WO2011021441A1 - カチオン重合性接着剤及びそれを用いて得られた偏光板 - Google Patents
カチオン重合性接着剤及びそれを用いて得られた偏光板 Download PDFInfo
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- WO2011021441A1 WO2011021441A1 PCT/JP2010/060953 JP2010060953W WO2011021441A1 WO 2011021441 A1 WO2011021441 A1 WO 2011021441A1 JP 2010060953 W JP2010060953 W JP 2010060953W WO 2011021441 A1 WO2011021441 A1 WO 2011021441A1
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- Prior art keywords
- mass
- group
- polymerizable adhesive
- parts
- glycidyl ether
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- 0 *OC(*1CC(*2)[C@]2CC1)=O Chemical compound *OC(*1CC(*2)[C@]2CC1)=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/18—Oxetanes
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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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- 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
Definitions
- the present invention relates to a cationic polymerizable adhesive that can be used in various applications including the production of polarizing plates used for liquid crystal displays, for example.
- cationic polymerizable adhesives that are less likely to cause curing inhibition due to oxygen in the atmosphere and that can proceed with a curing reaction even after stopping the supply of energy such as ultraviolet rays have attracted attention.
- Cationic polymerizable adhesives with various properties have been reported.
- the cationic polymerizable adhesive includes at least one resin selected from an epoxy resin, an oxetane resin, a vinyl ether resin, and a benzoxazine resin, and a polyol liquid at 40 ° C. having a number average molecular weight of 300 or more.
- a resin selected from an epoxy resin, an oxetane resin, a vinyl ether resin, and a benzoxazine resin and a polyol liquid at 40 ° C. having a number average molecular weight of 300 or more.
- the polarizing plate generally has a structure in which a transparent protective film made of triacetyl cellulose or a thermoplastic saturated norbornene resin is laminated on a polarizer made of a polyvinyl alcohol film impregnated with a dichroic material such as iodine.
- a transparent protective film made of triacetyl cellulose or a thermoplastic saturated norbornene resin
- a polarizer made of a polyvinyl alcohol film impregnated with a dichroic material such as iodine.
- an adhesive having various optical characteristics and excellent adhesive strength is used for bonding the polarizer and the protective film.
- the conventional adhesive since the polarizing plate is usually installed near the backlight that constitutes the television receiver, the conventional adhesive has a decrease in adhesive strength over time due to the influence of heat generated by the backlight, In some cases, the agent layer cracked.
- liquid crystal displays As the use of liquid crystal displays is further expanded as the size of liquid crystal displays is reduced, the number of cases in which liquid crystal displays are installed and used in an environment where the temperature can be extremely high such as in an automobile is increasing. Even when used under such a high temperature environment, although a liquid crystal display capable of displaying a clear image over a long period of time is required, in the polarizing plate obtained using the above-described adhesive, In some cases, the adhesive layer cracks over time due to the influence of heat.
- the optical components that make up liquid crystal displays are required to have various characteristics at a very high level.
- a cationically polymerizable adhesive that does not cause a significant decrease in adhesive strength and that can prevent cracking of the adhesive layer has not yet been found.
- the problem to be solved by the present invention is a cationic polymerizable adhesive capable of achieving both a heat-resistant adhesive strength at a level capable of preventing a decrease in adhesive strength over time due to the influence of heat and the like, and prevention of cracking of the adhesive layer. Is to provide.
- the present invention is to provide a polarizing plate that does not cause peeling between the protective film and the polarizer due to the influence of heat or the like, or cracking of the adhesive layer.
- the inventors of the present invention have studied various combinations of cationically polymerizable compounds while advancing studies to solve the above problems.
- an oxetanyl group-containing compound having a molecular weight of 100 to 800, an aromatic glycidyl ether, and an adhesive containing a cationic polymerization initiator are good to some extent even when they are affected by heat for a long period of time. It was found that a sufficient adhesive strength can be maintained.
- the adhesive layer may also cause cracks and the like when it is repeatedly affected by heat for a long period of time.
- polyether polyol examples include polyether polyol, oxetanyl group-containing compound (B) including oxetanyl group-containing compound (b) having a molecular weight of 100 to 800, and aromatic glycidyl ether (c).
- oxetanyl group-containing compound (B) including oxetanyl group-containing compound (b) having a molecular weight of 100 to 800
- aromatic glycidyl ether c
- a cationic polymerizable adhesive containing glycidyl ether (C) and a cationic polymerization initiator (D) was examined.
- the polyol has a number average molecular weight of 300 to 5000 having at least one structure selected from the group consisting of a polyoxyethylene structure and a polyoxypropylene structure.
- the polyether polyol (a) is used as an essential component, and the polyether polyol (a) is added to a total mass of 100 parts by mass of the polyol (A), the oxetanyl group-containing compound (B), and the glycidyl ether (C).
- a cationically polymerizable adhesive capable of solving the problems of the present invention can be obtained only when a specific amount of 0.05 to 3 parts by mass is used.
- the present invention relates to a polyol (A) comprising a polyether polyol (a) having a number average molecular weight of 300 to 5000 having at least one structure selected from the group consisting of a polyoxyethylene structure and a polyoxypropylene structure, Cation containing oxetanyl group-containing compound (B) including oxetanyl group-containing compound (b) having a molecular weight of 800, glycidyl ether (C) including aromatic glycidyl ether (c), and cationic polymerization initiator (D) A polymerizable adhesive, wherein the polyether polyol (a) is 0.05 to 100 parts by mass with respect to 100 parts by mass of the total mass of the polyol (A), the oxetanyl group-containing compound (B), and the glycidyl ether (C). Cationic polymerizable adhesive characterized by containing 3 parts by mass and polarized light using the same It relates polarizing plate
- the cationically polymerizable adhesive of the present invention is capable of exhibiting excellent adhesive strength over a long period of time regardless of the influence of heat and the like, and it is difficult to cause cracks and the like of the adhesive layer itself.
- the present invention relates to a polyol (A) comprising a polyether polyol (a) having a number average molecular weight of 300 to 5000 having at least one structure selected from the group consisting of a polyoxyethylene structure and a polyoxypropylene structure, Oxetanyl group-containing compound (B) including oxetanyl group-containing compound (b) having molecular weight, glycidyl ether (C) including aromatic glycidyl ether (c), cationic polymerization initiator (D), and other if necessary
- the polyether polyol (a) is a total mass of 100 parts by mass of the polyol (A), the oxetanyl group-containing compound (B), and the glycidyl ether (C).
- Cationic polymerizable adhesive characterized in that it is contained in an amount of 0.05 to 3 parts by mass A.
- the polyol (A) used in the present invention comprises, as an essential component, a polyether polyol (a) having a number average molecular weight of 300 to 5000 having at least one structure selected from the group consisting of a polyoxyethylene structure and a polyoxypropylene structure. If necessary, other hydroxyl group-containing compounds are included.
- a polyether polyol (a) having a number average molecular weight of 300 to 5000 having at least one structure selected from the group consisting of a polyoxyethylene structure and a polyoxypropylene structure a polyether polyol (a) having a number average molecular weight of 300 to 5000 having at least one structure selected from the group consisting of a polyoxyethylene structure and a polyoxypropylene structure
- the specific polyether polyol (a) is in a range of 0.05 to 3 parts by mass with respect to 100 parts by mass of the total mass of the polyol (A), the oxetanyl group-containing compound (B), and the glycidyl ether (C). It is important in order to achieve both excellent heat-resistant adhesive strength and prevention of cracking of the adhesive layer.
- the polyether polyol (a) preferably has a number average molecular weight of 300 to 4000, and more preferably in the range of 300 to 3000.
- the amount used thereof is the polyol (A), the oxetanyl group-containing compound (B), and glycidyl contained in the cationic polymerizable adhesive.
