycol (400) diacrylate to form
Described cationically polymerizable compound (c) is 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexane carboxylate.
8. according to the photocurable adhesive for forming polarizing plate described in claim 6 or 7, wherein, contain acrylic acid 4-hydroxyl butyl ester 10～99.8 quality %, ω-carboxyl-polycaprolactone single-acrylate 0～50 quality % as described free-radical polymerised compound (a).
9. according to the photocurable adhesive for forming polarizing plate described in claim 6 or 7, wherein, further contain and can form the free-radical polymerised compound (b) that glass temperature is the homopolymer of 60 ℃～250 ℃.
10. a manufacture method for Polarizer, it is the manufacture method of the Polarizer described in any one in claim 1～5, it is characterized in that,
Described Polarizer comprises described polarizer, described Photocurable adhesive agent solidifies the 1st and the 2nd adhesive linkage, the 1st and the 2nd diaphragm forming,
A face separately that described Photocurable adhesive agent is coated to respectively to the 1st and the 2nd diaphragm forms the 1st and the 2nd Photocurable adhesive agent layer,
At two sides the stacked the described the 1st and the 2nd diaphragm of described polarizer, make the described the 1st and the 2nd Photocurable adhesive agent layer become inner side,
By the described the 1st and/or the 2nd diaphragm, irradiate active energy beam, make the described the 1st and the 2nd Photocurable adhesive agent layer be solidified to form the 1st and the 2nd adhesive linkage.
The manufacture method of 11. 1 kinds of Polarizers, it is the manufacture method of the Polarizer described in any one in claim 1～5, it is characterized in that,
Described Polarizer comprises described polarizer, described Photocurable adhesive agent solidifies the 1st and the 2nd adhesive linkage, the 1st and the 2nd diaphragm forming,
A face that described Photocurable adhesive agent is coated to described polarizer forms the 1st Photocurable adhesive agent layer, at stacked the 1st diaphragm in the surface of described the 1st Photocurable adhesive agent layer,
Another face that described Photocurable adhesive agent is coated to described polarizer forms the 2nd Photocurable adhesive agent layer, at stacked the 2nd diaphragm in the surface of described the 2nd Photocurable adhesive agent layer,
By the described the 1st and/or the 2nd diaphragm, irradiate active energy beam, make the described the 1st and the 2nd Photocurable adhesive agent layer be solidified to form the 1st and the 2nd adhesive linkage.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-204197 | 2009-09-04 | ||
| JP2009204197 | 2009-09-04 | ||
| JP2010095020A JP4561936B1 (en) | 2009-09-04 | 2010-04-16 | Polarizing plate and light curable adhesive for forming polarizing plate |
| JP2010-095020 | 2010-04-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102012535A CN102012535A (en) | 2011-04-13 |
| CN102012535B true CN102012535B (en) | 2014-08-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010266175.9A Active CN102012535B (en) | 2009-09-04 | 2010-08-27 | Polarizing plate and photocurable adhesive for forming polarizing plate |
Country Status (4)
| Country | Link |
|---|---|
| JP (2) | JP4561936B1 (en) |
| KR (1) | KR101010574B1 (en) |
| CN (1) | CN102012535B (en) |
| TW (1) | TWI404784B (en) |
Families Citing this family (60)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3242131A1 (en) * | 1981-11-18 | 1983-05-26 | General Electric Co., Schenectady, N.Y. | Control arrangement for a metal rolling mill and a method for compensating shock loading |
| KR101072371B1 (en) * | 2010-09-20 | 2011-10-11 | 주식회사 엘지화학 | Adhesive for polarizing plate and polarizing plate comprising the same |
| JP5610307B2 (en) * | 2010-09-20 | 2014-10-22 | エルジー・ケム・リミテッド | Adhesive composition for polarizing plate, polarizing plate and optical element containing the same |
| JP5484282B2 (en) * | 2010-09-27 | 2014-05-07 | 日東電工株式会社 | Active energy ray-curable resin composition, adhesive layer and laminate |
| JP5313297B2 (en) * | 2010-12-24 | 2013-10-09 | 日東電工株式会社 | Active energy ray-curable adhesive composition, polarizing plate, optical film, and image display device |
| JP6298248B2 (en) * | 2010-12-24 | 2018-03-20 | 日東電工株式会社 | Active energy ray-curable adhesive composition, polarizing plate, optical film, and image display device |
| US20140045966A1 (en) * | 2011-03-07 | 2014-02-13 | Shihei Motofuji | Photosensitive composition. cured article, and method for producing actinically cured article |
| JP2013035968A (en) * | 2011-08-09 | 2013-02-21 | Toyo Ink Sc Holdings Co Ltd | Photocurable adhesive for forming polarizing plate and polarizing plate |
| KR101742335B1 (en) * | 2011-08-19 | 2017-06-01 | 주식회사 엘지화학 | Polarizer |
| KR101886193B1 (en) * | 2011-08-25 | 2018-08-08 | 토요잉크Sc홀딩스주식회사 | Photopolymerizable composition, photopolymerizable coating agent, laminate, and polarizing plate |