- the adhesive strength decreases with time due to the influence of heat. May cause peeling.
- the polyether polyol (a) is added in an amount of 0.001 part by mass relative to 100 parts by mass of the total mass of the polyol (A), the oxetanyl group-containing compound (B), and the glycidyl ether (C) contained in the cationic polymerizable adhesive.
- the use of 1 to 1.5 parts by mass is very preferable for further enhancing the effects of the present invention.
- the polyether polyol (a) is preferably used in the range of 90 to 100 parts by mass, more preferably in the range of 95 to 100% by mass with respect to the total amount of the polyol (A).
- polyether polyol (a) one having at least one structure selected from the group consisting of a polyoxyethylene structure and a polyoxypropylene structure can be used.
- polyoxyethylene glycol, polyoxypropylene glycol, a random copolymer or a block copolymer having both a polyoxyethylene structure and a polyoxypropylene structure can be used.
- polyoxyethylene glycol “PEG # 300, 400, 600, 1000, 1500, 1540, 2000, 4000” manufactured by NOF Corporation, polyoxyethylene glycol and polyoxy manufactured by Mitsui Chemicals, Inc. Copolymers with propylene glycol such as “ED-26, ED-28, ED-36, ED-37A, ED-56” and the like can be used.
- the polyether polyol (a) is one having two or more hydroxyl groups at one end of a polyalkylene oxide chain having at least one structure selected from the group consisting of a polyoxyethylene structure and a polyoxypropylene structure. It can also be used. Specifically, Ymer N120 (manufactured by Perstorp) or the like can be used. By using one having two or more hydroxyl groups at one end of the polyalkylene oxide chain, it is possible to form an adhesive layer having a relatively good heat-resistant adhesive strength.
- polyether polyols (a) it is preferable to use those having a polyoxyethylene structure since the effect of preventing cracking of the adhesive layer is remarkable.
- the polyether polyol (a) one having 50 to 100% by mass of the polyoxyethylene structure with respect to the total amount of the polyether polyol (a) is preferably used, and is 95 to 100% by mass. It is particularly preferred to use polyoxyethylene glycol.
- the polyether polyol (a) can be produced by addition polymerization of an initiator composed of a compound having two or more active hydrogen atoms and an alkylene oxide essentially containing ethylene oxide or propylene oxide. Specifically, for example, in the presence of a catalyst such as boron trifluoride and the initiator, the alkylene oxide or the like can be supplied all at once, or separately supplied, mixed and reacted. When producing a copolymer having both a polyethylene oxide structure and a polypropylene oxide structure as the polyether polyol (a), ethylene oxide and propylene oxide are mixed together in the presence of the initiator.
- an initiator composed of a compound having two or more active hydrogen atoms and an alkylene oxide essentially containing ethylene oxide or propylene oxide.
- the alkylene oxide or the like can be supplied all at once, or separately supplied, mixed and reacted.
- Examples of the initiator used for producing the polyether polyol (a) include ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, glycerin, and trimethylolpropane. Trimethylolethane, hexanetriol, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol and the like can be used.
- alkylene oxides including ethylene oxide and propylene oxide can be used.
- the polyether polyol (a) may have other structural units as required in addition to the polyoxyethylene structure and the polyoxypropylene structure.
- Examples of the other structural units include a polyoxybutylene structure.
- the other structure can be obtained by using, for example, other initiators other than ethylene glycol and propylene glycol as the initiator, or using other alkylene oxides other than ethylene oxide and propylene oxide as the alkylene oxide. It can be introduced into the ether polyol (a).
- alkylene oxide for example, butylene oxide, styrene oxide, ⁇ -chloropropylene oxide (epichlorohydrin), tetramethylene oxide (tetrahydrofuran) and the like can be used.
- the polyol (A) may contain a hydroxyl group-containing compound other than the polyether polyol (a) as necessary.
- a hydroxyl group-containing compound for example, polyether polyols other than the polyether polyol (a), polyester polyols, polycarbonate polyols, and other low molecular weight polyols can be used as appropriate.
- the polyol (A) is based on 100 parts by mass of a total mass of the polyol (A), the oxetanyl group-containing compound (B) and the glycidyl ether (C) contained in the cationic polymerizable adhesive of the present invention. It is preferably used in the range of 0.05 to 5 parts by weight, more preferably used in the range of 0.05 to 3 parts by weight, and it is preferably used in the range of 0.1 to 1.5 parts by weight. It is preferable for achieving both excellent heat-resistant adhesive strength and prevention of cracking of the adhesive layer.
- the oxetanyl group-containing compound (B) used in the present invention essentially comprises an oxetanyl group-containing compound (b) having a molecular weight of 100 to 800, and optionally contains an oxetanyl group-containing compound having a molecular weight outside the above range. .
- the oxetanyl group-containing compound (b) used in the present invention it is important to use a compound having a molecular weight of 100 to 800.
- the adhesive layer is usually formed as a thin film (thickness of several ⁇ m) in many cases.
- the adhesive In order to apply uniformly with a film thickness, the adhesive must have a low viscosity. And in order to obtain the said low-viscosity adhesive agent, it becomes essential to use the above-mentioned comparatively low molecular weight oxetanyl group containing compound.
- an adhesive obtained by using an oxetanyl group-containing compound having a molecular weight of about 1500 has a relatively high viscosity, so that it is difficult to form a thin film. It may cause a decrease in the curability of the layer and a decrease in adhesive strength over time due to the influence of heat or the like.
- the coating workability and curability of the cationic polymerizable adhesive of the present invention are further enhanced, and as a result, the deterioration of the adhesive strength over time due to the influence of heat and the like is prevented.
- the said molecular weight shows what is calculated
- oxetanyl group-containing compound (b) a compound (b1) having two or more oxetanyl groups or a compound (b2) having one oxetanyl group can be used. Especially, it is preferable to use the compound (b1) which has a 2 or more oxetanyl group from a viewpoint of preventing the fall of the adhesive strength by the influence of a heat
- the compound (b1) having two or more oxetanyl groups a compound having a plurality of, preferably 2 to 4, oxetane ring structures contributing to cationic polymerization can be used.
- compounds represented by the following general formulas (1) and (2) can be used alone or in combination of two or more.
- each R 1 is independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, or an aralkyl group.
- a furyl group or a thienyl group each R 2 independently represents a divalent organic residue, and each Z independently represents an oxygen atom or a sulfur atom.
- Examples of the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms represented by R 1 include, for example, methyl group, ethyl group, n- or i-propyl group, n-, i- or t- A butyl group, a pentyl group, a hexyl group, a cyclohexyl group, and the like; and an aryl group such as a phenyl, naphthyl, tolyl, and xylyl group; and an aralkyl group such as a benzyl and phenethyl group It is.
- Examples of the divalent organic residue represented by R 2 in the general formula (1) include, for example, a linear, branched or cyclic alkylene group and a poly (oxy) having 4 to 30 carbon atoms.
- the linear, branched or cyclic alkylene group constituting R 2 has 1 carbon atom such as methylene group, ethylene group, 1,2- or 1,3-propylene group, butylene group, cyclohexylene group and the like.
- An alkylene group of ⁇ 15 is preferred.
- the poly (oxyalkylene) group having 4 to 30 carbon atoms is preferably one having 4 to 8 carbon atoms, such as a poly (oxyethylene) group or a poly (oxypropylene) group. Is preferred.
- R 3 in the general formula (3) represents an oxygen atom, a sulfur atom, CH 2 , NH, SO, SO 2 , C (CF 3 ) 2 or C (CH 3 ) 2 .
- R 4 in the general formula (4) represents an alkylene group having 1 to 6 carbon atoms, an arylene group, and a functional group represented by the following general formula (5).
- a represents an integer of 1 to 6
- b represents an integer of 1 to 15.
- b is preferably an integer of 1 to 3.
- Examples of the oxetane compound having 2 to 4 oxetane ring structures include Aron Oxetane OXT-221, Aron Oxetane OXT-121, Aron Oxetane OXT-223 (above, manufactured by Toagosei Co., Ltd.), Etanacol OXBP (above , Ube Industries, Ltd.) are commercially available.
- the above-mentioned compound (b1) those having a molecular weight of 100 to 800 are preferably used, and in particular, those represented by the general formula (1) are preferably used.
- the use of bis [1-ethyl (3-oxetanyl)] methyl ether in which 1 is an ethyl group, R 2 is methylene, and Z is an oxygen atom can reduce the thickness of the cured adhesive. Further, it is preferable because the curability can be further improved and the decrease in adhesive strength due to heat, light, or the like can be prevented for a long period of time.
- R 1 in the general formula (6) represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms.
- R 2 represents a hydrogen atom, an optionally branched alkyl group having 1 to 10 carbon atoms, an aliphatic cyclic structure, or an aromatic structure.
- Examples of the alkyl group having 1 to 8 carbon atoms that can constitute R 1 in the general formula (6) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a 2-ethylhexyl group. Is mentioned.
- Examples of the alkoxyalkyl group having 1 to 5 carbon atoms that can constitute R 1 in the general formula (6) include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, and an ethoxyethyl group. And propoxyethyl group.
- Examples of the hydroxyalkyl group having 1 to 6 carbon atoms that can constitute R 1 in the general formula (6) include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
- the optionally branched alkyl group having 1 to 10 carbon atoms that can constitute R 2 in the general formula (6) is a linear alkyl group such as a methyl group, an ethyl group, or a propyl group. And a branched alkyl group such as 2-ethylhexyl group.
- aliphatic cyclic structure may constitute R 2 in the general formula (6), such as cyclohexyl group and the like.
- the cyclohexyl group or the like may have an alkyl group or the like instead of a hydrogen atom.
- the aromatic structure may constitute R 2 in the general formula (6), for example, a phenyl group and the like.
- the phenyl group or the like may have an alkyl group or the like instead of a hydrogen atom.
- those having a molecular weight of 100 to 500 are preferably used, among which 3-hydroxymethyl-3-ethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3- It is more preferable to use one or more selected from the group consisting of ethyl-3- (2-ethylhexyloxymethyl) oxetane and 3-ethyl-3- (cyclohexyloxy) methyloxetane.
- an oxetanyl group-containing compound having a molecular weight outside the range of 100 to 800 may be used in combination with the oxetanyl group-containing compound (b), if necessary. good.
- the compound (b1) having two or more oxetanyl groups is used in the range of 90 to 100 parts by mass with respect to 100 parts by mass of the oxetanyl group-containing compound (B). It is preferable to use in the range of 95 to 100 parts by mass in order to make the adhesive thin and to achieve both excellent curability and heat resistant adhesive strength.
- the oxetanyl group-containing compound (B) is a total mass of 100 parts by mass of the polyol (A), the oxetanyl group-containing compound (B) and the glycidyl ether (C) contained in the cationic polymerizable adhesive of the present invention. It is preferably used in the range of 20 to 80 parts by mass, and in the range of 40 to 70 parts by mass, the adhesive can be made thin and has excellent curability and heat resistant adhesive strength. It is preferable to achieve both.
- the glycidyl ether (C) used in the present invention essentially contains an aromatic glycidyl ether (c) and contains other glycidyl ether as necessary.
- the adhesive obtained by using the aliphatic glycidyl ether instead of the total amount of the aromatic glycidyl ether (c) cannot give good adhesive strength and causes peeling of the adherend over time. There is a case.
- aromatic glycidyl ether (c) for example, bisphenol A type glycidyl ether, bisphenol F type glycidyl ether, bisphenol S type glycidyl ether, and bisphenol AD type glycidyl ether can be used.
- aromatic glycidyl ether (c) it is possible to further improve the curability and moderately adjust the hardness of the cured product, and it is possible to prevent a decrease in adhesive strength due to heat, light, etc. over a long period of time.
- Bisphenol A glycidyl ether and bisphenol F glycidyl ether are preferably used, and at least one selected from the group consisting of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether is preferably used.
- aromatic glycidyl ether (c) those having two or more glycidyl ether groups are preferably used for imparting good adhesive strength, and more preferably 2 to 6 are used. .
- the aromatic glycidyl ether (c) can be produced by reacting bisphenol A or bisphenol F with epichlorohydrin or the like. In the obtained aromatic glycidyl ether, it is derived from the epichlorohydrin or the like. Some chlorine may remain. Further, in general, commercially available glycidyl ether group-containing compounds usually contain several percent to several tens of percent of chlorine.
- the aromatic glycidyl ether (c) when producing the aromatic glycidyl ether (c), it is possible to give a further excellent adhesive strength by performing treatment such as removal of chlorine by rectification or the like, and discoloration of the polarizer, etc. It is preferable from the viewpoint of preventing.
- the rectification is preferably performed, for example, at a temperature of about 50 to 200 ° C. for about 1 to 200 hours.
- the amount of chlorine remaining in the aromatic glycidyl ether (c) can be measured based on JIS K 1200-3-2: 2000.
- the aromatic glycidyl ether (c) is preferably contained in an amount of 5 to 50% by mass with respect to the total mass of the oxetanyl group-containing compound (A) and glycidyl ether (B) in the cationic polymerizable adhesive, The content within the range of 10 to 40% by mass is more preferable for maintaining excellent heat resistant adhesive strength for a long period of time.
- the said glycidyl ether (B) is the meaning including other glycidyl ethers, such as aliphatic glycidyl ether mentioned later other than the said aromatic glycidyl ether (c), for example.
- glycidyl ether (C) used in the present invention other glycidyl ethers can be used as necessary in addition to the aromatic glycidyl ether (c).
- Examples of the other glycidyl ethers include aliphatic glycidyl compounds having three glycidyl ether groups such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, polyglycerol triglycidyl ether, and diglycerol triglycidyl ether, and trimethylol.
- Two glycidyl ether groups such as propane diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, etc.
- Glycidyl compounds having the following can be used:
- As the other glycidyl ether hydrogenated bisphenol A glycidyl ether, hydrogenated bisphenol F glycidyl ether or other aromatic glycidyl ether obtained by hydrogenating the aromatic glycidyl ether (C) may be used. it can.
- the aromatic glycidyl ether (c) is preferably used in the range of 20 to 80% by mass, and in the range of 40 to 60% by mass with respect to the total amount of the glycidyl ether (C). More preferably.
- the other glycidyl ether is preferably used in the same amount as the aromatic glycidyl ether (c). Specifically, the other glycidyl ether is used in a range of 20 to 80% by mass with respect to the total mass of the oxetanyl group-containing compound (A) and the glycidyl ether (C) in the cationic polymerizable adhesive. It is preferable to use in the range of 40 to 60% by mass in order to maintain good heat-resistant adhesive strength for a long period of time.
- the glycidyl ether (C) is used in a range of 20 to 80 parts by mass with respect to a total of 100 parts by mass of the polyol (A), the oxetanyl group-containing compound (B) and the glycidyl ether (C). It is preferable.
- the cationic polymerization initiator (D) used in the present invention is, for example, a photo cationic polymerization initiator that generates an acid capable of initiating cationic polymerization by irradiation of energy rays such as ultraviolet rays, or a heat that generates an acid by heating or the like.
- Cationic polymerization initiator when producing a polarizing plate by bonding a polarizer and a protective film, or when producing other optical materials, from the viewpoint of preventing deformation or discoloration of the substrate due to heat, photocationic polymerization starts. It is preferable to use an agent.