| JP5989469B2 (en) * | 2011-09-06 | 2016-09-07 | 三洋化成工業株式会社 | Photosensitive composition |
| WO2013055158A2 (en) * | 2011-10-14 | 2013-04-18 | 주식회사 엘지화학 | Adhesive for polarizing plate, and polarizing plate comprising same |
| KR101560033B1 (en) | 2011-10-14 | 2015-10-16 | 주식회사 엘지화학 | Polarizer having protection films in two sides and optical device comprising the same |
| US9523792B2 (en) | 2011-10-14 | 2016-12-20 | Lg Chem, Ltd. | Polarizer having protection films in two sides and optical device comprising the same |
| KR101378817B1 (en) * | 2011-10-14 | 2014-04-03 | 주식회사 엘지화학 | Adhesive for polarizing plate and polarizing plate comprising the same |
| JP2013182162A (en) * | 2012-03-02 | 2013-09-12 | Sumitomo Chemical Co Ltd | Manufacturing method of polarizing plate |
| WO2013129693A1 (en) * | 2012-03-02 | 2013-09-06 | 住友化学株式会社 | Method for manufacturing polarizing plate |
| JP2013200445A (en) * | 2012-03-26 | 2013-10-03 | Sumitomo Chemical Co Ltd | Circularly polarizing plate |
| JP5530470B2 (en) | 2012-03-09 | 2014-06-25 | チェイル インダストリーズ インコーポレイテッド | Adhesive for polarizing plate |
| JP6205180B2 (en) * | 2012-06-08 | 2017-09-27 | 日東電工株式会社 | Active energy ray-curable adhesive composition, polarizing film and method for producing the same, optical film and image display device |
| JP6205179B2 (en) * | 2012-06-08 | 2017-09-27 | 日東電工株式会社 | Active energy ray-curable adhesive composition, polarizing film and method for producing the same, optical film and image display device |
| KR20130139134A (en) | 2012-06-12 | 2013-12-20 | 제일모직주식회사 | Adhesive composition, polarizing plate using the same, method for preparing the same and optical member comprising the same |
| JP6371031B2 (en) * | 2012-07-02 | 2018-08-08 | 住友化学株式会社 | Polarizing plate manufacturing method and manufacturing apparatus |
| JP6265590B2 (en) * | 2012-08-31 | 2018-01-24 | 日東電工株式会社 | Manufacturing method of polarizing film |
| JP6103687B2 (en) * | 2012-11-22 | 2017-03-29 | チェイル インダストリーズ インコーポレイテッド | Adhesive composition for polarizing plate |
| JP5519760B1 (en) * | 2012-11-30 | 2014-06-11 | 日東電工株式会社 | Active energy ray-curable adhesive composition, polarizing film and method for producing the same, optical film and image display device |
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| JP7491457B1 (en) | 2023-11-24 | 2024-05-28 | ａｒｔｉｅｎｃｅ株式会社 | Active energy ray curable adhesive and laminate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101114123A (en) * | 2006-07-28 | 2008-01-30 | 富士胶片电子材料有限公司 | Photo-setting property composition and color filter using the composition |
| CN101845286A (en) * | 2009-03-06 | 2010-09-29 | 住友化学株式会社 | Photocurable adhesive agent composition, polarization plates and manufacturing process thereof, optics and liquid crystal indicator |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05117592A (en) * | 1991-10-25 | 1993-05-14 | Ricoh Co Ltd | Adhesive |
| JPH08100163A (en) * | 1994-09-29 | 1996-04-16 | Nippon Zeon Co Ltd | Epoxy resin-based adhesive composition |
| JP3825506B2 (en) * | 1996-09-02 | 2006-09-27 | Ｊｓｒ株式会社 | Liquid curable resin composition |
| US6949297B2 (en) * | 2001-11-02 | 2005-09-27 | 3M Innovative Properties Company | Hybrid adhesives, articles, and methods |
| JP2008007694A (en) * | 2006-06-30 | 2008-01-17 | Sanyo Chem Ind Ltd | Photosensitive composition for adhesive agent |
| WO2008111584A1 (en) * | 2007-03-15 | 2008-09-18 | Sumitomo Chemical Company, Limited | Photocurable adhesive agent, polarizing plate using the photocurable adhesive agent, method for production of the polarizing plate, optical member, and liquid crystal display device |
| JP2009075192A (en) * | 2007-09-19 | 2009-04-09 | Jsr Corp | Method for manufacturing polarizing plate |
| JP2009073896A (en) * | 2007-09-19 | 2009-04-09 | Nippon Carbide Ind Co Inc | Adhesive composition and optical film |
-
2010
- 2010-04-16 JP JP2010095020A patent/JP4561936B1/en active Active
- 2010-04-21 TW TW099112470A patent/TWI404784B/en active
- 2010-07-21 JP JP2010164200A patent/JP5459128B2/en active Active
- 2010-08-27 CN CN201010266175.9A patent/CN102012535B/en active Active
- 2010-09-02 KR KR1020100086119A patent/KR101010574B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101114123A (en) * | 2006-07-28 | 2008-01-30 | 富士胶片电子材料有限公司 | Photo-setting property composition and color filter using the composition |
| CN101845286A (en) * | 2009-03-06 | 2010-09-29 | 住友化学株式会社 | Photocurable adhesive agent composition, polarization plates and manufacturing process thereof, optics and liquid crystal indicator |
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| CN102012535A (en) | 2011-04-13 |
| JP4561936B1 (en) | 2010-10-13 |
| TW201109404A (en) | 2011-03-16 |
| TWI404784B (en) | 2013-08-11 |
| JP2011076058A (en) | 2011-04-14 |
| JP2011076067A (en) | 2011-04-14 |
| KR101010574B1 (en) | 2011-01-25 |
| JP5459128B2 (en) | 2014-04-02 |
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