- the cation moiety may be aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrhenium, thioxanthonium, (2,4-cyclopentadien-1-yl ) [(1-methylethyl) benzene] -Fe cation, and the anion moiety is BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , [BX 4 ] ⁇ (where X is at least two fluorine or tri
- An onium salt composed of a phenyl group substituted with a fluoromethyl group can be used alone or in combination of two or more.
- aromatic sulfonium salt examples include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, and bis [4- (diphenyl).
- aromatic iodonium salt examples include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, Bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium Hexafluorophosphate, 4-methylphenyl-4- (1 -Meth
- aromatic diazonium salt for example, phenyldiazonium ⁇ ⁇ hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate and the like can be used.
- aromatic ammonium salt examples include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl -2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-Cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate and the like can be used.
- thioxanthonium salt S-biphenyl 2-isopropyl thioxanthonium hexafluorophosphate or the like can be used.
- the (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe salt includes (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene.
- Examples of the cationic photopolymerization initiator include CPI-100P, CPI-101A, CPI-200K (manufactured by San Apro Co., Ltd.), a syracure photocuring initiator UVI-6990, a syracure photocuring initiator UVI-6922, Syracure photocuring initiator UVI-6976 (manufactured by Dow Chemical Japan Co., Ltd.), Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172, Adeka Optomer SP-300 (above, manufactured by ADEKA Corporation), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L, Sun-Aid SI-180L, Sun-Aid SI-110, Sun-Aid SI-180 ( As above, manufactured by Sanshin Chemical Industry Co., Ltd.
- thermal cationic polymerization initiator for example, benzylsulfonium salt, thiophenium salt, thiolanium salt, benzylammonium salt, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, amine imide and the like can be used.
- thermal cationic polymerization initiator examples include “Adeka Opton® CP77”, “Adeka Opton® CP66” (above, manufactured by ADEKA Corporation), “Sun Aid® SI-60L”, “Sun Aid® SI-80L”, “Sun Aid® SI-100L” (and above) Commercial products such as Sanshin Chemical Industry Co., Ltd.) can also be used.
- the amount of the cationic polymerization initiator (D) used is not particularly limited, but is preferably in the range of 0.1 to 20% by mass, more preferably based on the total amount of the cationic polymerizable adhesive. The range of 1 to 15% by mass is desirable.
- the cationic polymerizable adhesive of the present invention is necessary.
- an alicyclic epoxy compound (E), an epoxy group-containing silane compound (F) and the like may be used in combination.
- alicyclic epoxy compound (E) those having a plurality of, preferably 2 to 4, alicyclic epoxy groups can be used.
- examples of the alicyclic epoxy compounds having two alicyclic epoxy groups include 3,4-epoxycyclohexenylmethyl-3 represented by the following general formula (7): , 4-Epoxycyclohexanecarboxylate (compound of general formula (7) where a is 0), its caprolactone modified product (compound of general formula (7) where a is 1), its trimethylcaprolactone modified product (structure)
- the compounds represented by the formula (8) and the structural formula (9)) and their valerolactone-modified products the structural formula (10) and the structural formula (11)
- the structural formula (12) can be used.
- adipic ester-based alicyclic epoxy compound represented by the general formula (12) for example, Cyracure UVR-6128 (above, manufactured by Dow Chemical Japan Co., Ltd.) is commercially available.
- R 1 to R 6 in the general formula (13) each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- R 1 to R 6 in the general formula (13) each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- dicyclohexyl-3,3′-diepoxide can be used as the compound represented by the general formula (13).
- alicyclic epoxy compound having three alicyclic epoxy groups a compound represented by the following general formula (14) can be used.
- a and b in the general formula (14) are each independently 0 or 1, and they may be the same or different.
- Epolide GT301 Epolide GT302 (manufactured by Daicel Chemical Industries, Ltd.) and the like are commercially available.
- alicyclic epoxy compound having four alicyclic epoxy groups for example, a compound represented by the following general formula (15) can be used.
- a to d each independently represent 0 or 1, and they may be the same or different.
- Epolide GT401 Epolide GT403 (manufactured by Daicel Chemical Industries, Ltd.) and the like are commercially available.
- the alicyclic epoxy compound (E) is preferably used in a range of 0.5 to 10% by mass, and in a range of 0.7 to 5% by mass, based on the total amount of the cationic polymerizable adhesive of the present invention. Is preferably used in order to rapidly cure the adhesive.
- the epoxy group-containing silane compound (F) that can be used in the cationic polymerizable adhesive of the present invention can further increase the normal adhesive strength of the obtained adhesive and prevent discoloration of the polarizer.
- an aminosilane such as 3-aminopropyltriethoxysilane or a vinylsilane such as vinyltriacetoxysilane is used instead of the compound (F)
- the effect of preventing discoloration of the polarizer may be slightly reduced. is there.
- Examples of the epoxy group-containing silane compound (F) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl.
- methyldimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc., among which 3-glycidoxypropyltri One selected from the group consisting of ethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane Using more than heat Without causing reduction in adhesion strength due also preferable in preventing the fading or the like of the polarizer.
- silicone oils represented by the following general formulas (16) and (17) can also be used.
- n represents an integer of 1 or more.
- the epoxy group-containing silane compound (F) is used in the range of 0.1 to 1.5% by mass with respect to the total amount of the cationic polymerizable adhesive of the present invention. This is preferable in that it does not cause a decrease and prevents fading of the polarizer.
- the amount of chlorine remaining in the total amount of the cationic polymerizable adhesive is set to 1500 ppm or less to give a further excellent heat-resistant adhesive strength, and a polarizer. From the viewpoint of preventing discoloration and the like, it is very preferable. If the chlorine content exceeds 1500 ppm, the adhesive layer or the resulting polarizing plate may be discolored or the strength may be reduced.
- the chlorine referred to in the present invention can be used in combination with chlorine and chloride derived from raw materials such as epichlorohydrin used for the production of the aromatic glycidyl ether (c), and the adhesive of the present invention. It refers to inorganic chlorides such as sodium chloride resulting from various additives.
- the amount of chlorine By setting the amount of chlorine to 1500 ppm or less, preferably 1000 ppm or less, and more preferably 800 ppm or less, based on the total amount of the cationic polymerizable adhesive, both fading of a polarizer and the like and long-term normal adhesive strength can be achieved. It becomes possible.
- the amount of chlorine remaining in the total amount of the cationic polymerizable adhesive of the present invention can be measured based on JIS K 1200-3-2: 2000.
- the epoxy group-containing silane compound (F) in order to further prevent discoloration or the like of the polarizer, it is preferable to use the epoxy group-containing silane compound (F) and adjust the amount of chlorine remaining in the cationic polymerizable adhesive to 1500 ppm or less. .
- the cationic polymerizable adhesive of the present invention can be produced, for example, by the following method.
- the cationic polymerizable adhesive of the present invention is prepared by using, for example, a closed planetary mixer or the like, a polyol (A) containing the polyether polyol (a) produced in advance, and an oxetanyl group containing the oxetanyl group-containing compound (b).
- the cationically polymerizable adhesive obtained by the above method preferably has a viscosity of 100 mPa ⁇ s or less at 25 ° C. from the viewpoint of reducing the thickness of the adhesive layer to be formed as much as possible.
- This viscosity can be adjusted mainly by using a diluent such as an oxetane compound or an alicyclic epoxy compound, or by using a liquid having a low molecular weight as the aromatic glycidyl ether (c).
- the cationically polymerizable adhesive of the present invention may contain various additives as necessary so long as the effects of the present invention are not impaired.
- the additive examples include a thixotropic agent, a sensitizer, the various polyols described above and other polyols, a leveling agent, an antioxidant, a tackifier, a wax, a heat stabilizer, a light stabilizer, and a fluorescent enhancement agent.
- thixotropic agent for example, surface-treated calcium carbonate, fine powder silica, bentonite, zeolite or the like can be used.
- the additive is, for example, the polyol (A), the oxetanyl group-containing compound (B), the glycidyl ether (C), or the photocation using a sealed planetary mixer or the like.
- the polymerization initiator (D) and if necessary, the alicyclic epoxy compound (E), the epoxy group-containing silane compound (F), and the like, they can be mixed together.
- the cationically polymerizable adhesive of the present invention obtained by the above method is excellent in adhesion by proceeding with polymerization quickly by a method such as light irradiation or heating corresponding to the kind of the cationic polymerization initiator (D) to be used. Strength can be expressed.
- a photocationic polymerization initiator is used as the cationic polymerization initiator (D)
- curing of the cationic polymerizable adhesive of the present invention can be promoted by irradiating active energy rays such as ultraviolet rays and electron beams. .
- the irradiation of energy rays such as ultraviolet rays is preferably in the range of 10 to 2000 mJ / cm 2 , more preferably 20 to 1000 mJ / cm 2 , and particularly preferably 30 to 800 mJ / cm 2 .
- a source of ultraviolet rays for example, a known lamp such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high pressure mercury lamp, or a low pressure mercury lamp can be used.
- the amount of ultraviolet irradiation was based on a value measured in a wavelength range of 300 nm to 390 nm using a UV checker UVR-N1 (manufactured by Nippon Battery Co., Ltd.).
- curing may be further promoted by heating at 30 to 100 ° C., more preferably about 40 to 80 ° C., if necessary.
- a thermal cationic polymerization initiator is used as the cationic polymerization initiator (D), for example, by heating to about 50 to 200 ° C. using a heating device such as a far infrared heater or a hot plate, Curing of the cationic polymerizable adhesive can proceed.
- the cationic polymerizable adhesive of the present invention can be used for bonding various substrates.
- a plastic substrate or a metal substrate can be used.
- the plastic base material polyester base material, polyolefin base material, acrylonitrile-butadiene-styrene resin (which is generally used for plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, OA equipment, etc.) ABS resin) base material, polyacrylic base material, polyurethane base material, epoxy resin base material, polyvinyl chloride base material and the like.
- polyester base material for example, a sheet or film made of polyethylene terephthalate or a cellulose-based resin that is preferably used for manufacturing a polarizing plate can be used.
- the cellulose resin include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, and cellulose acetate phthalate.
- polystyrene-based substrate for example, a sheet or film-like material made of cycloolefin polymer, polybutadiene, or the like can be used.
- examples of the metal substrate include stainless steel plate, aluminum plate, aluminum alloy plate, electromagnetic steel plate, copper plate, stainless steel plate and the like.
- Examples of the method for applying the adhesive of the present invention to the substrate surface include a coating method using a dispenser, a T-die coater, a knife coater, a micro gravure coater, or the like.
- the base material to be bonded is a transparent base material that transmits light such as ultraviolet rays
- the base material is an adhesive comprising the cationically polymerizable composition of the present invention containing a photocationic polymerization initiator as the cationic polymerization initiator (D).
- D cationic polymerization initiator
- the cationic polymerizable adhesive of the present invention containing the thermal cationic polymerization initiator as the cationic polymerization initiator (D) is applied to the substrate surface.
- the thermal cationic polymerization initiator as the cationic polymerization initiator (D)
- curing can proceed and the substrate can be bonded.
- a cationic polymerization initiator it is also possible to apply an adhesive on the surface of the substrate, irradiate the coated surface with ultraviolet rays, etc., and then quickly place and cure another substrate.
- the substrate can be glued.
- the film thickness of the adhesive layer varies depending on the use of the laminate, but is preferably in the range of about 0.1 ⁇ m to 5 ⁇ m.
- the cationic polymerizable adhesive of the present invention can maintain excellent heat-resistant adhesive strength regardless of heat or the like and can prevent cracking of the adhesive layer. It can be used for production and lamination of optical films.
- the polarizing plate of the present invention is generally formed by bonding a protective film and a polarizer through an adhesive layer made of the cationic polymerizable adhesive.
- cellulose resins such as triacetyl cellulose, resins having a cycloolefin structure, acrylic resins, norbornene resins, etc. It is preferable to use a cellulose resin such as triacetyl cellulose.
- cellulose resin examples include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, and cellulose nitrate. These can be used alone or 2 More than one species can be used in combination, and among these, it is preferable to use cellulose acetate because a film having excellent mechanical properties and transparency can be obtained.
- the polarizer is not particularly limited, and various types of polarizers can be used.
- a hydrophilic polymer such as polyvinyl alcohol, partially formalized polyvinyl alcohol, ethylene / vinyl acetate copolymer partially saponified product, etc.
- dichroic materials such as iodine and dichroic dyes on a plastic base material
- polyene-based oriented films such as dehydrated polyvinyl alcohol and dehydrochlorinated polyvinyl chloride can do.
- the thickness of the protective film used when producing the polarizing plate of the present invention varies depending on the application used, but is preferably in the range of about 20 ⁇ m to 100 ⁇ m.
- the thickness of the polarizer is usually preferably in the range of about 5 ⁇ m to 50 ⁇ m.
- the cationic polymerizable adhesive is applied on the protective film, and then the above-mentioned application surface is irradiated with the above-mentioned amount of ultraviolet light, and then a polarizer is placed on the application surface and adhered. Can be manufactured.
- the thickness of the adhesive layer made of the cationic polymerizable adhesive is preferably as thin as possible for reasons such as impaired optical properties, and specifically, it is preferably 5 ⁇ m or less.
- the polarizing plate of the present invention obtained by the above method can be used for a member constituting a display such as a mobile communication terminal such as a mobile phone, a liquid crystal television, a personal computer, and a portable game machine.
- a display such as a mobile communication terminal such as a mobile phone, a liquid crystal television, a personal computer, and a portable game machine.
- Example 1 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 58.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, PEG # 400 (polyoxyethylene glycol manufactured by NOF Corporation, number average molecular weight 400) 0.13 part by mass, KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass of sidoxypropyltriethoxysilane) and CPI-100P (manufact
- Example 2 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 58.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, PEG # 1000 (polyoxyethylene glycol manufactured by NOF Corporation, number average molecular weight 1000) 0.32 part by mass, KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass of glycidoxypropyltriethoxysilane) and CPI-100P (man
- Example 3 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 58.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, PEG # 2000 (polyoxyethylene glycol manufactured by NOF Corporation, number average molecular weight 2000) 0.65 part by mass, KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass of glycidoxypropyltriethoxysilane) and CPI-100P (man
- Example 4 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 58.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, PEG # 4000 (polyoxyethylene glycol manufactured by NOF Corporation, number average molecular weight 4000) 1.28 parts by mass, KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass of glycidoxypropyltriethoxysilane) and CPI-100P
- Example 5 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 58.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, Ymer N-120 (polyoxyethylene glycol manufactured by Perstorp) 0.3 part by mass, KBE-403 (3-glycidoxypropyltriethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.5 part by mass, and CPI-100P (diphenyl-4- (phenyl
- Example 6 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 58.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, Actol ED-56 (Copolymer of polyoxyethylene glycol and polyoxypropylene glycol manufactured by Mitsui Chemicals, Inc., number average molecular weight 2000) 0.64 part by mass, KBE-403 (3-glycidoxypropyltriethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd
- Example 7 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 58.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, Actol ED-36 (Mitsui Chemicals polyoxyethylene glycol and polyoxypropylene glycol copolymer, number average molecular weight 3000) 1 part by mass, KBE-403 (Shin-Etsu) 0.5 part by mass of 3-glycidoxypropyltriethoxysilane manufactured by Chemical Industry Co
- Example 8 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-223 (Toa Gosei Co., Ltd.) 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene) 58.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′ manufactured by Daicel Chemical Industries, Ltd.) , 4′-epoxycyclohexenecarboxylate) 1.0 part by mass, PEG # 400 (polyoxyethylene glycol manufactured by NOF Corporation, number average molecular weight 400) 0.13 part by mass, KBE-403 (Shin-Etsu Chemical ( 0.5 part by mass of 3-glycidoxypropyltriethoxysilane) manufactured by Co., Ltd., and D
- Example 9 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-2) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 58.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, PEG # 400 (polyoxyethylene glycol manufactured by NOF Corporation) 0.13 part by mass, KBE-403 (3-glycidoxypropyltri produced by Shin-Etsu Chemical Co., Ltd.) Ethoxysilane) 0.5 part by mass, and CPI-100P (diphenyl-4- (phenylthio)
- Example 10 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-4), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 58.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, PEG # 400 (polyoxyethylene glycol manufactured by NOF Corporation, number average molecular weight 400) 0.13 part by mass, KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass of glycidoxypropyltriethoxysilane) and CPI-100P (S-100P
- chlorine content contained in the total amount of the obtained cationic polymerizable adhesive (10) was determined according to the method described later, it was 302 ppm.
- Example 11 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 58.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, PEG # 400 (polyoxyethylene glycol manufactured by NOF Corporation, number average molecular weight 400) 1 part by mass, KBE-403 (Shin-Etsu Chemical Co., Ltd.
- Example 12 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) 57.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether), Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, PEG # 400 (polyoxyethylene glycol manufactured by NOF Corporation, number average molecular weight 400) 2 parts by mass, KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 3-glycid 0.5 parts by mass of xylpropyltriethoxysilane) and CPI-100P
- a cationically polymerizable adhesive (12) was prepared by mixing and stirring 8.0 parts by weight of thio) phenylsulfonium hexafluorophosphate in a 50% by weight propylene carbonate solution.
- chlorine content contained in the total amount of the obtained cationic polymerizable adhesive (12) was determined according to the method described later, it was 205 ppm.
- Example 13 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 56.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, PEG # 400 (polyoxyethylene glycol manufactured by NOF Corporation, number average molecular weight 400) 2.8 parts by mass, KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass of glycidoxypropyltriethoxysilane) and CPI-100P (man
- Example 14 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 58.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, Ymer N-120 (Perstorp polyoxyethylene glycol) 1.0 part by mass, KBE-403 (Shin-Etsu Chemical Co., Ltd.
- Example 15 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) 57.0 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether), Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by weight, Ymer N-120 (Perstorp polyoxyethylene glycol) 2.0 part by weight, KBE-403 (Shin-Etsu Chemical Co., Ltd.
- Example 16 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-3), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) Bis [1-ethyl (3-oxetanyl)] methyl ether) 56.0 parts by mass, Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene manufactured by Daicel Chemical Industries, Ltd.) Carboxylate) 1.0 part by mass, Ymer N-120 (polyoxyethylene glycol manufactured by Perstorp) 2.8 parts by mass, KBE-403 (3-glycidoxypropyltriethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.5 part by mass, and CPI-100P (diphenyl-4- (phenyl
- Example 17 In a closed planetary mixer, 20.0 parts by mass of aromatic glycidyl ether (C-1) and 20.0 parts by mass of aliphatic glycidyl ether (C′-5), Aron Oxetane OXT-221 (Toa Gosei Co., Ltd.) 58 parts by mass of bis [1-ethyl (3-oxetanyl)] methyl ether), Celoxide 2021P (3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate manufactured by Daicel Chemical Industries, Ltd.) ) 1.0 part by mass, PEG # 400 (polyoxyethylene glycol manufactured by NOF Corporation, number average molecular weight 400) 0.13 part by mass, KBE-403 (3-glycid manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass of xylpropyltriethoxysilane) and CPI-100P (manu).
- a cationically polymerizable adhesive (3 ′) was prepared by mixing and stirring 8.0 parts by mass of propylene carbonate (mass solution of-(phenylthio) phenylsulfonium hexafluorophosphate).
- propylene carbonate mass solution of-(phenylthio) phenylsulfonium hexafluorophosphate.
- Kuraraypoval PVA-117H Polyvinyl alcohol manufactured by Kuraray Co., Ltd., degree of polymerization 1700, completely saponified product, powder
- an aqueous polyvinyl alcohol solution non-volatile content 8% by mass
- the film was applied onto a release film and then dried under an environment of 80 ° C. for 5 minutes, and then the previous release film was removed to prepare a polyvinyl alcohol film having a thickness of 75 ⁇ m.
- the obtained polyvinyl alcohol film was fixed to a stretching machine, and the film was stretched in hot water at 40 ° C. until it became three times larger in a uniaxial direction.
- the stretched film was adjusted to 30 ° C. containing 0.02 parts by mass of iodine, 2 parts by mass of potassium iodide, and 100 parts by mass of water. Soaked in.
- the stretched film was immersed in an aqueous solution adjusted to 56.5 ° C. containing 12 parts by mass of potassium iodide, 5 parts by mass of boric acid and 100 parts by mass of water.
- the polarizer obtained by the above method thickness of 42 ⁇ m, length of 297 mm, width of 210 mm is bonded to each of the two triacetyl cellulose films, and they are pressed using a rubber roller and bonded to each other.
- a polarizing plate was produced by heating for 1 minute in a dryer at 0 ° C.
- Coloring, discoloration, etc. of the polarizing plate are such that the polarizing plate produced by the above method is left in a dryer set at 85 ° C. for 1500 hours, and the appearance of the polarizer constituting the polarizing plate does not change at all before and after the standing. Was evaluated as “C”, and the polarizer constituting the polarizing plate after being left as colored or discolored was evaluated as “X”.
- the chlorine content contained in the cationic polymerizable adhesive was measured based on JIS K 1200-3-2: 2000. Specifically, for an adhesive whose amount of chlorine in the present invention is 0.05% or more as sodium chloride, the value obtained by the Forhardt modification method is taken as the chlorine content of the adhesive, 0.05% For adhesives that are less than 1, the value obtained by ion chromatography analysis was used as the chlorine content of the adhesive.
- PEG # 400 manufactured by NOF Corporation, polyoxyethylene glycol “PEG # 1000” having a number average molecular weight of 400; manufactured by NOF Corporation, polyoxyethylene glycol “PEG # 2000” having a number average molecular weight of 1000; NOF Corporation, polyoxyethylene glycol “PEG # 4000” with a number average molecular weight of 2000; NOF Corporation, polyoxyethylene glycol with a number average molecular weight of 4000 “PEG # 6000”; NOF Corporation Polyoxyethylene glycol “PEG # 11000” having a number average molecular weight of 6000; manufactured by NOF Corporation, polyoxyethylene glycol “Ymer N-120” having a number average molecular weight of 11,000; polyoxyethylene glycol having a molecular weight of 1000, manufactured by Perstorp “ED-56”; manufactured by Mitsui Chemicals, Inc., number average molecular weight 2000, polyoxy Copolymer “ED-36”
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Abstract
Description
本発明で使用するポリオール(A)は、ポリオキシエチレン構造及びポリオキシプロピレン構造からなる群より選ばれる1種以上の構造を有する数平均分子量300~5000のポリエーテルポリオール(a)を必須成分とし、必要に応じてその他の水酸基含有化合物を含むものである。
本発明で使用するオキセタニル基含有化合物(B)は、100~800の分子量を有するオキセタニル基含有化合物(b)を必須とし、必要に応じて前記範囲外の分子量を有するオキセタニル基含有化合物を含むものである。
本発明で使用するグリシジルエーテル(C)は、芳香族グリシジルエーテル(c)を必須とし、必要に応じてその他のグリシジルエーテルを含むものである。
本発明で使用するカチオン重合開始剤(D)は、例えば紫外線等のエネルギー線の照射によりカチオン重合を開始することのできる酸を発生する光カチオン重合開始剤や、加熱等によって酸を発生する熱カチオン重合開始剤である。なかでも、偏光子と保護フィルムとを接着し偏光板を製造する場合や、その他の光学材料を製造する場合には、熱による基材の変形や変色等を防止する観点から、光カチオン重合開始剤を使用することが好ましい。
前記一般式(13)に示される化合物としては、具体的には、ジシクロヘキシル-3,3’-ジエポキシドを使用することができる。
前記プラスチック基材としては、一般に、携帯電話、家電製品、自動車内外装材、OA機器等のプラスチック成型品に採用されている素材として、ポリエステル基材、ポリオレフィン基材、アクリロニトリル-ブタジエン-スチレン樹脂(ABS樹脂)基材、ポリアクリル基材、ポリウレタン基材、エポキシ樹脂基材、ポリ塩化ビニル系基材等が挙げられる。
JIS K 1200-3-2:2000に準じて求めた塩素含有量が3.5%であるビスフェノールF型ジグリシジルエーテルの異性体混合物を、1.3kPa及び185℃の条件で蒸留し、次いで、0.02MPa及び70℃の条件で精留を行うことで、塩素含有量が600ppmの芳香族グリシジルエーテル(C-1)を得た。
JIS K 1200-3-2:2000に準じて求めた塩素含有量が3.5%であるビスフェノールA型ジグリシジルエーテルの異性体混合物を、1.3kPa及び185℃の条件で蒸留し、次いで、0.02MPa及び70℃の条件で精留を行うことで、塩素含有量が600ppmの芳香族グリシジルエーテル(C-2)を得た。
JIS K 1200-3-2:2000に準じて求めた塩素含有量が6.5%であるシクロヘキサンジメタノールジグリシジルエーテルを、1.3kPa及び185℃の条件で蒸留し、次いで、0.02MPa及び70℃の条件で精留を逐次行うことで、塩素含有量が500ppmの脂肪族グリシジルエーテル(C’-3)、塩素含有量が1000ppmの脂肪族グリシジルエーテル(C’-4)、塩素含有量が10000ppmの脂肪族グリシジルエーテル(C’-5)を得た。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#400(日油(株)製のポリオキシエチレングリコール、数平均分子量400)0.13質量部、KBE-403(信越化学工業株式会社製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(1)を調製した。得られたカチオン重合性接着剤(1)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、190ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#1000(日油(株)製のポリオキシエチレングリコール、数平均分子量1000)0.32質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(2)を調製した。得られたカチオン重合性接着剤(2)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、201ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#2000(日油(株)製のポリオキシエチレングリコール、数平均分子量2000)0.65質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(3)を調製した。得られたカチオン重合性接着剤(3)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、197ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#4000(日油(株)製のポリオキシエチレングリコール、数平均分子量4000)1.28質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(4)を調製した。得られたカチオン重合性接着剤(4)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、195ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、Ymer N-120(パーストープ社製のポリオキシエチレングリコール)0.3質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(5)を調製した。得られたカチオン重合性接着剤(5)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、206ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、アクトコールED-56(三井化学(株)製のポリオキシエチレングリコールとポリオキシプロピレングリコールの共重合体、数平均分子量2000)0.64質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(6)を調製した。得られたカチオン重合性接着剤(6)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、210ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、アクトコールED-36(三井化学(株)製のポリオキシエチレングリコールとポリオキシプロピレングリコールの共重合体、数平均分子量3000)1質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(7)を調製した。得られたカチオン重合性接着剤(7)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、198ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-223(東亜合成(株)製の1,3-ビス[(3-エチルオキセタン-3-イル)メトキシ]ベンゼン)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#400(日油(株)製のポリオキシエチレングリコール、数平均分子量400)0.13質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(8)を調製した。得られたカチオン重合性接着剤(8)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、200ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-2)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#400(日油(株)製のポリオキシエチレングリコール)0.13質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(9)を調製した。得られたカチオン重合性接着剤(9)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、198ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-4)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#400(日油(株)製のポリオキシエチレングリコール、数平均分子量400)0.13質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(10)を調製した。得られたカチオン重合性接着剤(10)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、302ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#400(日油(株)製のポリオキシエチレングリコール、数平均分子量400)1質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(11)を調製した。得られたカチオン重合性接着剤(11)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、196ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)57.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#400(日油(株)製のポリオキシエチレングリコール、数平均分子量400)2質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(12)を調製した。得られたカチオン重合性接着剤(12)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、205ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)56.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#400(日油(株)製のポリオキシエチレングリコール、数平均分子量400)2.8質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(13)を調製した。得られたカチオン重合性接着剤(13)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、199ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、Ymer N-120(パーストープ社製のポリオキシエチレングリコール)1.0質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(14)を調製した。得られたカチオン重合性接着剤(14)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、193ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)57.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、Ymer N-120(パーストープ社製のポリオキシエチレングリコール)2.0質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(15)を調製した。得られたカチオン重合性接着剤(15)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、198ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)56.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、Ymer N-120(パーストープ社製のポリオキシエチレングリコール)2.8質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(16)を調製した。得られたカチオン重合性接着剤(16)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、205ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-5)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#400(日油(株)製のポリオキシエチレングリコール、数平均分子量400)0.13質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(17)を調製した。得られたカチオン重合性接着剤(17)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、2087ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(1’)を調製した。得られたカチオン重合性接着剤(1’)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、198ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#6000(日油(株)製のポリオキシエチレングリコール、数平均分子量6000)0.5質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(2’)を調製した。得られたカチオン重合性接着剤(2’)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、200ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)58.0質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#11000(日油(株)製のポリオキシエチレングリコール、数平均分子量11000)0.5質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(3’)を調製した。得られたカチオン重合性接着剤(3’)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、210ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)55.5質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#400(日油(株)製のポリオキシエチレングリコール、数平均分子量400)3.3質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(4’)を調製した。得られたカチオン重合性接着剤(4’)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、200ppmであった。
密閉型プラネタリーミキサー中で、芳香族グリシジルエーテル(C-1)20.0質量部及び脂肪族グリシジルエーテル(C’-3)20.0質量部、アロンオキセタンOXT-221(東亜合成(株)製のビス[1-エチル(3-オキセタニル)]メチルエーテル)54質量部、セロキサイド2021P(ダイセル化学工業(株)製の3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート)1.0質量部、PEG#400(日油(株)製のポリオキシエチレングリコール、数平均分子量400)5.0質量部、KBE-403(信越化学工業(株)製の3-グリシドキシプロピルトリエトキシシラン)0.5質量部、ならびに、CPI-100P(サンアプロ(株)製のジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液)8.0質量部を混合、攪拌することによって、カチオン重合性接着剤(5’)を調製した。得られたカチオン重合性接着剤(5’)の全量中に含まれる塩素含有量を、後述する方法に従って求めたところ、208ppmであった。
クラレポバールPVA-117H((株)クラレ製のポリビニルアルコール、重合度1700、完全ケン化物、粉末状)を水中に溶解して得られたポリビニルアルコール水溶液(不揮発分8質量%)を、バーコーターを用いて離型フィルム上に塗布し、次いで、80℃の環境下で5分間乾燥した後、前期離型フィルムを除去することによって、厚さ75μmのポリビニルアルコールフィルムを作製した。
コロナ処理をした2枚のトリアセチルセルロースフィルム(厚み80μm、縦297mm、横210mm)の片表面に、アプリケーターを用いて実施例及び比較例で得たカチオン重合性接着剤を約2μmの厚みになるようそれぞれ塗布し、該塗布面にコンベアタイプの紫外線照射装置CSOT-40(日本電池(株)製の高圧水銀ランプ、強度120W/cm)を用い、30~100mJ/cm2の紫外線を照射した。
実施例及び比較例で得た偏光板を、85℃に設定した乾燥機中に3000時間放置した後、引張試験機((株)今田製作所製、引張速度=50mm/分 T型剥離)を用いて、各偏光板を構成するトリアセチルセルロースと偏光子との界面の剥離強度を測定した。前記剥離強度が10N/25mm以上またはトリアセチルセルロースフィルムの破断(MB)を引き起こしたものを「良好」、10N/25mm未満のものを「不良」と評価した。
上記で得た偏光板を、-20℃の環境下に1時間放置した後、直ちに70℃の環境下に1時間放置することを1サイクルとして、これを200サイクル繰り返し行う試験を行った。前記試験終了後の接着剤層のひび割れの有無を目視により評価した。
不良:ひび割れが1箇所以上発生した。
偏光板の着色、変色等は、前記方法で作製した偏光板を85℃に設定した乾燥機中に1500時間放置し、前記放置前後で偏光板を構成する偏光子の外観に全く変化がないものを「○」、放置後の偏光板を構成する偏光子が着色または変色していたものを「×」と評価した。
前記カチオン重合性接着剤中に含まれる塩素含有量は、JIS K 1200-3-2:2000に基づいて測定した。具体的には、本発明でいう塩素の量が、塩化ナトリウムとして0.05%以上である接着剤については、ホルハルト改良法により求めた値をその接着剤の塩素含有量とし、0.05%未満である接着剤については、イオンクロマトグラグ分析法により求めた値をその接着剤の塩素含有量とした。
「PEG#400」;日油(株)製、数平均分子量400のポリオキシエチレングリコール
「PEG#1000」;日油(株)製、数平均分子量1000のポリオキシエチレングリコール
「PEG#2000」;日油(株)製、数平均分子量2000のポリオキシエチレングリコール
「PEG#4000」;日油(株)製、数平均分子量4000のポリオキシエチレングリコール
「PEG#6000」;日油(株)製、数平均分子量6000のポリオキシエチレングリコール
「PEG#11000」;日油(株)製、数平均分子量11000のポリオキシエチレングリコール
「Ymer N-120」;パーストープ社製、分子量1000のポリオキシエチレングリコール
「ED-56」;三井化学(株)製、数平均分子量2000、ポリオキシエチレングリコールとポリオキシプロピレングリコールの共重合体
「ED-36」;三井化学(株)製、数平均分子量3000、ポリオキシエチレングリコールとポリオキシプロピレングリコールの共重合体
「OXT-221」;アロンオキセタンOXT-221、東亜合成(株)製、ビス[1-エチル(3-オキセタニル)]メチルエーテル
「OXT-223」;アロンオキセタンOXT-223、東亜合成(株)製、1,3-ビス[(3-エチルオキセタン-3-イル)メトキシ]ベンゼン
「C-1」;調製例1で得た塩素含有量が600ppmの芳香族グリシジルエーテル基含有化合物
「C-2」;調製例2で得た塩素含有量が600ppmの芳香族グリシジルエーテル基含有化合物
「C’-3」;調製例3で得た塩素含有量が500ppmのグリシジルエーテル基含有化合物
「C’-4」;調製例3で得た塩素含有量が1000ppmのグリシジルエーテル基含有化合物
「CEL2021P」;セロキサイド2021P、ダイセル化学工業(株)製、3,4-エポキシシクロヘキセニルメチル-3’,4’-エポキシシクロヘキセンカルボキシレート
「KBE-403」;信越化学工業(株)製、3-グリシドキシプロピルトリエトキシシラン
「CPI-100P」;サンアプロ(株)製、ジフェニル-4-(フェニルチオ)フェニルスルホニウムヘキサフルオロフホスフェートのプロピレンカーボネート50質量%溶液
「C’-5」;調製例3で得た塩素含有量が10000ppmのグリシジルエーテル基含有化合物
「ポリエーテルポリオールの含有割合」;前記接着剤中に含まれるポリオール(A)とオキセタニル基含有化合物(B)とグリシジルエーテル(C)との全量に対する前記ポリエーテルポリオール(a)の質量割合を示す。
Claims (12)
- ポリオキシエチレン構造及びポリオキシプロピレン構造からなる群より選ばれる1種以上の構造を有する数平均分子量300~5000のポリエーテルポリオール(a)を含むポリオール(A)、100~800の分子量を有するオキセタニル基含有化合物(b)を含むオキセタニル基含有化合物(B)、芳香族グリシジルエーテル(c)を含むグリシジルエーテル(C)、ならびに、カチオン重合開始剤(D)を含有するカチオン重合性接着剤であって、前記ポリエーテルポリオール(a)が、前記ポリオール(A)とオキセタニル基含有化合物(B)とグリシジルエーテル(C)との合計質量100質量部に対して0.05~3質量部含まれるものであることを特徴とするカチオン重合性接着剤。
- 前記カチオン重合性接着剤の全量中に残存する塩素が1500ppm以下である、請求項1に記載のカチオン重合性接着剤。
- 前記ポリエーテルポリオール(a)がポリオキシエチレングリコールである、請求項1に記載のカチオン重合性接着剤。
- 前記オキセタニル基含有化合物(b)がビス[1-エチル(3-オキセタニル)]メチルエーテルである、請求項1に記載のカチオン重合性接着剤。
- 前記芳香族グリシジルエーテル(c)がビスフェノールAジグリシジルエーテル及びビスフェノールFジグリシジルエーテルからなる群より選ばれる1種以上である、請求項1に記載のカチオン重合性接着剤。
- 更に脂環式エポキシ化合物(E)を含有する、請求項1に記載のカチオン重合性接着剤。
- 前記脂環式エポキシ化合物(E)が、3,4-エポキシシクロヘキセニルメチル-3,4-エポキシシクロヘキサンカルボキシレート、及び、1-メチル-4-(2-メチルオキシラニル)-7-オキサビシクロ[4.1.0]ヘプタンからなる群より選ばれる1種以上を含むものである、請求項6に記載のカチオン重合性接着剤。
- 更にエポキシ基含有シラン化合物(F)を含有する、請求項1に記載のカチオン重合性接着剤。
- 前記エポキシ基含有シラン化合物(F)が、前記カチオン重合性接着剤の全量に対して0.1~1.5質量%含まれる、請求項8に記載のカチオン重合性接着剤。
- 前記エポキシ基含有シラン化合物(F)が3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、2-(3、4-エポキシシクロヘキシル)エチルトリエトキシシラン及び2-(3、4-エポキシシクロヘキシル)エチルトリメトキシシランからなる群より選ばれる1種以上である、請求項8記載のカチオン重合性接着剤。
- 偏光板を構成する偏光子と保護フィルムとの接着に使用する請求項1~10の何れかに記載のカチオン重合性接着剤。
- 保護フィルムと偏光子とがカチオン重合性接着剤を介して接着された偏光板であって、前記カチオン重合性接着剤が請求項11に記載のカチオン重合性接着剤であることを特徴とする偏光板。
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KR1020127000020A KR101674519B1 (ko) | 2009-08-21 | 2010-06-28 | 양이온 중합성 접착제 및 그것을 사용하여 얻어진 편광판 |
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WO2013146556A1 (ja) * | 2012-03-30 | 2013-10-03 | 住友化学株式会社 | 偏光板 |
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JP2016191926A (ja) * | 2016-06-09 | 2016-11-10 | 住友化学株式会社 | 偏光板及びそれを用いた積層光学部材 |
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JP2017072728A (ja) * | 2015-10-07 | 2017-04-13 | 住友化学株式会社 | 偏光板 |
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JP4877429B2 (ja) | 2012-02-15 |
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EP2468835B1 (en) | 2019-01-02 |
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